CN1922104A

CN1922104A - Metal oxide particle and its use

Info

Publication number: CN1922104A
Application number: CN 200580005446
Authority: CN
Inventors: 武田光生; 相泽龙司; 森弓子; 桑本知幸
Original assignee: Nippon Shokubai Co Ltd
Current assignee: Nippon Shokubai Co Ltd
Priority date: 2004-02-18
Filing date: 2005-02-17
Publication date: 2007-02-28

Abstract

An object of the present invention is to provide a metal oxide particle which exercises more excellent ultraviolet absorbency. As a means of achieving this object, a metal oxide particle according to the present invention is a metal oxide particle such that a component derived from a metal element (M') other than a metal element (M) is contained in a particle comprising an oxide of the metal element (M), with the metal oxide particle being characterized in that : the metal element (M) is at least one member selected from the group consisting of Zn, Ti, Ce, In, Sn, Al, and Si ; and the metal element (M') is at least one member selected from the group consisting of Cu, Ag, Mn, and Bi.

Description

Metal oxide particle and its application

Technical field

The present invention relates to a kind of metal oxide particle and its applications, wherein the metal oxide particle has fabulous ultraviolet-absorbing.In detail, the present invention relates to a kind of metal oxide particles with better ultraviolet-absorbing, such as even in being added to substrate or in the case where being coated on substrate, which will not damage the transparency or tone (hue) of substrate；Such a metal oxide particle is further related to, it is mobile to longer wavelength side that ultraviolet radiation absorption limits (absorption edge), and also has fabulous absorption efficiency to the ultraviolet light of long wavelength range；And a kind of composition containing above-mentioned particle and a kind of film containing above-mentioned particle.

Background technique

So far, in order to provide ultraviolet light blocking ability, have been carried out such method, ultraviolet absorption material is added in such as fiber, plate, plastic molded article (such as film), coating and cosmetic material in these methods, or such method has been carried out, it is coated on such as glass and plastic foil together with the coating agent containing ultraviolet absorption material and solvent and adhesive resin in these methods.

Such as in recent years, for different field (such as cosmetics, construction material, automobile or display glass pane and flat-panel monitor) ultraviolet absorption material do not require nothing more than to the ultraviolet light (ultraviolet light of especially close 380nm) no more than 380nm usually said so far, and have fabulous absorbent properties to the ultraviolet light of more long wavelength range (short-wavelength visible light).The reason is that the visible light of the short wavelength range in visible light has so high energy, so that worrying that plastics are caused to deteriorate and are harmful to the human body.Furthermore, it is required that above-mentioned ultraviolet absorption material has high visible light transmission, and not scatter visible light, and there is good transparency, and it requires above-mentioned ultraviolet absorption material not cause coloring (such as jaundice) and does not make the tone reversal of substrate, and have fabulous durability and heat resistance.

As the ultraviolet absorption material of ultraviolet light blocking ability can be provided, for durability and heat resistance, what inorganic material was desirable to.In particular, it is effective that for example known ultraviolet light to wavelength no more than 370nm, which has the zinc oxide for blocking physical property completely, and usually using particle form.But these materials are not able to satisfy above-mentioned requirement.For example, there is also lack effectiveness: UV absorbing properties are insufficient, so that per unit area must use a large amount of ultra-fine grains, therefore film becomes too thick in order to block the ultraviolet light no more than 380nm completely.

Therefore, a kind of method as the more preferable UV absorbing properties for improving ultraviolet absorption material, proposes the combination of zinc oxide and miscellaneous metal (hetero-metal).For example, proposing following scheme: the i) material (such as with reference to following patent document 1 and non-patent literature 1) of the zinc oxide containing (doped with) Fe and/or Co；Ii) the composite oxides (such as with reference to following patent document 2) selected from least one of Ce, Ti, Al, Fe, Cr and Zr with zinc；And iii) material (such as with reference to following patent document 3) containing the zinc oxide selected from least one of Ce, Ti, Al, Fe, Co, La and Ni.

In addition, proposing that a kind of wherein quantity is 10 even if not as a purpose ultraviolet absorption material, being intended only as a kind of technology for obtaining the zinc oxide containing miscellaneous metal²The Cu of ppm is present in the zinc oxide (such as with reference to following non-patent literature 2) in solid solution.It seems that also expectable such zinc oxide can improve UV absorbing properties.

[patent document 1] JP-A-188517/1997 (Kokai)

[patent document 2] JP-A-275182/1987 (Kokai)

[patent document 3] JP-A-222317/1993 (Kokai)

[non-patent literature 1] Jun OHTSUKA, " Inorganic Pigments ComprisingZnO as a Main Component ", Ceramics, published by CorporateJuridical Party:The Society of Ceramics, Japan, published in1983, Vol.18, No.11, p.958-964

[non-patent literature 2] Noboru SAKAGAMI and another person, " Optical Properties of Impurities-doped Hydrothermally GrownZinc Oxide ", The Journal of the Society of Ceramics, Japan, published by Corporate Juridical Party:The Society of Ceramics, Japan, published in 1969, Vol.77 [9] , p.309-312

But in recent years, in the case where needing the application of higher ultraviolet light blocking ability to be continuously increased, existing metal oxide is as escribed above i) cannot still to have said enough ultraviolet absorption abilities to iii).In detail, about these metal oxides, the absorbent properties of the light for wavelength greater than 380nm may improve, but still insufficient towards the mobile effect of longer wavelength side to ultraviolet radiation absorption limit.Furthermore, in the above-mentioned i containing Fe and/or Co) in the case where, so that there is the absorbent properties under the 380nm of maximum blocking demand to generate sizable decline, additionally since in visible-range, there are absorption bands, Fe and Co makes material distinguish obvious yellow and blue-colored, therefore there are such a problems, if such existing metal oxide is used as ultraviolet absorption material and is added to or is coated on substrate, the transparency or tone of substrate can be damaged.In addition, for the prior art, or even be substantially difficult to produce doped with above-mentioned metal and with fabulous separating capacity and dispersed fine grained.

As reported in non-patent literature 2, it is a kind of product synthesized with hydro-thermal method that wherein Cu, which is present in the existing zinc oxide in solid solution, it has very big particle size (10-25mm), and yellowish.Therefore, in the case where such existing zinc oxide is used as ultraviolet absorption material, it can not obtain the property of the visible light transmission and good transparency that have high, therefore it leads to the problem of such a, if such existing metal oxide is used as ultraviolet absorption material and is added to or is coated on substrate, the transparency or tone of substrate can be damaged.

Disclosure of the invention

Goal of the invention

Therefore, it is an object of the present invention to provide: one kind having better ultraviolet-absorbing metal oxide particle, and it is combined with following advantage, such as ultraviolet radiation absorption is limited to the movement of longer wavelength side, and to the absorption efficiency that the ultraviolet light of long wavelength range has had, or there is good transparency, and, for example, even in being added to substrate or in the case where being coated on substrate, the transparency or tone of substrate will not be damaged；It also provides: a kind of composition containing above-mentioned particle；A kind of film containing above-mentioned particle；A kind of product of the containing metal oxide containing above-mentioned particle；And a kind of ultraviolet absorption material containing above-mentioned particle.

By the way, the ultraviolet range to be blocked in the present invention is defined as not only including the range no more than 380nm usually said so far, but also the visible light (specifically, wave-length coverage is 380-450nm) including short wavelength range.Hereafter, ultraviolet light and those ultraviolet lights those of in ultraviolet light blocking (cutting) and ultraviolet radiation absorption are defined as light of the wavelength within the above range (no more than 450nm).

Summary of the invention

To solve the above-mentioned problems, the present inventor, which sufficiently has studied, makes the oxide of metallic element (M) contain the miscellaneous element different from metallic element (M) (such as miscellaneous metallic element (M ')).As a result, they have found first, for the viewpoint that fabulous effect enhancing can be generated, selection is containing selected from Zn, Ti, Ce, In, Sn, oxide and selection Cu of the single oxide (singleoxide) or composite oxides of the metallic element of at least one of Al and Si as metallic element (M), Ag, at least one of Mn and Bi are suitable as contained miscellaneous metallic element (M '), if such metal oxide particle containing miscellaneous metal is fine particulate form, so this particle has better ultraviolet-absorbing and has good transparency, such as even in being added to substrate or in the case where being coated on substrate, the transparency or tone of substrate will not be damaged.

Secondly, the inventor has discovered that such a metal oxide particle containing metal oxide, so that making containing selected from Zn, Ti, Ce, In, Sn, the single oxide or composite oxides of at least one of Al and Si metallic element as the oxide of metallic element (M) also contain at least two specific miscellaneous metallic elements of intercombination, and (metallic element (M ') is selected from Co, Cu, Fe, Bi, In, Al, Ga, Ti, Sn, Ag, Mn, Ni and Ce), it is with better ultraviolet-absorbing, and it is mobile to longer wavelength side to limit ultraviolet radiation absorption, therefore also there is fabulous effect to the absorption efficiency aspect of the ultraviolet light of long wavelength range.

Third, the present inventors have additionally discovered that: if at least one of oxide and Co, Fe and Ni for being elected to be metallic element (M) in the single oxide containing the metallic element selected from least one of Zn, Ti, Ce, In, Sn, Al and Si or composite oxides is (for ultraviolet light blocking ability (ultraviolet-absorbing), it may have particularly preferred effect) in the case that at least part for being elected to be in contained miscellaneous metallic element (M ') and these Co, Fe and Ni is divalent, then very useful metal oxide particle is made.Specifically, if it is trivalent, it makes particle obviously be colored as yellow to brown, it is possible that being unfavorable for needing more colorless and transparent various applications for Fe.But if Fe is that divalent or divalent are existed simultaneously with trivalent, particle is colored as green or light green.So its coloring is unconspicuous when film is made by such particle.Even if coloring slightly occurs, it can still drop to such flexible tone, so that can be used to completely need more colorless and transparent application.For Co, there are better UV absorbing properties the case where it is only trivalent than it that it is for divalent or the case where include divalent.For Ni, if it is divalent, it obtains pale green powder, so that expectable effect identical with above-mentioned Fe, and UV absorbing properties are also fabulous.Furthermore, the inventors have further noted that, in the case where at least one of oxide and Co, Fe and Ni that the single oxide containing Zn or composite oxides are elected to be metallic element (M) are elected to be contained miscellaneous metallic element (M '), it is important in the size of the crystal grain of specific direction, and the present inventors have additionally discovered that, this size is advantageous within the scope of nano-scale, this size range has never seen in the existing oxide particle also containing Co, Fe and Ni.

4th, present inventors have discovered that if oxide containing single oxide or composite oxides selected from least one of Zn, Ti, Ce, In, Sn, Al and Si metallic element as metallic element (M) and if make the oxide of this metallic element (M) contain it is at least one selected from least one of N, S and the 17th race (7B race) element and if various conditions for example form (surface composition, internal form) it is optimised, a kind of particle for having fabulous UV absorbing properties, visible transmission performance and tone can be made.

Furthermore, the present inventors have additionally discovered that: if above-mentioned metal oxide particle as the metal oxide particle of metal component and/or with comprising combining selected from least one of Ag, Cu, Au and platinum group as the ultra-fine metallic particles of metallic element, blocks the effect enhancing of short wavelength range visible light with containing special metal element (metallic element selected from Cu, Fe, Ag and Bi).

The present invention is accomplished by these knowledge and discovery.

Therefore, metal oxide particle of the invention is as follows.

That is, first invention is a kind of metal oxide particle of fine particulate form, it is such a metal oxide particle, so that the metal oxide particle is characterized in that containing the component for being originated from the metallic element (M ') different from metallic element (M) in the particle of the oxide containing metallic element (M): metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And metallic element (M ') is selected from least one of Cu, Ag, Mn and Bi.By the way, in this first invention, " fine grained " refers to that primary particle diameter is not more than 0.1 μm of particle.In detail, above-mentioned primary particle diameter can be judged by crystal grain diameter or specific surface area diameter, and the particle of crystal grain diameter or specific surface area diameter no more than 0.1 μm is considered as " fine grained ".

Second invention is a kind of metal oxide particle, it is such a metal oxide particle, so that the metal oxide particle is characterized in that containing the component for being originated from the metallic element (M ') different from metallic element (M) in the particle of the oxide containing metallic element (M): metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And metallic element (M ') includes different from metallic element (M) and selected from Co, Cu, Fe, Bi, In, Al, Ga, Ti, Sn, Ce, Ni, Mn and Ag at least two.

Third invention is a kind of metal oxide particle, it is such a metal oxide particle, so that the metal oxide particle is characterized in that containing the component for being originated from the metallic element (M ') different from metallic element (M) in the particle containing metallic element (M) oxide: metallic element (M ') is selected from least one of Co, Fe and Ni；And be or i): metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And at least part Co, Fe and Ni as metallic element (M ') are divalent；Or ii): metallic element (M) is Zn；And metal oxide particle is not more than 30nm in the crystal grain diameter perpendicular to (002) face direction, and it is not less than 8nm in the crystal grain diameter perpendicular to (100) face direction.

4th invention is a kind of metal oxide particle, it contains the metal oxide particle of the oxide of metallic element (M) for one kind, and the metal oxide particle is characterized in that: metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And it is: i) contains in the oxide of metallic element (M) selected from least one of N, S and the 17th race (7B race) element and there are also acyl groups；Or ii) metallic element (M) oxide in contain at least two in N, S and the 17th race (7B race) element；Or iii) metallic element (M) oxide in containing be selected from least one of N, S and the 17th race (7B race) element；And contain the component for being originated from the metallic element (M ') different from metallic element (M) in particle.

Composition of the invention contains metal oxide particle and medium, and wherein metal oxide particle disperses in the medium, and includes above-mentioned metal oxide particle of the invention as basic component.

In above-mentioned composition of the invention, the composition of the invention formed for film includes following basic component: the present invention above-mentioned metal oxide particle and dispersion solvent and/or adhesive.

Film of the invention includes metal oxide as basic component, and wherein metal oxide includes following basic component: above-mentioned metal oxide particle of the invention and/or the metal oxide crystal from this particle.

The product of containing metal oxide of the present invention is a kind of product of metal oxide crystal containing metal oxide particle and/or from this particle, wherein product include above-mentioned metal oxide particle of the invention with: include the metal oxide particle selected from least one of Cu, Fe, Ag and Bi as metallic element；And/or comprising being selected from least one of Cu, Ag, Au and platinum group as the composition of the ultra-fine metallic particles of metallic element as basic component.

Ultraviolet absorption material of the invention includes above-mentioned metal oxide particle of the invention.

Invention effect

The present invention can provide a kind of: the metal oxide particle with more preferable UV absorbing properties and with various combinations, such as ultraviolet radiation absorption is limited to the movement of longer wavelength side, the absorption efficiency also having had to the ultraviolet light of long wavelength range, or there is the good transparency, even for example in being added to substrate or in the case where being coated on substrate, the transparency or tone of substrate will not be damaged；A kind of composition (such as composition of film forming) containing above-mentioned particle；A kind of film containing above-mentioned particle；A kind of product of the containing metal oxide containing above-mentioned particle；And a kind of ultraviolet absorption material containing above-mentioned particle.

Brief description

Fig. 1 is the figure for indicating absorbent properties evaluation (4-1) result in embodiment A1 series and 1 series of comparative example A.

Fig. 2 is the figure for indicating absorbent properties evaluation result (transmitted spectrum) in embodiment A3-1.

Fig. 3 is the figure for indicating absorbent properties evaluation result (transmitted spectrum) in embodiment A3-2.

Fig. 4 is the figure for indicating absorbent properties evaluation result (transmitted spectrum) in embodiment A3-3.

Fig. 5 is to indicate by the figure of the diffusing reflection spectrum result of the obtained metal oxide particle of embodiment A1-17 and comparative example A 1-1.

Fig. 6 indicates the transmitted spectrum for the glass that dispersion film obtained in the evaluation of metal oxide particle coats in the reaction liquid obtained to embodiment B1-1 and comparative example B1-1.

Fig. 7 indicates the transmitted spectrum for the glass that dispersion film obtained in the evaluation of metal oxide particle coats in the reaction liquid obtained to embodiment B1-2 and comparative example B1-2.

Fig. 8 shows the transmitted spectrums of the glass of the obtained dispersion film coating of embodiment B3-1 (three kinds of different thickness of dry film based on different wet-film thickness).

Detailed description of the invention

The present invention is described in detail below.But the scope of the present invention is not limited to these descriptions.It can also be to the following change for illustrating to make appropriate form in the range of without prejudice to purport of the invention.

[metal oxide particle]

As above-mentioned, any metal oxide particle of the invention is all a kind of metal oxide particle for containing metallic element (M) oxide, and wherein metal oxide particle contains the specific miscellaneous element different from metallic element (M).In detail, above-mentioned first, second metal oxide particle invented with third is such, so that containing the component for being originated from the metallic element (M ') (hereinafter it can be described as " miscellaneous metallic element ") different from special metal element (M) in the particle containing metallic element (M) oxide, the above-mentioned metal oxide particle of 4th invention is such, so that containing selected from N in the oxide of special metal element (M), at least one of S and the 17th race (7B race) element (hereafter can be described as " miscellaneous nonmetalloid ").In more detail, in the present invention, contained is originated from for the component of above-mentioned miscellaneous metallic element or above-mentioned miscellaneous nonmetalloid, if the metal oxide for constituting metal oxide particle of the present invention is the metal oxide containing above-mentioned miscellaneous metallic element or miscellaneous nonmetalloid, and there are not important in the form of what for above-mentioned miscellaneous metallic element or miscellaneous nonmetalloid.By the way, hereinafter, above-mentioned miscellaneous metallic element and above-mentioned miscellaneous nonmetalloid are commonly known as " miscellaneous (metal/non-metal) element ".

In the metal oxide for constituting metal oxide particle of the invention, the specific example of the existence form of above-mentioned miscellaneous (metal/non-metal) element includes: that (I) wherein miscellaneous (metal/non-metal) element is present in the form in solid solution in the oxide crystal of metallic element (M)；(II) wherein form existing for metal component (best composite oxides) of miscellaneous (metal/non-metal) element in contained state as the oxide of metallic element (M)；(III) wherein miscellaneous (metal/non-metal) element is adsorbed on the form on the plane of crystal of metallic element (M) oxide；And (IV) wherein miscellaneous (metal/non-metal) element is attached on metallic element (M) oxide in the form of particle or film as metal or simple material.In a word, for the effect that miscellaneous (metal/non-metal) element provides, above-mentioned miscellaneous (metal/non-metal) element is preferred in the form of the solid solution in the oxide crystal that state of atom (including ionic condition) is dispersed in metallic element (M), that is, has coloring degree caused by fabulous ultraviolet-absorbing, the addition of miscellaneous (metal/non-metal) element small and can retain good transparency.

For above-mentioned miscellaneous (metal/non-metal) element is in the dispersity in metal oxide particle of the invention, (i) above-mentioned miscellaneous (metal/non-metal) element can be with homogeneously dispersed state containing in the grain, or (ii) above-mentioned miscellaneous (metal/non-metal) element can be partially containing (such case does not mean that segregation in the grain, and be the case that when choosing a particle, above-mentioned miscellaneous (metal/non-metal) element with high local concentrations by comprising).The example of above situation (i) includes such a case, in above-mentioned shape formula (I), above-mentioned miscellaneous (metal/non-metal) element is equably included in metallic element (M) oxide crystal (from superficial layer to intra-die) in solid solution.The example of above situation (ii) includes such a case, wherein miscellaneous (metal/non-metal) element is with metal oxide solid solution phase existing for solid solution (above-mentioned shape formula (I)), or such a phase (above-mentioned shape formula (II)), if miscellaneous (metal/non-metal) element is miscellaneous metallic element (M '), the composite oxides of so miscellaneous metallic element (M ') and metallic element (M), or if miscellaneous (metal/non-metal) element is miscellaneous nonmetalloid, so metal oxide nitride object (wherein miscellaneous nonmetalloid is N), metal oxide vulcanization object (wherein miscellaneous nonmetalloid is S) or metal oxide halide (wherein miscellaneous nonmetalloid is the 17th race's element) form superficial layer on the surface of the oxide crystal of metallic element (M).In the present invention, these are also contained in referred to as " metal oxide ".

By the way, metal oxide is usually categorized into the metal oxide of crystallinity (crystal structure) or without the metal oxide of crystallinity (non-crystal structure).Above-mentioned crystal structure may be defined as the metal oxide containing crystal grain, so that seeing periodically regular atom layout.Above-mentioned crystal structure refers to can be by the metal oxide for lattice constant and/or the diffraction pattern identification that electron diffraction analysis and/or X-ray diffraction analysis obtain.The metal oxide for not corresponding to this may be defined as non-crystal structure.For fabulous ultraviolet-absorbing, metal oxide is that crystal structure is preferred.Equally it is also suitable the metal oxide for constituting metal oxide particle of the invention.In particular, being invented about third, in the case where above-mentioned metallic element (M) is Zn, then the metal oxide for constituting metal oxide particle is crystal structure.

Above-mentioned crystal structure can be mono-crystalline structures or polycrystalline structure.The example for constituting these grain shape includes spherical shape, elliposoidal, cube, cuboid, polyhedron, pyramid, column, tube, slice substance (such as scale object, hexagon plate object) and arborizations object and skeleton crystal (being prolonged by the seamed edge of crystal under the conditions of high degree of supersaturation and the pre- of corner angle to be formed).The orientation of crystal grain is unrestricted.The orientation of crystal grain can be all aligned or at random.Can also a part have an identical orientation, and remaining arbitrary arrangement.Therefore there is no limit.

The shape of metal oxide particle of the invention is unrestricted.Specifically, the shape of particle is identical as the shape of above-mentioned crystal grain when metal oxide particle of the invention is the particle of the metal oxide containing mono-crystalline structures.But; in the case where metal oxide particle of the invention is the particle that the particle containing polycrystalline structure or crystal grain are fixed or flocks together; the shape of particle is not always identical with the shape of above-mentioned crystal grain, such as is illustrated with spherical (true spheres), elliposoidal, cube, cuboid, pyramid, spicule, column, club, tube and slice substance (such as scale object, hexagon plate object).

Constitute the solid solution metal oxide (solid solution, oxide) that the metal oxide of metal oxide particle of the present invention is formed in single oxide (the specifically oxide of metallic element (M)) or composite oxides (oxide for containing at least two metallic elements (M)) preferably by miscellaneous (metal/non-metal) element solid solution (doping).In addition, this metal oxide has stoichiometric composition or the nonstoichiometric composition of metallic element and oxygen.Therefore there is no limit.

Above-mentioned solid solution, oxide may be known as interstitial solid solution oxide or substitution solid solution oxide or combinations thereof.Therefore there is no limit.

In the present invention (first, second, third and the 4th invention), above-mentioned metallic element (M) is selected from least one of Zn (zinc), Ti (titanium), Ce (cerium), In (indium), Sn (tin), Al (aluminium) and Si (silicon).Wherein, Zn, Ti, Ce, In and Sn are preferably as there is fabulous UV absorbing properties and because when semiconductor is made by particle, and the effect that (M ') containing metallic atom is obtained is high.Especially, can have for fabulous UV absorbing properties, Zn, Ti and Ce are preferred, even in its single oxide, so having high barrier effect to the ultraviolet light (ultraviolet light usually said so far) no more than 380nm, the effect provided by miscellaneous nonmetalloid can also be provided significantly, that is, ultraviolet radiation absorption is made to limit the effect mobile to longer wavelength side.

The oxide of above-mentioned metallic element (M) can be single oxide or composite oxides.The example of composite oxides includes the composite oxides containing at least two M and metal component is the composite oxides of metallic element (M) and other metallic elements different from this metallic element (M), such as ZnIn₂O₄、Zn₂In₂O₅、Zn₃In₂O₆、GaInO₃、In₄Sn₃O₁₂、Zn₂SnO₄And ZnSnO₃.In detail, usually in the case where metallic element (M) is Zn, preferred example includes ZnAl₂O₄、Zn₂B₆O₁₁、ZnFe₂O₄、ZnMoO₄、ZnSeO₃、Zn₂SiO₄And ZnWO₄.In addition, the form of a part of oxygen is also contained in the oxide of above-mentioned metallic element (M) in miscellaneous element (miscellaneous nonmetalloid as escribed above) substituted metal oxide in the present invention (first to the 4th invention).Especially, in the 4th kind of metal oxide particle (the 4th invention), include such form: for example a kind of solid solution, so that miscellaneous nonmetalloid is in solid solution the oxygen substituted in above-mentioned oxide, in addition there are the nitrogen oxide of metal, sulfur oxide compound and oxidative halogenation objects.

Especially, for there are also fabulous visible transparency, for Zn more preferably as metallic element (M), the particle containing zinc oxide is the preferred embodiment of the present invention (first, second, third and the 4th invention) metal oxide particle.

(first invention)

The first metal oxide particle (first invention) of the invention is a kind of metal oxide particle (such metal oxide particle hereafter can be described as " fine-grained metals oxide ") of fine particulate form, so that: metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And metallic element (M ') is selected from least one of Cu, Ag, Mn and Bi.By the way, the first above-mentioned metal oxide particle is fine grained, that is, its particle diameter is not more than 0.1 μm of particle.In other words, the primary particle diameter of the particle containing above-mentioned metallic element (M) oxide is not more than 0.1 μm.

In the first above-mentioned metal oxide particle, above-mentioned metallic element (M) and its oxide are as described above.

About the first above-mentioned metal oxide particle, the preferred example of the copper contained in the oxide of metallic element (M) (Cu) includes Cu (0), Cu (I) and Cu (II).In particular, Cu (I) and Cu (II) are preferred in the case where solid solution.For all right ultraviolet-absorbing, Cu (II) is particularly preferred.

About the first above-mentioned metal oxide particle, the preferred example of the silver contained in the oxide of metallic element (M) (Ag) includes Ag (0) and Ag (I).In particular, for all right ultraviolet-absorbing, Ag (I) is preferred in the case where solid solution.

About the first above-mentioned metal oxide particle, the example of the manganese contained in the oxide of metallic element (M) (Mn) includes the manganese of 1-7 valence.In particular, 2 or the manganese of trivalent be preferred.

About the first above-mentioned metal oxide particle, the example of the bismuth contained in the oxide of metallic element (M) (Bi) includes the bismuth of 0-3 valence.In particular, the bismuth of trivalent is preferred.

By the way, in the case where Cu, Ag, Mn and Bi are in solid solution, respective solid solution thereof can be interstitial solid solution or substitution solid solution.Therefore there is no limit.

In the first above-mentioned metal oxide particle, based on the total atom number of above-mentioned metallic element (M), the content of the above-mentioned miscellaneous metallic element (M ') (Cu, Ag) contained in the oxide of metallic element (M) is preferably 0.01-10 atom %, more preferable 0.1-10 atom %, more preferable 0.2-10 atom %, more preferable 0.7-10 atom %.It compares, in the case where miscellaneous metallic element is Mn, content is preferably 0.01-30 atom %, particularly preferred 3-10 atom %.In addition, content is preferably 0.01-10 atom %, particularly preferred 0.1-5 atom % in the case where miscellaneous metallic element is Bi.If the content of above-mentioned miscellaneous metallic element (M ') (Cu, Ag, Mn, Bi) is less than 0.01 atom %, ultraviolet absorption ability is often difficult to give full play to.On the other hand, if the content of above-mentioned miscellaneous metallic element (M ') is greater than the respective upper limit, it can be seen that the transmissivity of light is usually very low.

About the first above-mentioned metal oxide particle, the oxide of above-mentioned metallic element (M) can also contain the other metallic elements of its content within the scope of the effect of the invention in addition to above-mentioned miscellaneous metallic element (M ') (Cu, Ag, Mn, Bi).Although there is no limit the preferred example different from the metallic element of miscellaneous metallic element (M ') (Cu, Ag, Mn, Bi) includes Al, In, Sn, Fe, Co, Ce, alkali metal element and alkali earth metal.

(second invention)

Second of metal oxide particle (second invention) of the invention is a kind of metal oxide particle, so that: metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And metallic element (M ') includes being different from metallic element (M) and in Co, Cu, Fe, Bi, In, Al, Ga, Ti, Sn, Ce, Ni, Mn and Ag at least two.

In second above-mentioned of metal oxide particle, above-mentioned metallic element (M) and its oxide are as described above.

In second above-mentioned of metal oxide particle, above-mentioned metallic element (M ') includes at least two in Co (cobalt), Cu (copper), Fe (iron), Bi (bismuth), In (indium), Al (aluminium), Ga (gallium), Ti (titanium), Sn (tin), Ag (silver), Mn (manganese), Ni (nickel) and Ce (cerium).But as above-mentioned, metallic element (M ') is necessarily different from the metallic element of metallic element (M).If they be different from above-mentioned metallic element (M) at least two in above-mentioned group of metallic element, to the combinations of at least two metallic elements (M ') there is no limit.By the way, provide that above-mentioned one group In, Al, Ga, Ti, Ce and Sn that may be selected as metallic element (M ') is commonly referred to as n-type dopant herein.

About second above-mentioned of metal oxide particle, the example that may be selected as the Co of metallic element (M ') includes Co (II) and Co (III).The example of Fe includes Fe (II) and Fe (III).In the case where Co and Fe is solid solution component, the Co and Fe of divalent have better ultraviolet-absorbing than trivalent.So only Co and Fe than only trivalent coexists in the presence of more preferable in Co and the Fe presence of divalent or divalent and the Co and Fe of trivalent.In particular, divalent is the obvious flavescence of use generation preferably as the Fe of trivalent, and the use of divalent Fe generates light green in the case where Fe.

In addition, the example that may be selected as the Cu of metallic element (M ') includes Cu (0), Cu (I) and Cu (II) about second above-mentioned of metal oxide particle.The example of Bi includes Bi (III).The example of In includes In (I) and In (III).The example of Al includes Al (III).The example of Ga includes Ga (III).The example of Ti includes Ti (IV) and Ti (III).The example of Sn includes Sn (II) and Sn (IV).The example of Ag includes Ag (0), Ag (I) and Ag (III).The example of Mn includes Mn (I), Mn (II), Mn (III), Mn (IV), Mn (V), Mn (VI) and Mn (VII).The example of Ni includes Ni (0), Ni (II), Ni (I) and Ni (III).The example of Ce includes Ce (IV) and Ce (III).Wherein, Cu, Ag and Ni can also play effect adhering in (adhesion) to the surface of metal oxide particle in the form of Cu (0), Ag (0) and Ni (0) (in other words with metal).Wherein for all right ultraviolet light blocking ability, Bi (III) is preferred as Ni as Mn and Ni (II) as Ag, Mn (II) and Mn (III) as In, Ag (I) as Bi, In (III).

About second above-mentioned of metal oxide particle, preferably as at least two combined mode for being selected as above-mentioned metallic element (M ') are as follows: the combination comprising following basic component: selected from least one of Co, Cu and Fe；With selected from least one of Bi, In, Al, Ga, Ti, Sn and Ce (combination (i) cited below)；It and include a kind of combination (combination (ii) cited below to (v)) as basic component in Co, Cu, Fe, Ag, Mn, Ni and Bi.It by the way, is preferred certainly including following (i) at least two combined mode into (v).

(i) when compared with following two situation, i.e. in being selectable as above-mentioned metallic element (M ') group, in the case where containing only Co, Fe and Cu group in the case where containing only In, Ag, Ga, Ti, Sn and Ce group in the oxide of metallic element (M) and in the oxide of metallic element (M), there is such effect in the case where containing two groups of metallic element (M ') so in the oxide of metallic element (M), so that the absorbability within the scope of 370-450nm improves.It is believed that by being contained in metallic element in such combination, since the function and effect synergism of two groups of metallic elements (M ') play a role, to improve the absorption efficiency within the scope of 370-450nm.For example, the ability for absorbing 380nm ultraviolet light greatly improves, and to apply, less amount of material therefor can sufficiently cut off ultraviolet light in the case where metallic element (M) is Zn.

(ii) contain combination of the Cu as basic component.The performance for absorbing the light of higher energy (no more than 380nm, the range is commonly referred to as ultraviolet light) is greatly improved as basic component comprising Cu, can also reduce jaundice.Furthermore, such as in the case where metal oxide particle has yellow tone (such as in the case where containing Ti and/or Ce as metallic element (M) and in the case where containing Fe, Bi and/or Mn as metallic element (M ')), said combination is also preferred, this is because: can also play the function of reducing jaundice or keep it colourless by the way that Cu coexists as basic component.Any element combinations of the Cu preferably with the group that may be selected as above-mentioned metallic element (M ').But, it can more cooperate with and improve for the effect for the performance for absorbing the light (range is commonly referred to as ultraviolet light) no more than 380nm range, in such a combination as the metallic element (M ') of the partner of Cu, above-mentioned n-type dopant (especially In, Al, Sn, Ce) is preferred.It is improved for the effect for the performance for absorbing high energy range (380-450nm) visible light in addition, can more cooperate with, as the metallic element (M ') of Cu partner in said combination, Co, Fe, Bi, Mn, Ag and Ni are preferred.For the tight security of metal oxide particle, as the metallic element (M ') of Cu partner in said combination, Fe, Mn and Bi are particularly preferred.About their combination, as particularly preferred mode, such as it is proposed that the combination containing Cu and Fe and above-mentioned n-type dopant, the combination containing Cu and Mn and above-mentioned n-type dopant, the combination containing Cu and Bi and above-mentioned n-type dopant, the combination containing Cu and Bi and Fe or Mn, the combination containing Cu and Bi and Fe or Mn and above-mentioned n-type dopant.

(iii) a kind of to contain the combination of Fe, Co, Ni and Mn as basic component.Since comprising Fe, Co, Ni and Mn, as basic component, these Fe, Co, Ni and Mn can larger improve the performance for absorbing high energy range (380-450nm) visible light.Especially, as above-mentioned, (in other words in the case where Fe (II) and/or Mn (II) are necessarily at least part in Fe, Co, Ni and Mn, in the case where being existed simultaneously there is only Fe (II) or there is only Mn (II) or Fe (II) and Fe (III) or Mn (II) and Mn (III) is existed simultaneously) it is preferred, cause are as follows: the absorption of visible light can be prevented, while caning absorb the ultraviolet light until more long wavelength.As the metallic element (M ') of Fe, Co, Ni and Mn partner in said combination, above-mentioned n-type dopant (especially Ce, In, Al, Sn) and/or Cu are preferred (they improve the performance for absorbing the light (range is commonly referred to as ultraviolet light) no more than 380nm range).

(iv) a kind of to contain combination of the Bi as basic component.The transmissivity not less than 450nm visible light can be kept as basic component comprising Bi, and simultaneously than the above-mentioned absorptivity for selectively improving shorter wavelength range (400-450nm) light.As the metallic element (M ') of Bi partner in said combination, (1) above-mentioned n-type dopant (especially In, Al, Ce, Sn), (2) Cu, (3) Co, Mn, Ni and Fe or (4) Ag are preferred.

(v) a kind of to contain combination of the Ag as basic component.The performance for absorbing high energy range (380-450nm, especially 410-440nm) visible light can be larger improved as basic component comprising Ag.As the metallic element (M ') of Ag partner in said combination, above-mentioned n-type dopant (especially In, Al, Sn, Ce) and Cu are preferred (they effectively improve the absorbability under 380nm).

About second above-mentioned of metal oxide particle, at least two be elected to be above-mentioned metallic element (M ') the preferred specific example of combination include Co (II) and In (III) combination, the combination of Co (II) and Bi (III), the combination of Fe (II) and In (III), the combination of Fe (II) and Bi (III), the combination of Co (III) and In (III), the combination of Co (III) and Bi (III), the combination of Co (II) and Al (III), the combination of Co (III) and Ga (III), the combination of Co (II) and Ti (IV), the combination of Fe (III) and In (III), the combination of Fe (III) and Bi (III), Fe (II) and Al (III) combination, the combination of Fe (III) and Cu (II), Fe (II), the combination of Cu (I) and In (III), Fe (II), the combination of Cu (II) and Al (III), Fe (III), the combination of Cu (I) and In (III), Fe (III), the combination of Cu (II) and Al (III), Fe (II), the combination of Fe (III) and Al (III), Fe (II), the combination of Fe (III) and Cu (I), the combination of Cu (I) and In (III), the combination of Cu (II) and In (III), the combination of Cu (I) and Al (III), the combination of Cu (II) and Al (III), Cu (I) and Sn ( IV combination), the combination of Cu (II) and Su (IV), the combination of Cu (I) and Ti (IV), the combination of Cu (II) and Ti (III), the combination of Cu (I) and Ce (IV), the combination of Cu (I) and Co (III), the combination of Cu (II) and Co (III), the combination of Cu (I) and Bi (III), the combination of Cu (II) and Bi (III), Cu (I), the combination of Cu (II) and Bi (III), Cu (I), the combination of Cu (II) and In (III), Cu (I), the combination of Cu (II) and Al (III), Cu (I), the combination of Cu (II) and Sn (IV), Cu (I), Cu (II) and Sn (I I combination), Cu (I), the combination of Cu (II) and Ti (IV), Cu (I), the combination of Cu (II) and Ti (III), the combination of Mn (II) and Bi (III), the combination of Ag (I) and Bi (III), the combination of Ni (II) and Bi (III), Cu (I), the combination of In (III) and Bi (III), Cu (I), the combination of Al (III) and Mn (II), Cu (I), the combination of Ga (III) and Fe (II), Cu (I), In (III), the combination of Bi (III) and Fe (II), Cu (I), In (III), the combination of Bi (III) and Mn (II), Sn (II) and In (III ) combination, the combination of Sn (IV) and Al (III), the combination of Ce (III) and Ga (III), the combination of Ce (IV) and Ti (III), the combination of Ag (I) and In (III), the combination of Ag (0) and In (III), the combination of Ag (I) and Cu (I), the combination of Sn (II) and Ce (III), the combination of Sn (IV) and Ti (IV), the combination of Mn (III) and In (III), the combination of Mn (II) and Al (III), Mn (II), the combination of Cu (I) and In (III).

In above-mentioned second of metal oxide particle, based on metallic element (M), the total amount of above-mentioned metallic element (M ') is preferably 0.02-20 atom %, more preferably 0.2-10 atom %.If above-mentioned content is lower than 0.02 atom %, then it is possible that UV absorbing properties are insufficient.If above-mentioned content is greater than 20 atom %, then it is possible that the transmittance of visible light is low.

About above-mentioned second of metal oxide particle, in the case where above-mentioned metallic element (M ') selection in said combination (i), based on metallic element (M), the total amount selected from least one of Co, Cu and Fe metallic element is preferably 0.01-20 atom %, more preferable 0.1-5 atom %, more preferable 0.2-3 atom %.If above-mentioned content is less than 0.01 atom %, then it is possible that UV absorbing properties are insufficient.If above-mentioned content is greater than 20 atom %, then it is possible that the transmittance of visible light is low.On the other hand, in the case where above-mentioned metallic element (M ') selection in said combination (i), based on metallic element (M), the total amount selected from least one of Bi, In, Al, Ga, Ti, Ce and Sn metallic element is preferably 0.01-10 atom %, more preferable 0.1-5 atom %, more preferable 0.2-3 atom %.If above-mentioned content is less than 0.01 atom %, then it is possible that the synergy combined with Co, Cu and Fe is not enough to play.If above-mentioned content is greater than 10 atom %, exists and improve the effect of ultraviolet light blocking ability and be difficult to play and rather low situation, it is outer in the case where containing Bi, it is also possible to there are problems that coloring (jaundice).

About above-mentioned second of metal oxide particle, in the case where above-mentioned metallic element (M ') selection in said combination (ii), based on metallic element (M), the content of Cu is preferably 0.01-10 atom %, more preferable 0.1-5 atom %, more preferable 0.1-1 atom %.Furthermore, based on metallic element (M), in said combination (ii), the content different from the metallic element (M ') (for the metallic element (M ') of Cu partner) of Cu is preferably 0.01-10 atom %, more preferable 0.1-5 atom %, more preferable 0.2-3 atom %.

About above-mentioned second of metal oxide particle, in the case where above-mentioned metallic element (M ') selection in said combination (i ii), based on metallic element (M), the content of Fe, Co and Ni are preferably 0.01-10 atom %, more preferable 0.1-5 atom %.In the case where above-mentioned metallic element (M ') selection in said combination (iii), based on metallic element (M), the content of Mn is preferably 0.01-30 atom %, more preferable 1-20 atom %, more preferable 1-10 atom %.

Furthermore, based on metallic element (M) in said combination (iii), the content different from the metallic element (M ') (for the metallic element (M ') of Fe, Co, Ni and Mn partner) of Fe, Co, Ni and Mn is preferably 0.01-10 atom %, more preferable 0.1-5 atom %, more preferable 0.2-3 atom %.

In the case where above-mentioned metallic element (M ') selection in said combination (iv), based on metallic element (M), the content of Bi is preferably 0.01-10 atom %, more preferable 0.1-5 atom %.Furthermore, in said combination (iv), based on metallic element (M), the content different from the metallic element (M ') (for the metallic element (M ') of Bi partner) of Bi is preferably 0.01-10 atom %, more preferable 0.1-5 atom %, more preferable 0.2-3 atom %.

In the case where above-mentioned metallic element (M ') selection in said combination (v), based on metallic element (M), the content of Ag is preferably 0.01-10 atom %, more preferable 0.05-2 atom %, more preferable 0.1-1 atom %.

About above-mentioned second of metal oxide particle, in the effective scope that the present invention (being provided by metallic element (M ')) is not provided, it is allowed in the oxide of metallic element (M) containing other metallic elements in addition to above-mentioned metallic element (M ').Example different from this metallic element of metallic element (M ') includes B, Si, Ge, Sb, Hf, Y, lanthanide element, alkali metal element and alkali earth metal.

(third invention)

The third metal oxide particle (third invention) of the invention is a kind of metal oxide particle, which is characterized in that metallic element (M ') is selected from least one of Co, Fe and Ni；Also reside in or i): metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And as in Co, Fe and Ni of metallic element (M ') at least partially be divalent (" the third metal oxide particle A " hereafter can be described as according to the particle of this mode i))；Or ii): metallic element (M) is Zn；And the crystal grain diameter in the direction in vertical (002) face of metal oxide particle hereafter can be described as " the third metal oxide particle B " no more than the particle of the crystal grain diameter not less than 8nm (according to this mode ii) in 30nm and vertical (100) face direction).

In the third above-mentioned metal oxide particle, above-mentioned metallic element (M) and its oxide are as described above.

About Co, Fe and Ni in the third above-mentioned metal oxide particle as above-mentioned metallic element (M '), the identical description of the metallic element (M ') related to the above in second of metal oxide particle is may be used in entitled " (second invention) " part in front.

It is divalent as at least part in Co, Fe and Ni of metallic element (M ') about above-mentioned the third metal oxide particle A.In other words, as above-mentioned metallic element (M '), contain at least one of the Ni of the Co of essentially Co (II), the Fe and essentially Ni (II) of essentially Fe (II).

The Co of essentially Co (II) can only include Co (II) or in addition to Co (II) also may include other valences Co (such as Co (III)), therefore there is no limit.But, for all right ultraviolet light blocking ability (absorption of UV), the former or close to its composition be it is preferred (specifically, based on whole Co, Co (II) content of Co is not less than 50 atom %, preferably not less than 70 atom %, more preferably no less than 90 atom %).Hereafter unless otherwise noted, simple word " Co (II) " is defined as " Co of essentially Co (II) ".

Equally, the Ni of Fe and essentially Ni (II) about essentially Fe (II), they may contain only Fe (II) and Ni (II) respectively, or can also contain the Fe and Ni (such as being respectively Fe (III) and Ni (III)) of other valences respectively in addition to Fe (II) and Ni (II), therefore there is no limit.But, for all right ultraviolet light blocking ability (absorption of UV), the former or close to its composition be it is preferred (specifically, based on whole Fe or Ni, there are the content of the Fe or Ni of Fe (II) or Ni (II) not less than 50 atom %, be preferably not less than 70 atom %, more preferably no less than 90 atom %).Hereafter unless otherwise noted, simple word " Fe (II) " is defined as " Fe of essentially Fe (II) " and simple word " Ni (II) " is defined as " Ni of essentially Ni (II) ".

The example of the preferred embodiment of metallic element (M ') includes: only Co (II) in above-mentioned the third metal oxide particle A；Only Ni (II)；Only Fe (II)；At least two mixed state in Co (II), Ni (II) and Fe (II)；The mixed state of Co (II) and the Co different from divalent (preferably trivalent)；The mixed state of Fe (II) and the Fe different from divalent (preferably trivalent)；The mixed state of Ni (II) and the Ni different from divalent (preferably trivalent)；The mixed state of Co (II) and other metallic elements (Fe or Ni)；The mixed state of Fe (II) and other metallic elements (Co or Ni)；The mixed state of Ni (II) and other metallic elements (Co or Fe).

Wherein, (although being not particularly limited, it is particularly preferred mode that its valence mumber, which is preferably combination 2), by Co (II) and Fe.Due to there is Co, the existing metal oxide particle containing Co has apparent coloring (becoming blue).So these existing particles are possible to be difficult with and lack effectiveness in needing more colorless and transparent application.In addition, above-mentioned existing metal oxide particle has the performance of ultraviolet light of the lower absorbing wavelength no more than 370nm than Zinc oxide particles.So in some cases, above-mentioned existing metal oxide particle lacks practicability in the application for needing harsher absorption of UV.By the way that Co (II) and Fe is applied in combination, these problems can solve as follows.About the above-mentioned coloring due to caused by Co, even if it slightly occurs, it can also be reduced to soft tone, so that being completely suitable for needing more colorless and transparent application, the performance of ultraviolet light of the absorbing wavelength no more than 370nm also can be improved.On the other hand, so far, in the case where for example only containing trivalent Fe as miscellaneous metallic element, the problem of there are still coloring (becoming dark brown).But, since Fe is being applied in combination with Co (II), there is also such a spin-off, above-mentioned coloring problem can effectively be alleviated by coloring caused by Co (II) (becoming blue), therefore a kind of metal oxide particle that there is no problem in terms of effectiveness is made.

Furthermore, especially in the field that application aspect especially needs safety, containing Fe (II) and/or Fe (III) are as main component rather than to contain Co and/or Ni as the metallic element (M ') of main component be preferably as Co and Ni have very strong toxicity.On the other hand, compound in view of being used as Fe (III) raw material is usually that Fe (II) compound (such as ferric acetate (II)) that is cheap and being used as Fe (II) raw material is expensive reality, so for Fe, for cost, the raw material of trivalent Fe is preferred.There is the shortcomings that turning yellow in the particle containing Fe (III).But, in the case where coloring becomes problem, if the Fe (III) contained is used in conjunction with at least one microcomponent selected from Fe (II), Co (II) and Ni (II), can reduce containing jaundice caused by Fe (III).In addition, ultraviolet light blocking performance also can be improved in Fe (III) and being used in conjunction with for above-mentioned microcomponent.In the field for needing safety strongly, metallic element (M ') is as follows in the content (according to the atomic ratio measuring with metallic element (M)) of metal oxide particle: for Fe, the total amount of divalent and trivalent Fe are preferably 1-10 atom %；And for Co and Ni, their own content is preferably 0.01-1 atom %, more preferably less than 0.1 atom %.

About above-mentioned the third metal oxide particle A, based on metallic element (M), the total content of metallic element (M ') is preferably 0.1-10 atom %, more preferable 0.2-5 atom %, more preferable 0.5-3 atom %.If above-mentioned content is less than 0.1 atom %, then it is possible that the absorbent properties (it is the effect containing Co (II), Fe (II) and/or Ni (II)) of long wavelength range ultraviolet light may not enough.If above-mentioned content is greater than 10 atom %, then it is possible that the absorbent properties in (no more than 370nm ultraviolet light) the absorbing wavelength range of the oxide of metallic element (M) inherently may be too low.

About above-mentioned the third metal oxide particle B, above-mentioned metallic element (M) is Zn, and this metal oxide particle is the crystal structure for including the metal oxide crystal containing zinc oxide.The size of crystal grain in particular directions about this crystal structure of composition is (namely in the size of the crystal grain diameter perpendicular to (002) face (Ds (002)) and in the size (Ds (100)) of the crystal grain diameter perpendicular to (100) face, Ds (002) is not more than 30nm, and Ds (100) is not less than 8nm.Above-mentioned Ds (100) is preferably not less than 10nm.If above-mentioned Ds (100) is less than 8nm, then it is possible that occurring upper blue shift in ultraviolet radiation absorption wavelength.If above-mentioned Ds (002) is greater than 30nm, then it is possible that transparency is low.By the way, the size of above-mentioned crystal grain diameter is defined as the numerical value of the method as described in the examples measurement of certain preferred embodiments described in detail below.

About the third above-mentioned metal oxide particle (especially metal oxide particle B), primary particle is preferably mono-crystalline structures (crystal structure containing a crystal grain).Either mono-crystalline structures or polycrystalline structure can all be determined with TEM observation.

It by the way, is preferably divalent as at least part in Co, Fe and Ni of metallic element (M ') and about the third metal oxide particle B, the foregoing description in relation to metallic element (M ') can be suitable for this.

About the third above-mentioned metal oxide particle, within the scope of the effect of the invention, it is also possible to the oxide of above-mentioned metallic element (M) be made also to contain other metallic elements in addition to containing above-mentioned miscellaneous metallic element (M ').Such metallic element different from miscellaneous metallic element (M ') is not particularly limited.But such as be preferably, as above-mentioned metallic element (M) containing those of be selected from Al, In, Sn, Mn, Ce, alkali metal element and alkali earth metal.

(the 4th invention)

4th kind of metal oxide particle (the 4th invention) of the invention is a kind of metal oxide particle, the metal oxide particle is a kind of metal oxide particle for containing metallic element (M) oxide, and the metal oxide particle is characterized in that: metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And also reside in i): containing selected from least one of N, S and the 17th race (7B race) element and acyl group (hereafter can be described as " the 4th kind of metal oxide particle A " according to the particle of such mode i)) in the oxide of metallic element (M)；Or ii): the particle containing at least two (according to such mode ii) in N, S and the 17th race (7B race) element in the oxide of metallic element (M) hereafter can be described as " the 4th kind of metal oxide particle B ")；Or iii): the particle in the grain containing the component (according to such mode iii) for being originated from the metallic element (M ') different from metallic element (M) hereafter can be described as " the 4th kind of metal oxide particle C ").Due to containing above-mentioned miscellaneous nonmetalloid (N, S and the 17th race (7B race) element), the expectable effect for obtaining improving UV absorbing properties, specifically, providing the performance that absorbing wavelength is greater than the light of the intrinsic optical absorption edge of metallic element (M) oxide.

In above-mentioned 4th kind of metal oxide particle, above-mentioned metallic element (M) and its oxide are as described above.In particular, the preferred embodiment of the 4th kind of metal oxide particle is a kind of solid solution, wherein a part of oxygen atom in above-mentioned element (N, S, the 17th race (7B race) element) substituted metal element (M) oxide.In addition, other forms can be also chosen, nitrogen oxide, sulfur oxide compound and oxidative halogenation object as escribed above.

About the above-mentioned miscellaneous nonmetalloid (N, S, the 17th race (7B race) element) in above-mentioned 4th kind of metal oxide particle, optical absorption edge is effectively shifted to for longer wavelength side, nitrogen, fluorine and sulphur are preferably that especially nitrogen is preferred.

In above-mentioned 4th kind of metal oxide particle A, containing selected from least one of above-mentioned miscellaneous nonmetalloid and acyl group in the oxide of metallic element (M).Due to containing acyl group together with above-mentioned miscellaneous nonmetalloid, such effect can be obtained: dispersibility is increased to such degree, so that transparent film can be made.For example, if containing nitrogen, particle turns yellow, so that this turn yellow is it will be evident that even when dispersion film is made in particle.But due to containing acyl group, coloring degree is improved.By the way, as being mentioned below, also by the way that the product of alkoxide (alkoxide) or its (part) hydrolysis to be integrated on above-mentioned metallic element (M) oxide surface to (wherein alkoxide includes at least one metallic element (being preferably selected from least one of Si, Ti, Al and Zr) for being different from metallic element (M ') contained in oxide), identical effect can be obtained.If combined by the combination of alkoxide or its (part) hydrolysate and containing acyl group, then it is possible to provide the better effects for reducing coloring.

In above-mentioned 4th kind of metal oxide particle B, in above-mentioned miscellaneous nonmetalloid at least two are contained in metallic element (M) oxide.Bigger raising ultraviolet radiation absorption effect is used in combination at least two miscellaneous nonmetalloids.At least one of at least two miscellaneous nonmetalloids are preferably any in nitrogen, fluorine and sulphur.

In above-mentioned 4th kind of metal oxide particle C, in the grain containing the component for being originated from the metallic element (M ') different from metallic element (M).Here, to above-mentioned metallic element (M '), there is no limit.This metallic element (M ') can arbitrarily selected from it is above-mentioned the first, second, the miscellaneous metallic element that is drawn of the third metal oxide particle.But metallic element (M ') is preferably different from metallic element (M) and selected from least one of Co, Cu, Fe, Bi, In, Al, Ga, Ti, Sn, Ce, Ni, B, Mn, Ag, Au, platinum group, alkali metal element and alkali earth metal.The detailed content of this metalloid element is as the above-mentioned metallic element (M ') in second of metal oxide particle.Especially, Co, Fe, Bi, Ni, Mn and Ag are effective in terms of optical absorption edge is moved to longer wavelength side, Co (II), Fe (II), Ni (II), Cu (I) and Cu (II) in terms of caused dispersion film coloring are effective in the case where reducing above-mentioned miscellaneous nonmetalloid and being N, and In, Al, Ga, Ti, Sn, Ce and B are effective in terms of the absorption coefficient of light that the band absorption improved close to metallic element (M) oxide limits.

In above-mentioned 4th kind of metal oxide particle A, B and C, based on metallic element (M), the content of above-mentioned miscellaneous nonmetalloid (N, S, the 17th race (7B race) element) is preferably 0.01-20 atom %, more preferable 0.05-10 atom %.If this content less than 0.01 atom %, there is a situation where to improve the not sufficiently effective of UV absorbing properties.On the other hand, if above-mentioned content is greater than 20 atom %, there is a situation where that the absorbability at shorter than 370nm is low.

About the present invention the first any one of to the 4th kind of metal oxide particle, for bigger raising UV absorbing properties, preferably, other than above-mentioned miscellaneous (metal/non-metal) element, also containing the component from alkali metal element and alkali earth metal, based on metallic element (M), content is 0.001-5 atom %.Based on metallic element (M), the content of alkali metal element and/or alkali earth metal is more preferably 0.001-1 atom %.

About any one of metal oxide particle of the present invention, the presence of above-mentioned miscellaneous element (other metallic elements outside namely above-mentioned miscellaneous (metal/non-metal) element and removal of impurities (metal/non-metal) element that may contain in metallic element (M) oxide) can be confirmed with following methods: about the primary particle of metal oxide particle and the aggregation of these primary particles, when observing its transmission plot with FE-TEM (Flied emission transmission electron microscope), it was found that no metal is segregated but has the place of particle, then elemental analysis is carried out to this place with high-resolution XMA, to examine and determine out the peak for belonging to every kind of element.About the confirmation of segregation, if segregation is is generally impossible to the level directly confirmed from transmission plot (being observed with FE-TEM) or with the combination of XMA, segregation is considered being not present.

The measurement of above-mentioned miscellaneous element (metallic element outside namely above-mentioned miscellaneous (metal/non-metal) element and other removal of impurities (metal/non-metal) elements that may contain in metallic element (M) oxide), such as x-ray fluorescence analysis, atomic absorption spectrum and ICP (inductively coupled plasma atomic emission spectrum) are carried out possibly through microanalysis.But, preferably a kind of method carries out in this way for above-mentioned measurement: the above-mentioned elemental analysis wherein carried out with desired spatial resolution (spot diameter) with high-resolution XMA, to measure the peak intensity of each metallic element, above-mentioned content then is calculated from its result.About above-mentioned spot diameter, lower limit can be set to by the way that probe narrows down to 1nm φ, and above-mentioned spot diameter can also freely and continuously amplify.Specifically, in the transmission plot of FE-TEM observation, the aggregation for the metal oxide particle that about 10 have no segregation is generally selected to carry out elemental analysis comprising such spatial resolution (spot diameter) of all these about 10 (thin) particles.

By the way, whether contain miscellaneous element (metallic element outside namely above-mentioned miscellaneous (metal/non-metal) element and other removal of impurities (metal/non-metal) elements that may contain in metallic element (M) oxide) about each particle or whether be dispersed in each particle about miscellaneous element, local elemental analysis can be carried out by the way that beam diameter to be reduced to (such as dropping to 1nm φ) to confirm.

As above-mentioned FE-TEM, such as the Flied emission transmission electron microscope (HF-2000 type, acceleration voltage 200kV) of Hitachi Co., Ltd. production can be used.As above-mentioned high-resolution XMA, such as the X-ray microanalysis instrument (Sigma type, energy dispersion type, beam diameter: 10 φ of spatial resolution) of Kevex production can be used.

The size of the first of the invention to the 4th kind of metal oxide particle is as follows.As above-mentioned, about the first metal oxide particle, it is important that this particle is fine grained, that is, for primary particle diameter, and average grain diameter is not more than 0.1 μm of particle.About second to the 4th kind metal oxide particle, they include all referred to as ultra-fine grain and fine grain particles, therefore there is no limit.In general, the average grain diameter of primary particle is preferably 1-100nm.

About any of the invention the first to the 4th kind of metal oxide, preferred mode is that primary particle diameter is 3-50nm.In the case where the first metal oxide particle, primary particle diameter is more preferably 3-30nm, more preferable 5-20nm.In the case where second to the 4th kind of metal oxide particle, primary particle diameter is more preferably 5-30nm, more preferable 5-20nm, particularly preferred 10-20nm.If the average grain diameter of primary particle is greater than 100nm, then it is possible that transparency is low.If the average grain diameter of above-mentioned primary particle is too small, due to quantum effect, ultraviolet radiation absorption limit is usually mobile to shorter wavelength side, therefore the metal oxide particle is not preferred for use as ultraviolet absorption material.On the other hand, if the average grain diameter of above-mentioned primary particle is too big, then it is possible that transparency is low.

By the way, in the present invention, the average grain diameter of primary particle refers to crystal grain diameter (Dw) or specific surface area diameter (Ds).In detail, in the case where above-mentioned particle is crystal, refer to crystal grain diameter (Dw), and in the case where above-mentioned particle is non-crystal situation, refer to specific surface area diameter (Ds).It is preferred, therefore, that any one of crystal grain diameter (Dw) or specific surface area diameter (Ds) are within the above range.In more detail, crystal grain diameter (Dw) is used for the case where X-ray diffraction-crystallography crystal, refers to the crystallite dimension that Scherrer equation determines.About this crystal grain diameter (Dw), it is usually possible to: measure the x-ray diffractogram of powder of metal oxide particle, then about its three strong ray (maximum peak (1) of diffracted ray, the second maximum peak (2) of diffracted ray and the third maximum peak (3) of diffracted ray), the crystal grain diameter D1 of the vertical direction in diffracted ray (1)-(3) diffraction lattice face is belonging respectively to from the measurement of the full duration or integral breadth Scherrer equation of respective half maximum intensity, D2 and D3, then its average value ((D1+D2+D3)/3) is calculated, as crystal grain diameter (Dw).It on the other hand, can be by specific surface area diameter (Ds) be calculated as follows after the specific surface area of the true specific gravity and this powder that measure metal oxide particle powder.

Ds (nm)=6000/ (ρ × S)

Wherein ρ: the true specific gravity (dimensionless) of particle

S: with the specific surface area (m for the particle that B.E.T. method measures²/g)

About the first of the invention to the 4th kind of metal oxide particle, it is preferred that the oxide of above-mentioned metallic element (M) is crystal；And the crystal grain diameter (Dw) of metal oxide particle is no more than 30nm (by the average value for the numerical value that Scherrer equation is calculated with regard to the three strong ray at the peak XRD).

Especially, about the first of the invention to the 4th kind of metal oxide particle, in the case where metallic element (M) oxide is zincite crystal, for all right transparency and UV absorbing properties, preferably, in the crystal grain diameter of X-ray diffraction method measurement, it is not more than 30nm in the crystal grain diameter of the metal oxide particle of lattice plane (002) vertical direction, and is not less than 8nm in the crystal grain diameter of lattice plane (100) and/or the metal oxide particle of lattice plane (110) vertical direction.More preferably, it is not more than 20nm in the crystal grain diameter of the metal oxide particle of the vertical direction of lattice plane (002), and is not less than 10nm in the crystal grain diameter of lattice plane (100) and/or the metal oxide particle of lattice plane (110) vertical direction.Specifically, the crystal grain diameter in lattice plane (002) vertical direction (optical axis direction) does not have a great impact to UV absorbing properties, and about this crystal grain diameter, for enhancing the transparency, diameter is smaller the more preferred.On the other hand, crystal grain diameter about lattice plane (002) direction (vertical direction of optical axis), such as the crystal grain diameter of lattice plane (100) and/or lattice plane (110) vertical direction, if it is too small, it damages UV absorbing properties.By the way, then the crystal grain diameter of lattice plane vertical direction can be measured by powder X-ray diffractometry with Scherrer analysis.

About the first of the invention to the 4th kind of metal oxide particle (especially the first metal oxide particle), in order to improve the paint film of generation or the transparency of resin composite materials, preferably, in the state being dispersed in any solvent or resin, the discrete particles diameter of these metal oxide particles is not more than 500nm.Discrete particles diameter is more preferably no more than 200nm, more preferably no more than 100nm, and being especially desirable to primary particle can disperse with monodisperse status or close to monodisperse status, most preferably no greater than 50nm.By the way, the diameter of discrete particles can for example be measured with dynamic light scattering type particle diameter distribution measuring device (such as " LB-500 " of HoribaSeisakusho production).

The optical property of metal oxide particle of the invention can be evaluated with such a method, and the blocking performance (ultraviolet light blocking performance) of the light of middle-ultraviolet lamp (ultraviolet light no more than 380nm and the visible light no more than 450nm) range and the transmission performance (visible transmission performance) of visible light (450-780nm) are used as index.Preferably, ultraviolet radiation absorption functional material has high ultraviolet light to block performance and visible transmission performance.In general, ultraviolet light blocks performance and visible transmission performance that can judge evaluating spectral transmission property in the state of only particle, under the membrane stage made of following film-forming compositions or in the state that particle is dispersed in decentralized medium such as solvent.In detail, ultraviolet light blocks performance by evaluating the transmissivity under any wavelength (such as 380nm, 400nm, 420nm) of ultraviolet ray range as representative value or is being not more than 450nm by evaluating or is judging no more than the average transmittance under 380nm.On the other hand, it is seen that the transmission performance of light judges by evaluating the transmissivity under any wavelength (such as 500nm, 600nm, 700nm) of visible-range as representative value or by evaluating the average transmittance within the scope of 450-780nm or 380-780nm.The numerical value of these transmissivities can be obtained by the transmissivity measurement including parallel transmitted light and diffuse transmission light of each wavelength, such as can be measured with there is the spectrometer of integrating sphere.But be pole high degree of transparency so that diffuse transmission light can substantially ignore in the case where (specifically, the case where turbidity (haze) of sample is less than 5%) in sample, then only the transmissivity of directional light can be used as measured value.

In the preferred embodiment of metal oxide particle of the invention, such as when it is 0.1wt% that they, which are dispersed in organic solvent middle particle concentration, transmissivity under 380nm is preferably no greater than 10%, more preferably no more than 5%, and the transmissivity under 400nm is preferably no greater than 50%, more preferably no more than 20%, and the transmissivity under 600nm is preferably not less than 70%, more preferably no less than 80%.In addition, the transmissivity under 420nm is preferably no greater than 50%.

In addition, the use of metal oxide particle of the invention is not limited to the purpose of ultraviolet blocking-up, when film is made, preferably there is high degree of transparency.Specifically, its turbidity is preferably no greater than 10%, more preferably no more than 2%, more preferably no more than 1%.

By the way, the method as the optical absorption property of measurement particle (blocking property including ultraviolet light), also can be used such a method, wherein the diffusing reflection of measurement particle powder.In this case, if reflection is low, just height is absorbed, and on the other hand, if reflection is high, absorb just low.It is preferable that: as of the present invention, the reflection in ultraviolet ray range is low, and the reflection in the visible-range not less than 450nm is high.

About metal oxide particle of the present invention, all right visible transmission performance and only for ultraviolet selecting absorbent properties, preferably, this particle is such a particle, when the film for containing this particle and/or the metallic element obtained by this particle (M) oxide crystal as basic component is made in this particle, then the optical property of produced film meets the following conditions.About this point, such as about the form and its forming process of above-mentioned film, the description cited below in relation to inventive film is equally applicable to this.By the way, the following optical property of above-mentioned film is defined as the numerical value of the measurement of method described in the detailed description with the embodiment of certain preferred embodiments the following.In addition, they be further defined as the only physical property of membrane part (except substrate) and in view of film coating substrate optical property and only substrate optical property evaluate.In the case where metal oxide particle of the invention contains Co (II) as metallic element, furthermore among the optical property of film, the transmissivity (%) of 380nm wavelength light is an index of UV absorbing properties, is defined as T³⁸⁰, and the transmissivity (%) of 500nm wavelength light is an index of visible transmission performance, is defined as T⁵⁰⁰, and the minimum value of the transmissivity (%) of 500-700nm wavelength light is defined as T¹, and T¹And T⁵⁰⁰Absolute value of the difference (| T¹-T⁵⁰⁰|) it is defined as Δ T.

About metal oxide particle of the invention, in the case where film is made in this particle in aforementioned manners, if the coating amount (usage amount) of per unit substrate area changes, with this variation, the T of produced film³⁸⁰、T⁵⁰⁰Also change with Δ T value.Accordingly, with respect to the optical property of produced film, work as T³⁸⁰Value as standard when, they are defined as using T⁵⁰⁰With the evaluation of Δ T value.The preferred embodiment of above-mentioned film is expressed as follows in being classified as following situations: the case where containing the metal oxide particle of Co (II) (a)；With (b) the case where other metal oxide particles.

The case where metal oxide particle containing Co (II) (a):

(i) when above-mentioned film is with T³⁸⁰When a kind of method no more than 40% is made, then Δ T is preferably no greater than 10%, and it is even more preferred that Δ T is not more than 10% and T⁵⁰⁰Not less than 90%；And it is even more preferred that Δ T is not more than 5% and T⁵⁰⁰Not less than 95%.

Preferably, (ii) is when above-mentioned film is with T³⁸⁰When a kind of method no more than 30% is made, then Δ T is preferably no greater than 10%, and it is even more preferred that Δ T is not more than 10% and T⁵⁰⁰Not less than 90%；And it is even more preferred that Δ T is not more than 10% and T⁵⁰⁰Not less than 95%；And be particularly preferably: Δ T is not more than 5% and T⁵⁰⁰Not less than 95%.

It is further preferred that (iii) is when above-mentioned film is with T³⁸⁰When a kind of method no more than 20% is made, then Δ T is preferably smaller than 10%, and it is even more preferred that Δ T less than 10% and Y⁵⁰⁰Not less than 80%；And it is even more preferred that Δ T is not more than 5% and T⁵⁰⁰Not less than 85%；And be particularly preferably: Δ T is not more than 5% and T⁵⁰⁰Not less than 90%.

It is particularly preferred that (iv) is when above-mentioned film is with T³⁸⁰When a kind of method no more than 10% is made, then Δ T is preferably smaller than 10%, and it is even more preferred that Δ T less than 10% and T⁵⁰⁰Not less than 80%；And it is even more preferred that Δ T is not more than 5% and T⁵⁰⁰Not less than 85%；And be particularly preferably: Δ T is not more than 5% and T⁵⁰⁰Not less than 90%.

The case where metal oxide particle unlike those described above (b):

(i) when above-mentioned film is with T³⁸⁰When a kind of method no more than 20% is made, then T⁵⁰⁰Preferably not less than 90%, it is more preferably no less than 90%.

Preferably, (ii) is when above-mentioned film is with T³⁸⁰No more than 10% (more preferable T³⁸⁰When being made no more than a kind of method 5%), then T⁵⁰⁰Preferably not less than 70%, it is more preferably no less than 80%.

About the first of the invention to the 4th kind of metal oxide particle, it is preferred that the particle containing metallic element (M) oxide contains the acyl group of the molar ratio computing 0.1-14mol% by metallic element (M).The reason is that such metal oxide particle has fabulous dispersibility and obtains the composition and such film for generating the film for having good transparency.Especially, in the case where metallic element (M) is Zn, Ti, Ce, In or Sn, the refractive index of crystal is so high, so that usually there is the scattering of visible light, so the film of high muddy is usually made when the metal oxide particle is distributed in adhesive such as resin.But the above-mentioned particles generation containing acyl group has the low blushing of excellent clarity.Above-mentioned acyl group particularly preferably has 1-3 carbon atom.

About the first of the invention to the 4th kind of metal oxide particle, preferably, the oxide of metallic element (M) is such a oxide, alkoxide or its (part) hydrolysate combine on its surface, and wherein alkoxide includes at least one metallic element for being different from metallic element (M ') contained in oxide.Its reason with it is above-mentioned why preferred metal oxide particle be wherein the particle containing acyl group be identical.That is, such particle is preferred for the composition and such film of all right dispersibility and the film forming for obtaining good transparency.In particular, this mode is effective in the case where metallic element (M) is Zn, Ti, Ce, In or Sn.Above-mentioned at least one metallic element contained in metallic element (M) oxide different from metallic element (M ') is preferably selected from Si, Ti, Al and Zr.In order to which such particle is made in metal oxide particle, so that alkoxide or its (part) hydrolysate are integrated on metallic element (M) oxide surface, wherein alkoxide include at least one metallic element different from metallic element contained in oxide (M ') (preferably, selected from least one of Si, Ti, Al and Zr metallic element), it is suitable at least one of following metallic compound (1)-(3) surface-treated metal oxide particle.

Hereinafter, it provides in relation to above-mentioned metallic compound (1)-(3) description.

Metallic compound (1): metal alkoxide includes above-mentioned at least one metallic element for being different from metallic element (M ') contained in metallic element (M) oxide, such as tetramethoxy-silicane and four butoxy silanes.

Metallic compound (2): the metallic compound containing organic group indicated with following general formula (a).By the way, in these metallic compounds, the type of metallic element is unrestricted.

Y¹ _iM¹X¹ _j (a)

(wherein: Y¹For organo-functional group；M¹For metallic atom；X¹ _jFor hydrolyzable group；And i and j be 1 to (s-1) integer and meet i+j=s (wherein s be M¹Valence mumber)).

The example of the metallic compound containing organic group indicated with general formula (a) includes below.

Wherein M¹Example for the metallic compound containing organic group of aluminium includes the various coupling agents containing aluminium, such as diisopropoxy aluminium oacetic acid, diisopropoxy aluminium alkyl acetoacetates acetic acid, diisopropoxy aluminium monomethacrylate, aluminum stearate oxide trimer and diisopropoxy aluminium alkyl acetoacetates acetic acid list (dioctyl phosphoric acid).

Wherein M¹Example for the metallic compound containing organic group of silicon includes various silane coupling agents, such as: the silane coupling agent (such as vinyltrimethoxysilane, vinyltriethoxysilane, ('beta '-methoxy ethyoxyl) silane of vinyl three and vinyl triacyloxysilanes) containing vinyl；Amino-containing silane coupling agent (such as N- (2- aminoethyl) -3- aminopropyltriethoxy dimethoxysilane, 3-N- phenyl-γ-aminopropyltrimethoxysilane and bis- [3- (trimethoxysilyl) propyl] ethylenediamines of N, N ' -)；Silane coupling agent (such as γ-glycidoxypropyltrime,hoxysilane and 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane) containing epoxy group；Silane coupling agent (such as 3- r-chloropropyl trimethoxyl silane) containing chlorine；Silane coupling agent (such as acryloyloxypropyltrimethoxysilane and acryloxypropyl triethoxysilane) containing acryloxy (acryloxy)；Silane coupling agent (such as 3- methacryloxypropyl trimethoxy silane and 3- methacryloxypropyl) containing methacryloxy；Silane coupling agent (such as 3-mercaptopropyi trimethoxy silane) containing sulfydryl；Ketimide type silane coupling agent (such as N- (1,3- dimethylbutylene) -3- (triethoxysilyl) -1- propylamine)；Cationic silane coupling agent (such as hydrochloric acid N- [2- (vinyl-benzylamino) ethyl] -3- aminopropyl trimethoxysilane)；Silane coupling agent (such as methyltrimethoxysilane, trimethylmethoxysilane, ruthenium triethoxysilane and ethoxy trimethoxy silane) containing alkyl；Silicon compound (such as ten three fluoro- 1,1,2,2- tetrahydro octyl) triethoxysilane with fluorine-containing organic group)；Silane coupling agent (such as isocyanates conjunction propyl trimethoxy silicane) with the organic group containing isocyanate group；The silane coupling agent that following general formula (b) indicates:

R’O(C₂H₄O)_nC₃H₆Si(OR”)₃ (b)

(wherein: R ' is hydrogen or selected from least one of alkyl (such as methyl), naphthenic base, aryl, acyl group and aralkyl (can be with substituent group)；R " is selected from least one of alkyl (such as methyl), naphthenic base, aryl, acyl group and aralkyl (can be with substituent group)；And n is the integer not less than 1；And

γ-ureidopropyltriethoxysilane and hexa-methylene disilazane.

Wherein M¹Example for the metallic compound containing organic group of zirconium includes various zirconium compounds, such as (double -2,4- glutaric acid) two n-butoxy zirconiums, three n-butoxy zirconium of glutaric acid and dimethacrylate dibutoxy zirconium.

Metallic compound (3): (part) hydrolysate or condensation product of metal alkoxide (metal can be any metal) and above-mentioned (2), such as they with following general formula (c) indicate:

R¹-(O-M(-R² _m1)(-R³ _m2))_n-R⁴ (c)

(wherein: R¹And R²Each of for hydrogen atom or in alkyl, naphthenic base, aryl, aralkyl and acyl group any group (it can substituted base)；R³It is hydrolyzable group (with the X in above-mentioned general formula (a)¹It is identical) or hydroxyl；R⁴For R²Or R³；M is metallic atom；M1 and m2 is the chemical valence -2 of M)；And n is the integer of 2-10000；By the way, about the R being integrated on metallic atom M²And R³Type and number (m1 and m2), they can be identical or can be different between at least part metallic element (M) between all metallic atom M).

For example, the hydrolysis-condensation product about above-mentioned metallic compound (2), example includes: that metallic atom M is integrated in above-mentioned general formula (a)¹Some or all of upper hydrolyzable group X¹Compound made from the hydrolyzed method for generating OH group；And the M for passing through generation¹Further condensation reaction (such as dehydrating condensation) forms M between-OH key¹-O-M¹Compound made from the method for key.Its specific example includes (containing branch including those) or the cricoid hydrolysis-condensation product (from straight chain or cricoid trimer) of the straight chain as made from compound hydrolysis-condensation and/or partial hydrolysis-condensation containing organic group, and the compound containing organic group in metallic compound (2) as enumerating in the past.

The example of metallic compound (3) includes: four titanium n-butoxide tetramer (IV) (C₄H₉O-[Ti(OC₄H₉)₂O]4-C₄H₉(Wako Pure Chemical Industries, Ltd. production)；Tetramethoxy-silicane (IV) tetramer；Methyltrimethoxysilane tetramer；Tetramethoxy-silicane-methyltrimethoxysilane cohydrolysis-condensation product；And aluminium butoxide (III) tetramer.

Method for producing metal oxide particle of the invention is unrestricted.Any method for being contained the metal oxide particle of miscellaneous metallic element desired by (doped with) in this way all can be used, regardless of whether it is known method.Such as, such a production method is preferred (hereinafter referred to as production method (A)), the method includes a step, wherein metallic element (M) compound and/or its hydrolysis-condensation product, miscellaneous metallic element (M ') compound and/or miscellaneous nonmetalloid compound and alcohol are used as raw material, and their mixed system is in the condition of high temperature, to form (deposition) metal oxide particle.In detail, production method (A) is the method comprising such a step, wherein: metallic element (M) compound and/or its hydrolysis-condensation product, miscellaneous metallic element (M ') compound and/or miscellaneous nonmetalloid compound and the alcohol that will act as raw material are mixed as raw material, and while mixing or after mixing, the mixed system of generation is in the condition of high temperature.By making the mixed system generated be in the condition of high temperature, metal oxide particle can be formed in the reaction system with this method.

Can be used for metallic element (M) compound of production method (A) there is no limit.But the carboxylate of metallic element (M) is preferred.Furthermore, the hydrolysis-condensation product of metallic element (M) compound is that zinc compound hydrolyzes and/or be condensed hydrolysate and/or condensation product obtained, including monomeric compound to polymerizable compound (hereafter " metallic element (M) compound " can be related to " metallic element (M) compound and/or its hydrolysis-condensation product ").

The above-mentioned carboxylate of metallic element (M) is preferably such a compound, there is at least one substituent group in the molecule thereof, so that metallic element (M) atom replaces the hydrogen atom of carboxyl.Its preferred specific example includes converting carboxylate groups in carboxylic acid compound into above-mentioned substituent group, carboxylic acid compound is for example: chain carboxylic acid's (such as saturated monocarboxylic acid, unsaturated monocarboxylic acid, saturation polybasic carboxylic acid and unsaturated polybasic carboxylic acid), cyclic annular saturated carboxylic acid, aromatic carboxylic acid's (such as one dollar aromatic carboxylic acid and aromatics unsaturation polybasic carboxylic acid), and in these carboxylic acids, there are also functional group or atomic radicals (such as hydroxyl, amino, nitro, alkoxy, sulfuryl, cyano and halogen atom) in the molecule thereof for compound.

It is further preferred that the compound indicated in these carboxylates of metallic element (M) for following general formula (I):

M(O)_(m-x-y-z)/2(OCOR¹)_x(OH)_y(OR²)_z (I)

(wherein: M is the atom (selected from least one of Zn, Ti, Ce, In, Sn, Al and Si) of metallic element (M)；R¹For selected from least one of hydrogen atom, alkyl, naphthenic base, aryl and aralkyl (wherein these groups can substituted base)；R²For selected from least one of alkyl, naphthenic base, aryl and aralkyl (wherein these groups can substituted base)；And m, x, y and z are to meet x+y+z≤m, the number (the wherein chemical valence that m is above-mentioned M) of 0 < x≤m, 0≤y < m, 0≤z < m.

(such as the carboxylate for the metallic element (M) that hydroxyl or alkoxy replace a part of the example above to illustrate), saturated carboxylic acid salt, salt unsaturated carboxylic acid and alkaline acetate.More preferably above-mentioned logical formula (I) compound represented, the most preferably formates of metallic element (M), the propionate of the acetate of metallic element (M) and metallic element (M) and the basic salt there are also them.

By the way, the carboxylate of metallic element (M) can be the hydrate of the carboxylate containing the crystallization water, but preferred anhydride.

The compound described below indicated in relation to above-mentioned logical formula (I) is described in more detail.

As the R in logical formula (I)¹And R², make it easy to be made for highly dispersible metal oxide particle form, hydrogen and C₁-C₄Alkyl (such as methyl) is preferably that hydrogen, methyl and ethyl are particularly preferred.Further, since identical reason, in logical formula (I), x preferably satisfies 1≤x≤m, and y preferably satisfies 0≤y≤m/2, and z preferably satisfies 1≤z≤m/2.

It as the compound that logical formula (I) indicates, makes it easy to be made for highly dispersible metal oxide particle form, those of rate of dissolution is fast, and compound is preferred.Rate of dissolution is directly measured possibly through reaction.But, it is defined as time t, i.e. at 25 DEG C, the compound that the logical formula (I) of 2 parts by weight indicates is blended in 25 ± 3 DEG C of 200 parts by weight ion exchange waters (pH value 5-8), they are bound together, until passing through the time needed for being completely dissolved obtained clear solution.The rate of dissolution for the compound that logical formula (I) indicates is preferably no greater than 2min, more preferably no more than 1min, more preferably no more than 30s.

In the hydrolysis-condensation product for the compound that logical formula (I) indicates, condensation product preferably has marriage chain-(M-O)_nCompound (wherein n be not less than 1) so that metallic element (M) and oxygen (O) are metal oxygen alkane (metaloxane) combination.Although there is no limit, the condensation levels (average) of above-mentioned condensation product to be preferably no greater than 100, is more preferably no more than 10, because a kind of crystallite dimension and the uniform metal oxide particle of form can be made in this way.

About metallic element (M) compound, can be used alone only above-mentioned a kind of compound, or can be in combination with one another by least the above two classes compound.

Although there is no limit the example that can be used for miscellaneous metallic element (M ') compound of production method (A) includes carboxylic metallic salt and metal alkoxide.About miscellaneous metallic element (M ') compound, can be used alone only above-mentioned a kind of compound, or can be in combination with one another by least the above two classes compound.

As above-mentioned miscellaneous metallic element (M ') compound, substantially use the compound of such a metallic element (M ') (still, in the case where second of metal oxide particle, at least two metallic elements (M ')), it is contained in metal oxide as metallic element (M ').

There is no limit for above-mentioned miscellaneous nonmetalloid compound.But such as miscellaneous nonmetalloid be N in the case where, preferred example includes nitrogenous compound, such as ammonia, ammonium hydroxide, urea and ammonium carbonate.In the case where miscellaneous nonmetalloid is S, preferred example includes hydrogen sulfide and metal sulfide, such as vulcanized sodium.In the case where miscellaneous nonmetalloid is the 17th race's element, preferred example includes fluoride, chloride, bromide and the iodide of sour (such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid) and metal (preferably, metallic element (M) or (M ')).About miscellaneous nonmetalloid compound, can be used alone only above-mentioned a kind of compound, or can be in combination with one another by least the above two classes compound.

Although there is no limit, but the example of the alcohol suitable for production method (A) includes: monohydric alcohol, such as aliphatic monohydric alcohol (such as methanol, ethyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, octadecanol), aliphatic unsaturated monohydric alcohol (such as allyl alcohol, crotonyl alcohol, propargyl alcohol), alicyclic monohydric alcohol (such as cyclopentanol, cyclohexanol), aromatic mono-alcohols (such as benzylalcohol, cinnamyl alcohol, methyl phenyl carbinol), phenols (such as ethyl phenol, octyl phenol, catechol, dimethlbenzene, guaiacol, to cumylphenol, cresols, metacresol, o-cresol, paracresol, dodecylphenol, naphthols, nonyl phenol, phenol, benzylphenol, to methoxy ethyl phenol) and heterocycle monohydric alcohol (such as furfuryl alcohol)；Dihydric alcohol such as aklylene glycol (such as ethylene glycol, propylene glycol, trimethylene, 1, 4- butanediol, 1, 5- pentanediol, 1, 6- hexylene glycol, 1, 8- ethohexadiol, 1, 10- decanediol, quite any alcohol, diethylene glycol (DEG), triethylene glycol), alicyclic diol (such as ring amyl- 1, 2- glycol, hexamethylene -1, 2- glycol, hexamethylene -1, 4- glycol) and polyether polyols (such as polyethylene glycol, polypropylene glycol), the derivative (such as monoether or monoesters) obtained by above-mentioned glycol, such as propylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3- methyl -3- methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether (EGMBE), triethylene glycol monomethyl ether and ethylene glycol acetate；And the polyalcohol of no less than 3 functionalities, such as trihydroxylic alcohol (such as glycerol, trimethylolethane), tetrahydroxylic alcohol (such as erythrite, pentaerythrite), pentabasis alcohol (such as ribitol, xylitol) and hexahydroxylic alcohols (such as sorbierite), polybasic aromatic alcohol, such as benzyleneglycol, benzpinacol and phthalyl alcohol, polyphenol such as dihydric phenol (such as catechol, resorcinol, hydroquinone) and trihydric phenol (such as pyrogallol, phloroglucin) and its derivative, so that (1 to (n-1)) (the wherein OH number that n is each molecule) OH group is converted to ester bond or ehter bond to the part in these polyalcohols.About alcohols, can be used alone only above-mentioned a kind of compound, or can be in combination with one another by least the above two classes compound.

As above-mentioned alcohol, preferably it is easy to be formed the alcohol of metal oxide particle in above-mentioned alcohol with metallic element (M) compound, miscellaneous metallic element (M ') compound and/or miscellaneous nonmetalloid compound by reacting.Aliphatic alcohol and high water soluble alcohol are preferred, specifically, alcohol of the solubility not less than 1wt% is preferred relative to water, and relative to water, alcohol of the solubility not less than 10wt% is preferred.

Metallic element (M) for raw material between compound and alcohol it is mutual than (recipe ratio) there is no limit.But the ratio between atom number of metal preferably 0.8-1000, more preferable 0.8-100, more preferable 1-50, particularly preferred 1-20 in the hydroxy number and metallic element (M) compound for (being originated from alcohol) in alcohol.

In addition, between metallic element (M) compound used and miscellaneous metallic element (M ') compound or miscellaneous nonmetalloid compound it is mutual than (recipe ratio) there is no limit.But, this ratio is suitable for setting in this way, and the ratio between metallic atom number and the metallic atom number in miscellaneous metallic element (M ') compound or the atom number of the miscellaneous nonmetalloid in miscellaneous nonmetalloid compound in metallic element (M) compound meets the content of miscellaneous metallic element (M ') or the above-mentioned preferred scope of content of miscellaneous nonmetalloid.In addition, substantially using at least two miscellaneous metallic element (M ') compounds in second invention.Similar to the above, mutual between these the miscellaneous metallic compounds used is also suitable for adjusting to meeting numerical value as above-mentioned preferred scope than (recipe ratio).

The mixed system of above-mentioned raw materials is preferably the form of flowable liquids, such as paste, emulsion, suspended substance or solution.If desired, aforesaid liquid form can be made by further mixing it with following reaction dissolvents.In this mixed system, usual metallic element (M) compound and miscellaneous metallic element (M ') compound or miscellaneous nonmetalloid compound are to be dispersed into the state of particle form, dissolved state or be partly dissolved and remaining state for being dispersed into particle form exists.

In production method (A), reaction dissolvent also can be used.Specifically, above-mentioned raw materials are mixed or when the mixed system of above-mentioned raw materials is under the condition of high temperature, such operation can be carried out after reaction dissolvent is further added.

There is no limit for the quantity of the reaction dissolvent used.But the quantity of above-mentioned metallic element (M) compound used is preferably 0.1-50wt% with the ratio between the total amount of above-mentioned raw materials and reaction dissolvent used, because at this moment can be economically produced the metal oxide particle.

As above-mentioned reaction dissolvent, different from the solvent of water, in other words nonaqueous solvents is preferred.The example of nonaqueous solvents include: hydro carbons, various halogenated hydrocarbons, alcohols (further include such as phenols, polyalcohols and for its derivative hydroxyl compound), ethers and acetals, ketone and aldehydes, esters such as carboxylate and phosphate, amides, derivative compound is so that alkyl and/or acyl group replace hydrogen atom, carboxylic acids and its acid anhydrides in all hydroxyls of polyalcohol and silicone oil and mineral oil.As reaction dissolvent, hydrophilic solvent is particularly preferred.Specifically, reaction dissolvent preferably contains under normal temperature (25 DEG C) not less than 5wt% water and at the solvent of solution state, it is further preferred that containing any amount of water and at homogeneous solution state.The preferred example of alcohol as reaction dissolvent includes in the identical alcohol for enumerating the alcohol as raw material herein before.About reaction dissolvent, can be used alone only above-mentioned a kind of compound, or can be in combination with one another by least the above two classes compound.

In production method (A), the water content of the mixed system about such as above-mentioned raw materials (further include if necessary using reaction dissolvent) the low the more preferred, because the defect of the metal oxide particle generated tails off.Specifically, the metallic atom molar ratio relative to metallic element (M) compound for being used as raw material, preferably above-mentioned mixed system only has the water content less than 4, more preferably less than 1, particularly preferably less than 0.5, more preferably less than 0.1.If above-mentioned water content is too high, then it is possible that being so difficult in the crystal of metal oxide containing miscellaneous metallic element (M ') or miscellaneous nonmetalloid, so that the metal oxide particle that can be enough to play said effect of the present invention cannot be made.Above-mentioned water content can for example be measured with Karl Fisher method.

By the way, above-mentioned water content is often referred to free water content.But the in the case where containing the crystallization water in metallic element (M) compound and/or miscellaneous metallic element (M ') compound or miscellaneous nonmetalloid compound, it further include the water content of this crystallization water.In addition, above-mentioned water content be numerical value related with water contained in such as raw material (summation of water, such as: the free water in pure and mild other reaction dissolvent components used；And the crystallization water in metallic element (M) compound and/or miscellaneous metallic element (M ') compound or miscellaneous nonmetalloid compound).Do not considered by the way that above-mentioned mixed system is in the water generated in reaction caused by the condition of high temperature as by-product.

In production method (A), it is to be raised to the temperature of this mixed system not less than a temperature that the mixed system of above-mentioned raw materials, which is placed in the condition of high temperature, which is higher than normal temperature and can form metal oxide particle at such a temperature.Specifically, although depending on wanting the type (such as type of metallic element (M) and miscellaneous metallic element (M ')) of metal oxide particle obtained, but above-mentioned raised temperature is usually less than 50 DEG C, and in order to be made the metal oxide particle of high crystalline, above-mentioned raised temperature be preferably not less than 80 DEG C, it is 100-300 DEG C more preferable, 100-200 DEG C more preferable, 120-200 DEG C particularly preferred.By the way, the temperature of above-mentioned mixed system is defined as the bottom temp of reactor.

The above-mentioned condition of high temperature of mixed system is preferably kept at a predetermined temperature not less than 30 minutes, more preferably no less than 2 hours, because the crystallinity of metal oxide particle can be improved in this way, so that the metal oxide particle for having fabulous physical property such as ultraviolet light blocking ability be made.

About metal oxide particle obtained, if it is desired, for example in order to remove remaining organic group or the bigger growth for promoting crystal, can heat metal oxide particle at 300-800 DEG C.

When above-mentioned mixed system is placed in the condition of high temperature, specific heating means are usually to use heater, warm air or hot air.But it is not limited in this respect.For example, it is also possible to using other means, such as ultraviolet light irradiation.

When above-mentioned mixed system is placed in the condition of high temperature, it can be operated under any pressure of normal pressure, boosting and decompression, therefore there is no limit.But it is more preferable to such as raw material is placed in the condition of high temperature by heating under increased pressure.In addition, it is also preferred for carrying out using voltage-resistant reactor reaction in the case where the boiling point of such as raw material and/or reaction dissolvent (while using) is lower than the reaction temperature for forming metal oxide particle.About reaction temperature and about the gaseous pressure in reaction process, usually reaction carries out under the critical point not higher than the component as solvent.It is carried out at supercritical conditions but it is also possible to react.

In the case where raw material is placed in the condition of high temperature under boosting, there is no limit for pressure (pressure of gas phase portion) during heating.But this pressure preferably satisfies P > 1kg/cm², more preferable 1.5kg/cm²≤P≤100kg/cm², when being indicated with absolute pressure P, wherein normal pressure (atmospheric pressure) is defined as 1kg/cm².In addition, above-mentioned pressure particularly preferably meets 3kg/cm²≤P≤20kg/cm², because the effect for improving pressure is high and reaction can be carried out with economic equipment.There is no limit for the method for raising pressure.But suitable example includes: the method for heating the material to the temperature higher than alcohol boiling point；And with inert gas such as nitrogen or argon gas by gas phase portion be placed in boosting under method.

In production method (A), as above-mentioned, the above-mentioned condition of high temperature of mixed system is possible while raw material mixes or hereafter.In other words, it for example, obtains the raw material mixing of above-mentioned mixed system and can separate the heating that this mixed system is placed in the condition of high temperature to carry out or (further include part simultaneously) carries out simultaneously, therefore there is no limit.In detail, the limited means (such as heating) of the above-mentioned heating of mixed system can be carried out with any method and in office when limit, regardless of the above-mentioned mixing of raw material.For example, such as heating in advance can be carried out such as at least one of raw material before mixing, to increase the temperature of mixed system while mixing.Or while carrying out this mixing or after this mixing completion, the mixed system being mixed to prepare for example is heated, so that the temperature of mixed system be made to increase.Therefore there is no limit.Therefore, for for example for the heating of heating and above-mentioned mixed time, the preferred example for implementing mode of the invention includes: that (i) mixes metallic element (M) compound, miscellaneous metallic element (M ') compound or miscellaneous nonmetalloid compound and alcohol, then for example the temperature of the mixed system of generation is increased by heating, so that it be made to be placed in the mode under the condition of high temperature；(ii) alcohol is for example carried out mixing after being heated to scheduled temperature with metallic element (M) compound, miscellaneous metallic element (M ') compound or miscellaneous nonmetalloid compound, the temperature of mixed system to generate increases, so that it be made to be placed in the mode under the condition of high temperature；(iii) reaction dissolvent, metallic element (M) compound and miscellaneous metallic element (M ') compound or miscellaneous nonmetalloid compound and alcohol are mixed, then for example by being heated to scheduled temperature, it is mixed again with alcohol, the temperature of mixed system to generate increases, so that it be made to be placed in the mode under the condition of high temperature；And (iv) by various components (metallic element (M) compound, miscellaneous metallic element (M ') compound or miscellaneous nonmetalloid compound and alcohol, if necessary, also use reaction dissolvent) it is for example separated from each other and is for example heated, then it mixes, the temperature of the mixed system of generation is increased, so that it be made to be placed in the mode under the condition of high temperature.By the way, in the case where the 4th kind of metal oxide particle, the unstripped gas (such as ammonia, hydrogen sulfide) of miscellaneous nonmetalloid can provide in any stage, such as: system is placed in the stage of the condition of high temperature；The stage of this condition of high temperature；And form the metal oxide particle later stage.

In implementing aforesaid way (especially mode (ii) to (iv)) of the invention, there is no limit for the method mixed to such as raw material.But in such as raw material, the raw material to be added can once a large amount of (such as in 1min) additions or gradually (such as time with 1min or more) addition.Being gradually added can be to be continuously added to (continuous feed) or interruption addition (pulse mode addition) or combinations thereof, therefore there is no limit.It is added in (pulse mode addition) being interrupted, each subpulse can be to be continuously added to or be once largely added, therefore there is no limit.By the way, smaller the more preferred about the temperature change (caused by addition) of mixed system in above-mentioned mixed method, because it is easier that the metal oxide particle for having uniform primary particle diameter is made.In particular, it is preferred that be control for example addition rate, so as to make mixed system temperature change control within 10 DEG C.

In implementing aforesaid way (especially mode (ii)) of the invention, in the case where metallic element (M) compound, which is added to, mixes them in alcohol, it is preferably 0.0001-2, more preferable 0.0005-1.0 that rate (molal quantity of metallic element (M) compound being added per minute and the ratio between the molal quantity of alcohol that zinc compound is wherein added), which is added,.If above-mentioned addition rate is less than 0.0001, then it is possible that being difficult to that the product that average primary particle diameter is not more than 0.1 μm is made.If above-mentioned addition rate is greater than 2, then it is possible that the above-mentioned temperature control of the condition of high temperature is difficult (especially in the case where reaction scale is big), to be difficult to that the particle for having uniform particle diameter is made.

In production method (A), at least when above-mentioned mixture of raw materials system is placed in the condition of high temperature, this mixed system is preferably stirred, and stirs required power not less than 0.0001kw/m³, more preferably no less than 0.001kw/m³, more preferable 0.01-10kw/m³。

In production method (A), in order to improve generation metal oxide particle dispersibility, preferably by aliphatic carboxylic acid or aliphatic amine or above-mentioned metallic compound (1)-(3) being added during the mixed system containing raw material is placed in the condition of high temperature to form metal oxide particle, or it is added in any stage after metal oxide particle generation.By this addition, metal oxide particle Second Aggregation can be effectively prevented, so as to which the particle for having excellent dispersibility is made.In particular, the addition of above-mentioned metallic compound is particularly preferred, because the crystal grain diameter of metal oxide particle can for example be controlled to the particle diameter to very little.Based on the metallic element (M) in metallic element (M) compound, the amount (total amount of addition) that above-mentioned aliphatic carboxylic acid and aliphatic amine are added is preferably 0.1-10mol%.By the atomic ratio measuring of the metallic element (M) in the metallic element and metallic element (M) compound in these metallic compounds, above-mentioned metallic compound (1)-(3) amount (total amount of addition) of addition are preferably 0.1-10 atom %.

As above-mentioned, metal oxide particle of the invention is combined for the metal oxide particle with more preferable ultraviolet-absorbing and, for example, with following advantages: or ultraviolet radiation absorption is limited to longer wavelength side movement, there are also good long wavelength range ultraviolet light absorption efficiency or have the good transparency, and, for example, even be added to or be coated to do not damaged on substrate yet the transparency or substrate tone.

Metal oxide particle of the invention is for example suitable for electronic material, various films such as fluffy, train and aircraft windows, transparent plastic sheet (such as polycarbonate) the particle for the film of packaging material, for the glass, automotive window, the sun of building structure (such as building, house) object window for being contained in cosmetics, blocking for ultraviolet light, or is suitable for the feed particles that can be made into film for UV absorbing paint.

In detail; in the case that metallic element (M) in metal oxide particle of the invention is Zn, Ti or Ce; UV absorbing properties, good colourless property and the good visible transmission performance that this metal oxide particle can meet simultaneously; meet while wherein such and never obtained from the metal oxide particle of existing above-mentioned metallic element (M) or existing particle, so that the oxide of above-mentioned metallic element (M) contains the miscellaneous metallic element in addition to heretofore described miscellaneous metallic element.So, in these cases, metal oxide particle of the invention, which is for example suitable for blocking, is originated from display equipment (such as LCD (liquid crystal display), PDP (plasma scope), white LEDs, mercury lamp, fluorescent lamp) in by excitaton source and light source and the ultraviolet light from illumination ultraviolet absorption material, such as it is also useful as such as building structure, automobile (such as automobile, electric train) and air transportation machinery (such as aircraft, helicopter) various window materials and display various glass (such as unorganic glass such as single-glass, compound glass and laminated glass and organic glass such as polycarbonate resin) ultraviolet absorption material, and it is also useful as needing various films (such as the plastic film for agricultural use of ultraviolet light blocking ability, various packaging films) ultraviolet absorption material.

In the case that metallic element (M) in metal oxide particle of the invention is Zn, Si or Al, the titanium oxide of ultraviolet absorbing agent of this metal oxide particle than being mainly widely used as cosmetics so far has lower whiteness and higher transparent feeling.So in these cases, metal oxide particle of the invention is suitable for that the ultraviolet absorbing agent of the cosmetics of more preferable transparent feeling can be obtained.In particular, this metal oxide particle is particularly the low particle of refractive index in the case that the metallic element (M) in metal oxide particle of the invention is Si or Al.So in these cases, metal oxide particle of the invention is such a ultraviolet light occluding material with low refractive index in my innocent life, so being also useful as aforementioned display device material and electronic material.

In the case that metallic element (M) in metal oxide particle of the invention is Ti, Zn, Ce, In or Sn, metal oxide particle is a kind of particle of high index.So, in these cases, the film of any refractive index is made possibly through the recipe ratio of control metal oxide particle and resin or silicate as adhesive component, therefore metal oxide particle of the invention is suitable for being combined with the raw material of the ultraviolet absorbing agent film of antireflection property.

In addition, metal oxide particle of the invention can also be used in the other application in addition to ultraviolet light blocks application.Such as, in the case that metallic element (M) in metal oxide particle of the invention is Ti, Zn, Ce, In or Sn, metal oxide particle is a kind of particle of high index, so being further preferably suitable for for example improving the filler of the high index of the refractive index of resin and film (films and membranes).In particular, in the case where metal oxide particle of the invention is a kind of ultra-fine grain, it is possible to transparent and high index the film for being preferably used as antireflection film thus be made.

In addition, this metal oxide particle is also useful as the absorbing material of infrared ray (near infrared ray to far infrared) in the case that the metallic element (M) in metal oxide particle of the invention is Zn, In, Sn or Ti.Especially, wherein particle (the first, second or the third metal oxide particle) of the metallic element (M) for Zn's and containing the trivalent metallic element (such as In, Al, Ga, Bi, Fe, Co, Ni, Mn) as miscellaneous metallic element (M '), and wherein metallic element (M) is that Zn, In, Sn or Ti and containing the fluorine as miscellaneous nonmetalloid particle (the 4th kind of metal oxide particle) is suitable for the absorbing material of infrared ray.

Furthermore, in the case that metallic element (M) in metal oxide particle of the invention is Zn or Al, this metal oxide particle is a kind of particle of thermal conductivity having had, so be suitable for heat filling, and for example it is preferred for being made for requiring the white LEDs of thermorodiative property to apply or when the plate of the high thermal conductivity of circuit substrate application, film.

In addition, this metal oxide particle is a kind of particle of conductivity having had, therefore is suitable for semiconductor or dielectric in the case that the metallic element (M) in metal oxide particle of the invention is Zn, Ti, In or Sn.In particular, this particle is by being made the transparent antistatic film or transparent conductive film that coating is preferably for example used for such as film for this particle in the case where metal oxide particle of the invention is ultra-fine grain.

In addition, metal oxide particle of the invention contains a kind of or at least two miscellaneous metallic elements (M ') or miscellaneous nonmetalloid, so that forming new electron energy level in the band gap of metallic element (M) oxide.So this particle is also useful as photocatalyst material or phosphor material.For example, in recent years, photochemical catalyst is needed to have high day light utilization ratio (referred to as visible light work type photochemical catalyst).In the case that metallic element (M) in metal oxide particle of the invention is Zn or Ti, this metal oxide particle is also useful as the raw material of above-mentioned photochemical catalyst.

In addition, being any one in Zn, Ti, In and Sn at above-mentioned metallic element (M) about metal oxide particle of the invention；And contain in the case where at least one of Fe, Co, Ni and Mn as above-mentioned metallic element (M ')；Or containing selected from least one of Fe, Co, Ni and Mn and have higher chemical valence than metallic element (M) metallic element (such as, if M is Zn, metallic element such as In, Al, B, Ga or Sn are 3 or 4 valences) in the case where；This metal oxide particle is also useful as the particle of (iron) magnetic (transparent) semiconductor property.

Metal oxide particle of the invention can be adjusted to different colors according to the type of contained miscellaneous metallic element (M ') or miscellaneous nonmetalloid and combination, such as be also useful as color pigments.For example, the metal oxide particle is usually colored as following color: being bright-coloured yellow in the case where metallic element (M ') is Bi or Ag；It is yellow in the case where metallic element (M ') is Fe (III)；It is orange in the case where metallic element (M ') is Mn to cream-coloured；It is green in the case where metallic element (M ') is Fe (II) or Ni (II)；It is blue to green in the case where metallic element (M ') is In or Co；It is grey in the case where metallic element (M ') is Cu.It is coexisted by these metallic elements with other metallic elements (M ') or with miscellaneous nonmetalloid, the fine particle mixed colours or acutely mixed colours can be made.

[composition]:

Composition of the invention contains metal oxide particle and medium, and wherein metal oxide particle disperses in the medium, and contains the above-mentioned metal oxide particle of the present invention as basic component.

Metal oxide particle of the invention can be used for above-mentioned various applications in the form of various liquid compositions or solid composite.The example of liquid composition includes: the solvent dispersion that particle is dispersed in dispersion solvent；Particle is dispersed in the coating composition that can be formed in the adhesive of paint film；As laminated glass intermediate coat or resin formed product, particle dispersion in plasticizers as the dispersion of raw material；Particle is dispersed in the dispersion in liquid resin；And particle is dispersed in the polymerisable compound in polymerizable compound such as acrylic monomers.The example of solid composite includes: to use aforesaid liquid composition as film made from raw material, the substrate of film coating and threadiness, membranaceous or sheet resin formed product.Such as; above-mentioned liquid composition is easy to a kind of method in this way and is made, and is in the described method dispersed in the metal oxide particle of the invention of powder type or the reaction liquid produced by above-mentioned metal oxide particle in various decentralized media with well-known method so far.

Description described below in relation to the film-forming composition (in above-mentioned classification, this composition corresponds to solvent dispersion or coating composition) especially suitable for practical application.

About composition (further including composition of the present invention cited below for film forming) of the invention, for the good transparency of this composition or the film as made from it, the form preferably by metal oxide particle with dispersion granule diameter no more than 1 μm is dispersed.Dispersion granule diameter is more preferably no more than 0.2 μm, more preferably no more than 0.1 μm, especially preferably no more than 0.07 μm.

[composition of film forming]:

As above-mentioned, composition of the present invention for film forming is the composition containing following basic component: the present invention above-mentioned metal oxide particle and dispersion solvent and/or adhesive.By the way, about the metal oxide particle of the present invention of the basic component for the present composition, above description is equally applicable to this.

About the dispersion solvent and/or adhesive of the basic component for the present composition, between the amount of these (dispersion solvent and the adhesives) that use it is mutual than (recipe ratio) there is no limit.This ratio can be suitable for type (composition) and quantity according to the metal oxide particle for being used as basic component and be set according to the form of film to be formed.

The example of above-mentioned dispersion solvent includes: water, organic solvent (such as (various halogenations) hydro carbons, alcohols, ethers, acetals, ketone, aldehydes, carboxylic acid esters, amides and carboxylic acids (anhydride)), silicone oil and mineral oils.Wherein, can be used alone only above-mentioned one kind, or can will be at least above two in combination with one another.

The example of above-mentioned adhesive includes: for example various thermoplasticity of organic bond or heat cured (further including such as heat cure, ultraviolet curing, electronic beam curing, moisturecuring and combinations thereof) synthetic resin and natural resin and inorganic bond.The example of synthetic resin includes polyester resin, fluorine resin, alkyd resin, amino resins, vinylite, acrylic resin, epoxy resin, polyamide, polyurethane resin, thermosetting property unsaturated polyester resin, phenol resin, chlorinated polyolefin resin, butyral resin, organic siliconresin, acrylic acid organic siliconresin, fluorine resin, xylene resin, Petropols, ketone resin, Abietyl modified maleic acid resin, liquid polybutadiene and cumarone resin.Wherein, can be used alone a kind of only above-mentioned compound, or can will at least above two compound it is in combination with one another.The example of natural resin includes lac, rosin (rosin), ester gum, hardened rosin, decolorized shellac and bleaching shellac.Wherein, can be used alone a kind of only above-mentioned compound, or can will at least above two compound it is in combination with one another.As synthetic resin, it is also possible to for example using natural rubber or synthetic rubber (such as ethylene-propylene copolymer rubber, polybutadiene rubber, SBR styrene butadiene rubbers, acrylonitrile-butadiene copolymer rubber).The example for the component being used together with synthetic resin includes nitrocellulose, cellulose acetate butyrate, cellulose acetate, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl cellulose.

There is no limit for the form of adhesive component.Its example includes dissolving in type of solvent, water-soluble type, emulsion type and dispersal pattern (any solvent such as water/organic solvent can be used).

The example of water-soluble type adhesive component includes water soluble alkyd resin, water soluble oil-free alkyd resin (water soluble polyester resin), water soluble acryl-modified alkyd resin, water soluble acrylic resin, water soluble epoxy ester resin and water soluble melamine resin.

The example of emulsion type adhesive component includes (methyl) alkyl acrylate copolymer dispersion, vinyl acetate resin emulsion, vinyl acetate copolymer resin emulsion, ethylene vinyl acetate copolymer resin emulsion, acrylate (total) copolymer resin emulsion, cinnamic acrylic ester (total) copolymer resin emulsion, epoxy resin emulsion, polyurethane resin emulsion, acryloyl group-silicone emulsion and fluorine resin emulsion.

The example of inorganic bond includes: the product, (poly-) silazane and phosphate of metal oxide sol (such as silica sol, alumina sol, titanium oxide sol, zirconia sol and cerium oxide sol), alkaline silicate, metal alkoxide (such as alcoxyl SiClx, alkoxide zirconium and alkyl dioxide) and its (hydrolysis -) condensation.Furthermore, as an example, it is possible to which metal oxide metal compound can be formed by pyrolysis by referring to: such as metal carboxylate (such as metal formate, metal acetate and metal oxalate) and its basic salt and organometallic complex (such as beta-diketone complex such as metal acetylacetonates).

Since heat and/or moisture effect, these inorganic bonds generate metal oxide or metal hydroxides after coating.In these inorganic bonds, for the good ultraviolet-absorbing of above-mentioned metal oxide or metal hydroxides, preferably contain Ti, inorganic bond of the Ce or Zn as metallic element, and for the good chemical durability of the film of generation, preferably contain Si, Zr, inorganic bond of the Ti or Al as metallic element, and for the good dispersibility of metal oxide particle, preferably contain metal alkoxide, particularly preferably contain Si, Ti or Al is as the metal alkoxide of metallic element and its inorganic bond of the product of (hydrolysis -) condensation.

Composition of the invention preferably also contains: metal oxide particle, it includes selected from least one of Cu, Ag, Fe and Bi, as metallic element, (this metal oxide particle is added as second of component, it hereafter can be described as " metal oxide particle of addition "), and/or ultrafine metal oxide particles, it includes be used as metallic element selected from least one of Ag, Cu, Au and platinum group (this ultrafine metal oxide particles are added as second of component, hereafter can be described as " ultrafine metal oxide particles of addition ").Therefore, the effect for blocking short wavelength range visible light can larger be improved.

It as the example of the metal oxide particle of metallic element include the particle containing following composition comprising Cu: single oxide or composite oxides, such as cuprous oxide (Cu in the metal oxide particle of addition₂O), copper oxide (CuO), coppe ferrite (CuFe₂O₄), copper molybdate (CuMoO₄), copper tungstate (CuWO₄), copper titanate (CuTiO₃), cupric selenate (CuSeO₄) and copper chromate (CuCr₂O₄)；Solid solution, oxide, so that miscellaneous metallic element part replaces a part of metallic element in single oxide or composite oxides；Or solid solution, oxide, so that other elements (such as nitrogen, element sulphur, halogens) part replaces a part of oxygen in single oxide or composite oxides.By the way, in above-mentioned oxide, also comprising non-stoichiometric compound (such as Cu_1-iO).Especially; the particle that copper oxide particulate or organic group such as acyl group (such as acetyl group) and alkoxy (such as ethyoxyl) are integrated on these particle surfaces is preferred, and the particle that cuprous oxide particle or organic group such as acyl group (such as acetyl group) and alkoxy (such as ethyoxyl) are integrated on these particle surfaces is particularly preferred.

In the metal oxide particle of addition, containing Fe as the example of the metal oxide particle of metallic element includes the particle containing following component: single (hydrogen) oxide or composite oxides, such as ferriferous oxide (such as ferrous oxide (FeO), iron oxide (α-Fe₂O₃、γ-Fe₂O₃), ferroso-ferric oxide (Fe₃O₄)), iron hydroxide (III) (such as α-FeO (OH), γ-FeO (OH)), it is various use formula M (II) Fe₂O₄Ferrous acid salt compound (wherein M is any one or more of metallic element) (such as Manganese Ferrite, zinc ferrite, cobalt ferrite, nickel ferrite based magnetic loaded, barium ferrite, ferrous acid zinc-nickel), iron titanate (FeTiO of expression₃), iron molybdate (FeMoO₄) and iron tungstate (FeWO₄)；Solid solution, oxide, so that miscellaneous metallic element part replaces a part of metallic element in single (hydrogen) oxide or composite oxides；Or solid solution, oxide, so that other elements (such as nitrogen, element sulphur, halogens) partially replace a part of oxygen in single (hydrogen) oxide or composite oxides.By the way, in above-mentioned (hydrogen) oxide, also comprising non-stoichiometric compound (such as Fe_1-iO).In particular, the particle that (hydrogen) ferric oxide particles or organic group such as acyl group (such as acetyl group) and alkoxy (such as ethyoxyl) are integrated on these particle surfaces is preferred, and α-Fe₂O₃It is particularly preferred that particle or organic group such as acyl group (such as acetyl group) and alkoxy (such as ethyoxyl), which are integrated to the particle of these particle surfaces,.

In the metal oxide particle of addition, containing Bi as the example of the metal oxide particle of metallic element includes the particle containing following component: single oxide or composite oxides, such as bismuth trioxide (III) (Bi₂O₃), bismuth titanates (Bi₄Ti₃O₁₂), bismuth molybdate (Bi₂MoO₆), bismuth tungstate (Bi₂WO₆), bismuth stannate (Bi₂Sn₂O₇) and zirconic acid bismuth (2Bi₂O·3ZrO₂)；Solid solution, oxide, so that miscellaneous metallic element part replaces a part of metallic element in single oxide or composite oxides；Or solid solution, oxide, so that other elements (such as nitrogen, element sulphur, halogens) part replaces a part of oxygen in single oxide or composite oxides.By the way, in above-mentioned oxide, also comprising non-stoichiometric compound (such as Bi_2-iO₃).Especially; the particle that oxide particle or organic group such as acyl group (such as acetyl group) and alkoxy (such as ethyoxyl) are integrated to these particle surfaces is preferred, and it is particularly preferred that particle or organic group such as acyl group (such as acetyl group) and alkoxy (such as ethyoxyl) containing bismuth trioxide or bismuth titanates, which are integrated to the particle of these particle surfaces,.

In the metal oxide particle of addition, containing Ag as the example of the metal oxide particle of metallic element includes the particle containing following component: single oxide or composite oxides, such as silver oxide (Ag₂O)；Solid solution, oxide, so that miscellaneous metallic element part replaces a part of metallic element in single oxide or composite oxides；Or solid solution, oxide, so that other elements (such as nitrogen, element sulphur, halogens) part replaces a part of oxygen in single oxide or composite oxides.By the way, in above-mentioned oxide, also comprising non-stoichiometric compound (such as Ag_2-iO).In particular, the particle that oxide particle or organic group such as acyl group (such as acetyl group) and alkoxy (such as ethyoxyl) are integrated on these particle surfaces is preferred, and contain silver oxide (Ag₂O it is particularly preferred that particle or organic group such as acyl group (such as acetyl group) and alkoxy (such as ethyoxyl)), which is integrated to the particle of these particle surfaces,.

By the way, the metal oxide particle of addition can be the metal oxide particle comprising at least two metal oxide particle as metallic element in Cu, Fe, Ag and Bi, or also comprising the metallic element different from Cu, Fe, Ag and Bi.

Although being not particularly limited, for the transparency having had, based on the average particle size particle size of primary particle, the metal oxide particle of addition is preferably dimensioned to be 1-100nm, more preferable 5-30nm, more preferable 5-20nm.

The ultrafine metal oxide particles of addition are comprising being selected from the ultra-fine metallic particles of at least one of Cu, Ag, Au and platinum group as metallic element.In addition, as above-mentioned, part or all for include thing case where in this particle is oxidized to exist as oxide.The ultra-fine metallic particles of this addition preferably comprise the particle of single metal or alloy, and recommending its particle diameter is 1-100nm, preferably 1-20nm.It is preferred that being absorbed strongly no more than under 450nm by plasmon absorption, such example includes the ultra-fine metallic particles for containing Cu and/or Ag as metallic element.

The quantity of the metal oxide particle and dispersion solvent of basic component as composition of the invention and/or adhesive there is no limit.But specifically, the quantity of all metal oxide particles used is preferably 10-90wt%, more preferable 20-80wt% based on all solids constituent content of composition.If the above-mentioned quantity used is less than 10wt%, such as in composition in the case where making ultraviolet blocking film, so this film needs are made so thick, to give full play to ultraviolet light blocking ability, and especially in the case where the inorganic bond in addition to above-mentioned particle or solidified resin are used as other membrane component, it is possible to which the film of generation may be susceptible to be broken.If the above-mentioned quantity used is greater than 90wt%, such as in the case where composition is used to make film, then it is possible that the physical strength of the film generated may be insufficient.But, in the composition that composition of the invention is containing dispersion solvent as basic component, it is coated on substrate, then it is roasted by being heated to high temperature, in the case where film is made, based on the total solids content of the component in composition, the ratio of metal oxide particle can be greater than 90wt%, particularly 100wt% in composition.

Composition of the invention also contains other component, such as can also contain dispersing agent, inorganic bond and solidified resin.

As dispersing agent, such as above-mentioned metallic compound (1)-(3) are preferably, in particular, metallic compound (3) is particularly preferred.By the atomic ratio measuring of the metallic element (M) in the metallic element and metallic element (M) compound in these metallic compounds, the additional amount (total amount of addition) of above-mentioned metallic compound (1)-(3) is preferably 0.1-10 atom %.

There is no limit for the application of the present composition.For example, this composition can be used as producing the coating solution of ultraviolet blocking film or be used as ultraviolet light blocking coating.Specifically, this composition is for example when ultraviolet blocking film is formed in for by (such as LCD (liquid crystal display) in display equipment, PDP (plasma scope) white LEDs, mercury lamp, fluorescent lamp) excitaton source and light source and illumination generate ultraviolet light blocking film or glass on formed when be used as coating solution, and when ultraviolet blocking film is formed in for such as building structure, automobile (such as automobile, electric train) and air transportation machine (such as aircraft, helicopter) various window materials and display various glass (such as unorganic glass such as single-glass, compound glass and laminated glass and organic glass such as polycarbonate resin) on when be used as coating solution, and various films (such as the plastic film for agricultural use of ultraviolet light blocking ability is needed when ultraviolet blocking film is formed in, various packaging films) on when As painting feed liquid, and it is used as coating solution when ultraviolet blocking film forms the intermediate coat as the laminated glass for being used for for example above-mentioned window material.Furthermore, as above described in the part of title " [metal oxide particle] ", the type of the metallic element of the metal oxide particle according to contained in above-mentioned composition, composition of the invention is also useful as: for the coating solution of various functional membranes, such as infrared absorbing film, high index film, low refractive index film, antireflection film, heat conducting film, antistatic film, transparent conductive film, photocatalyst film, fluorescent substance film and magnetic substance film to be made；Or it is used as ink-jet ink.In particular, the present invention, which contains containing Zn as the composition of the metal oxide particle of main metal element (above-mentioned metallic element (M)), can have particularly preferred physical property in above-mentioned various applications, so being preferred.

[film]:

As above-mentioned, film of the invention is a kind of as containing the above-mentioned metal oxide particle of the present invention and/or containing the metal oxide crystal from this metal oxide particle as film obtained from basic component.Specifically, film of the invention includes composition of all compositions (such as intermediate composition) or the present invention by using containing metal oxide particle of the invention for forming a film as film made from raw material components, such as: (1) metal oxide particle of the invention is dispersed in the film in adhesive；(2) only contain the film of above-mentioned particle；(3) as being sintered film made from above-mentioned particle；And the film (the combined film for especially containing above-mentioned film (2) and above-mentioned film (3)) that (4) are combined containing these form membranes.

Above-mentioned film (1) is made by coating or forming the above-mentioned composition containing adhesive.Above-mentioned film (2) is made by coating the composition of above-mentioned solvent dispersion type.Above-mentioned film (3) is sintered the film for the metal oxide crystal to be formed and is made as example, by calcining above-mentioned film (1) or (2) at high temperature to oxidize metal composition granule.Above-mentioned film (4) is the combined films of the metal oxide crystal for example as metal oxide particle and from this particle to be made, wherein for example by calcining above-mentioned film (2) at high temperature, to make a part of metal oxide particle sintering combined films are made.Therefore, usually in above-mentioned film (1) and (2), metal oxide particle of the invention exists in the form of it to be kept substantially.But, in above-mentioned film (3) and in a part of above-mentioned film (4) (it can be the form of above-mentioned film (3)), including structure change (such as variation of the crystal grain diameter of particle), it is thus possible to have generation film be the polycrystalline film or single crystal film different from the crystal form of primary granule the case where.By the way, the metal oxide particle of the invention about the basic component (or base stock component) for film of the invention, above description can be equally used for this.

Inventive film it is preferable that, this film also contains: comprising selected from least one of Cu, Fe, Ag and Bi as the metal oxide particle of metallic element and/or the metal oxide crystal from this particle；And/or include the ultra-fine metallic particles (comprising ultrafine metal oxide particles obtained in such a way, comprising being oxidized in film forming step and/or in subsequent step selected from least one of Ag, Cu, Au and platinum group metal as the metal of metallic element) and/or the crystal of the metal comprising being originated from this particle and/or the crystal of the metal oxide comprising being originated from this particle selected from least one of Ag, Cu, Au and platinum group metal as metallic element.Therefore, block the effect of the visible light of short wavelength range can bigger raising.By the way, comprising selected from least one of Cu, Fe, Ag and Bi, as the metal oxide particle of metallic element and comprising identical as the ultra-fine metallic particles of the metal oxide particle of addition and addition respectively as the metal of metallic element selected from least one of Ag, Cu, Au and platinum group, they are described in the part of its above-mentioned title " [composition of film forming] ".

Although there is no limit, film of the invention is usually a kind of film that can be formed on desired substrate surface, its form can be the form continuously sprawled in the hope area portions of substrate, there is no any gap (such film hereafter can be described as continuous film), or the discontinuous existing form (such film hereafter can be described as discontinuous film) in the hope area portions of substrate, therefore there is no limit.About discontinuous film, partially there is (being disconnected) on substrate surface in the component of film.But there is no limit for size, area, thickness, shape etc..The example of the concrete form of discontinuous film includes: the component of film on substrate surface in the form of existing for choice refreshments；The component of film is on substrate surface in the form of existing for the similar referred to as structure on island；The component of film is on substrate surface in the form of having existing for candy strip；And the combining form containing these forms.

In the case where above-mentioned continuous film and discontinuous film contain only metal oxide particle as component (the namely aggregation of containing metal oxide particle), there is no limit for the structure of these films.Specifically, they may be the porous structure for having desired size gap or whole compact solid structure, they be not macroscopically such porous structure (namely substantially fine and close structures).But the structure the fine and close the more preferred, as it is possible that the ultraviolet light blocking ability having had and the film without scattering caused visible transparent damage is made.By the way, about discontinuous film, as above-mentioned, a part that such membrane structure could provide for single membrane part existing for all parts or be only them is provided.

The mode for completing film of the invention is defined as comprising two ways: being related to the mode of film formed on substrate surface itself and is related to the combined mode of film formed on the substrate He this substrate.

About the above-mentioned substrate for being suitable for the invention film, such as there is no limit for its material.Its preferred example includes: inorganic material, such as ceramic (such as oxide, nitride, carbide) and glass；Organic material, such as polyester resin (such as PET, PBT, PEN), polycarbonate resin, polyphenylene sulfide, polyethersulfone resin, polyetherimide resin, polyimide resin, amorphous polyolefin resin, poly-allylat resin (polyallylate resin), aromatic group amide resin, polyether-ether-ketone resin, the referred to as resin film and plate of heat-resistant resin (such as liquid crystal polymer) film, and in addition to this, well-known so far various resinous polymers (including various resins (such as (methyl) acrylate, polyvinyl chloride resin, PVDC resin, PVA resin, EVOH resin, polyimide resin, polyamide-imide resin, fluorine resin (such as PTFE, PVF, PGF, ETFE), epoxy resin, polyene Hydrocarbon resin)) film and plate, and the product (such as aluminium, aluminium oxide and silica are vapor-deposited film on these different resins polymer) and various metals of processing.

The shape of above-mentioned substrate and the example of form include film, sheet material, plate, fiber and laminate.But they are selected according to using with purposes.Therefore, there is no limit.In addition, above-mentioned substrate is not also limited by function aspect.For example, above-mentioned substrate can be to be optically transparent or opaque, they using with purposes according to for example selecting.

Film of the invention can be used for ultraviolet light in the case where not used limitation and block, and preferably have high transparency.Specifically, its turbidity (haze) is preferably no greater than 10%, more preferably no more than 2%, more preferably no more than 1%.

The optical property of inventive film can be evaluated with such a method, and wherein the transmission performance (visible transmission performance) of the blocking performance (ultraviolet light blocking performance) of the light of ultraviolet ray range (ultraviolet light no more than 380nm and the visible light no more than 450nm) and visible light (450-780nm) is used as index.In terms of ultraviolet light blocks performance and visible transmission performance, the material high to ultraviolet radiation absorption function is preferred.As above-mentioned, in general, the ultraviolet light of film blocks performance and visible transmission performance that can judge by evaluating spectral transmission property in the state that film is formed.How to judge that ultraviolet light blocks the detailed content of performance and visible transmission performance is as above-mentioned.

By the way, in the optical property of inventive film, film optical property below is defined as the numerical value of method measurement and evaluation described in the embodiment detailed description with certain preferred embodiments cited below.In addition, they are defined as the physical property of only membrane part (in addition to substrate), and consider the optical property of the substrate of film coating and only the optical property of substrate is evaluated.In addition, the transmissivity (%) of wavelength 380nm light is an index of UV absorbing properties, it is defined as T in the optical property of inventive film³⁸⁰, and the transmissivity (%) of wavelength 500nm light is an index of visible transmission performance, it is defined as T⁵⁰⁰, and the minimum value of the transmissivity (%) of wavelength 550-700nm light is defined as T¹, T¹And T⁵⁰⁰Between absolute value of the difference (| T¹-T⁵⁰⁰|) it is defined as Δ T.

In particular, the optical property about inventive film, in the case where metal oxide particle of the invention is used as ultraviolet absorption material, T³⁸⁰Preferably no greater than 40%, it is more preferably no more than 20%, more preferably no more than 10%, especially preferably no more than 5%.Equally, Δ T is preferably no greater than 10%, more preferably no more than 5%.Equally, T⁵⁰⁰Preferably not less than 80%, it is more preferably no less than 85%, 90% is more preferably no less than, is particularly preferably not less than 95%.Equally, haze values (subtracting the numerical value that the turbidity of substrate obtains) are an index of visible transparent, it is preferably smaller than 3%, more preferably less than 1%, more preferably less than 0.5%.

In addition, film of the invention can be a kind of film for meeting at least two above range in above-mentioned different optical properties simultaneously, and it can select in this way, to meet the requirement of such as purposes.Such as, it may be mentioned that (by the way, for any film, 1%) turbidity is all not more than film below.

(i) a kind of T³⁸⁰It is not more than 5% and T no more than 40%, Δ T⁵⁰⁰Film not less than 95%.

(ii) a kind of T³⁸⁰It is not more than 10% and T no more than 20%, Δ T⁵⁰⁰Film not less than 90%.

(iii) a kind of T³⁸⁰It is not more than 10% and T no more than 10%, Δ T⁵⁰⁰Film not less than 80%.

There is no limit for the method for formation inventive film.But such as preferably such a method, wherein film is made of the above-mentioned present composition for being used to form film.By the way, about the present composition for this forming method, the description above is equally applicable to this.

The description in relation to forming the method for film by composition of the invention is described below.

To wherein film method made of the present composition, there is no limit.But, the following method can be used: such a method, wherein forming film by applying the composition to substrate surface with the method such as cladding process (such as stick applies (bar coater) method, rolling method, cutter painting method, mouth mold formula coating (diecoater) method and spin-coating method) for forming film well-known so far and spray coating method；And a kind of method for being known as dip coating, film is formed wherein being coated by then a part of substrate or the leaching of whole substrate are taken out substrate from composition in the present compositions.In addition, for example in the case where dispersion solvent is used as the basic component of the present composition, it is also possible to form film by coat then calcining at high temperature.For example, it may be possible to a kind of crystalline film be made, so that at least part metal oxide particle is fused together.

Film of the invention is for example suitable for for as the above-mentioned ultraviolet blocking film for various purposes in title " [metal oxide particle] " and " [composition of film forming] " part, and various functional membranes are also useful as, such as infrared absorbing film, high index film, low refractive index film, antireflection film, heat conducting film, antistatic film, transparent conductive film, photocatalyst film and fluorescent substance film.Furthermore, film of the invention is also useful as the film at least two functions, and ultraviolet blocking film is combined (such as ultraviolet blocking film with high index, there is transparent and electric conductivity ultraviolet blocking film) with any in above-mentioned various functional membranes by it.

[product of containing metal oxide]:

The product of containing metal oxide of the present invention is a kind of product of metal oxide crystal containing metal oxide particle and/or from this particle, wherein the product include aforementioned present invention metal oxide particle with: include the metal oxide particle selected from least one of Cu, Ag, Fe and Bi as metallic element；And/or comprising being selected from the combination of at least one of Cu, Ag, Au and platinum group as the ultra-fine metallic particles of metallic element as main component.Due to such combination, the product of containing metal oxide of the invention is not only good in terms of the effect of ultraviolet blocking-up but also in terms of blocking the effect of visible light of short wavelength range.It by the way, is respectively identical with the metal oxide particle of addition described in above-mentioned title " [composition of film forming] " part and the ultra-fine metallic particles of addition comprising being selected from least one of Cu, Ag, Fe and Bi as the metal oxide particle of metallic element and comprising being selected from least one of Ag, Cu, Au and platinum group as the ultra-fine metallic particles of metallic element.

In the product of containing metal oxide of the invention, there is no limit for the ratio of the metal oxide particle of the ultra-fine metallic particles and aforementioned present invention of the metal oxide particle of above-mentioned addition and/or above-mentioned addition.But based on the metal oxide particle of the present invention of 100 parts by weight, this ratio is preferably 0.1-50 parts by weight, more preferable 1-10 parts by weight.If the ratio of the metal oxide particle of above-mentioned addition and/or the ultra-fine metallic particles of above-mentioned addition is less than above range, there is a situation where that combination generates not sufficiently effective.On the other hand, if this ratio is greater than above range, there are problems that the case where decline of visible transmission property and coloring degree increase occur.

[ultraviolet absorption material]:

Ultraviolet absorption material of the invention contains metal oxide particle of the invention.By the way, about the metal oxide particle of the invention of the basic component as ultraviolet absorption material of the invention, foregoing description may be equally applied to this.

In addition, ultraviolet absorption material of the invention preferably also contains: including the metal oxide particle selected from least one of Cu, Ag, Fe and Bi as metallic element；And/or comprising being selected from the ultra-fine metallic particles of at least one of Ag, Cu, Au and platinum group as metallic element.Therefore, block the effect of the visible light of short wavelength range can bigger raising.It by the way, is respectively identical with the metal oxide particle of addition described in above-mentioned title " [composition of film forming] " part and the ultra-fine metallic particles of addition comprising being selected from least one of Cu, Ag, Fe and Bi as the metal oxide particle of metallic element and comprising being selected from least one of Ag, Cu, Au and platinum group as the ultra-fine metallic particles of metallic element.

About ultraviolet absorption material of the invention, this ultraviolet absorption material also contain above-mentioned addition metal oxide particle and/or above-mentioned addition ultra-fine metallic particles in the case where in, the ratio of the metal oxide particle of the ultra-fine metallic particles and aforementioned present invention of the metal oxide particle of above-mentioned addition and/or above-mentioned addition there is no limit.But based on the metal oxide particle of the present invention of 100 parts by weight, this ratio is preferably 0.1-50 parts by weight, more preferable 1-10 parts by weight.If the metal oxide particle of above-mentioned addition and/or the ratio of the ultra-fine metallic particles of above-mentioned addition are less than above range, there is a situation where that combination generates not sufficiently effective.On the other hand, if this ratio is greater than above range, there are problems that the case where decline of visible transmission property and coloring degree increase occur.

The detailed description of preferred embodiment

Hereafter, the present invention is further illustrated compared with not being comparative example of the invention by the embodiment of following some embodiments.But the present invention is not limited to these Examples.Hereafter for convenience's sake, unit " parts by weight " can refer to be reduced to " part ", and unit " weight % " can be reduced to " wt% ".

By the way, unless otherwise noted, the preparation for the powder sample of each embodiment and comparative example evaluation carries out by the following method.That is, reaction is formed the reaction solution that metal oxide particle obtains to be centrifuged, then the deposit (a kind of deposit to be dispersed back into reaction dissolvent and then by the operation of deposit centrifuge separation) generated is washed with reaction dissolvent to be repeated 3 times, then the deposit of generation is dried in vacuo 12 hours at 60 DEG C with vacuum desiccator, so that the powder sample of metal oxide particle be made.

[the first metal oxide particle]:

Evaluation method in embodiment and comparative example cited below is described as follows.

(1) the crystal identification of metal oxide particle:

About above-mentioned powder sample, the crystallographic system and crystal structure of metal oxide particle are had rated by powder X-ray diffractometry with powder x-ray diffraction equipment (by Rigaku Denki K.K. production, ProductName: RINT 2400).Measuring condition is illustrated below.

X-ray: 1 ray of CuK α (wavelength: 1.54056)/40kV/200mA

Scanning range: 2 θ=20-80 °

Scanning speed: 5 °/min

By the way, in the case where metal oxide particle contains Zn as main metal component, by whether observing that the three strong ray peak of ZnO of characterization hexagonal crystal system judges whether metal oxide particle has crystallographic system identical with ZnO and crystal structure.Specifically, judging the metal oxide particle and ZnO crystallographic system having the same and crystal structure if having diffraction maximum in all positions following three angle of diffraction (a)-(c).

(a) 2 θ=31.65-31.95 °

(b) 2 θ=34.30-34.60 °

(c) 2 θ=36.10-36.40 °

By the way, the diffraction maximum existing for the position above-mentioned (a) is judged as the diffracted ray in (100) face based on ZnO crystal, and the diffraction maximum existing for the position above-mentioned (b) is judged as the diffracted ray in (002) face based on ZnO crystal, and the diffraction maximum existing for the position above-mentioned (c) is judged as the diffracted ray in (101) face based on ZnO crystal.

Similar, in the case where containing the metallic element different from Zn in metal oxide particle as main metal component, whether metal oxide particle has crystallographic system identical with the oxide of above-mentioned metallic element and crystal structure by whether observing that characterizing the three strong ray peak of the oxide crystal of above-mentioned metallic element judges.

(2) particle diameter of metal oxide particle:

(2-1) primary particle diameter:

The crystal grain diameter (Dw) of metal oxide particle is measured and evaluates as primary particle diameter.

Crystal grain diameter (Dw) is evaluated using the following method: about above-mentioned powder sample, the crystal grain diameter (Dw) of metal oxide particle is evaluated with powder x-ray diffraction (Rigaku Denki K.K. production, ProductName: RINT 2400) by powder X-ray diffractometry.Specifically, crystal grain diameter Ds (hkl) (wherein hkl indicates Miller index: Ds (hkl) is the crystallite dimension perpendicular to the direction of Miller index (hkl) lattice plane) is measured with Scherrer equation (analysis) by the width of the diffracted ray in obtained X-ray diffractogram, and using the average value of each Ds numerical value of three strong ray as Dw.That is, unless otherwise noted, crystal grain diameter (Dw) usually calculates using the following method.Measure the x-ray diffractogram of powder of metal oxide particle, about three intensity rays (the third-largest peak (3) of the maximum peak (1) of diffracted ray, the second largest peak (2) of diffracted ray and diffracted ray), crystal grain diameter Ds1, Ds2 and the Ds3 being belonging respectively in the vertical direction of diffracted ray (1)-(3) diffraction surfaces by respective maximum intensity half overall with or integral breadth measured according to Scherrer equation, then regard its average value ((Ds1+Ds2+Ds3)/3) as crystal grain diameter (Dw).

(2-2) discrete particles diameter:

The reaction solution of generation, or it is used as sample by this reaction solution solvent dispersions as made from solvent displacement, its median diameter is measured with dynamic light scattering type particle diameter distribution analyzer (" LB-500 " that is produced by HoribaSeisakusho), and as discrete particles diameter.In the case where being diluted in the preparation of measurement, the solvent used in the reaction is used as retarder thinner.Evaluation criterion is as follows:

●: 0.05 μm of discrete particles diameter <

0.1 μm of ◎: 0.05 μm≤discrete particles diameter <

1 μm of zero: 0.1 μm≤discrete particles diameter <

×: 1 μm≤discrete particles diameter

By the way, about discrete particles diameter fine grain in coating, the median diameter for using dynamic light scattering type particle diameter distribution analyzer (" LB-500 " that is produced by Horiba Seisakusho) to measure is as similar to above-mentioned discrete particles diameter.

(2-3) dispersion and aggregation state:

The reaction solution of generation is diluted with reaction dissolvent, so that the sample of 0.1wt% granule density be made, then uses its dispersity of determination of transmission electron microscopy.Its evaluation criterion is as follows:

A: primary particle is monodispersed, even if they assemble, it is also one-dimensional or bidimensional aggregation.

B: primary particle is three-dimensional aggregate, therefore forms granular (granular) material.

(3) composition of metal oxide particle:

The content for the metallic element that (3-1) is added:

Sample is used as by the reaction solution that the reaction of generation metal oxide particle obtains, this sample is carried out to the quantitative analysis of metallic element with x-ray fluorescence analysis, content to measurement relative to main metallic element (such as Zn) metallic element (such as Cu, Ag) being added, and in the case where metallic compound is used as additive during particles generation, the content of the metallic element (Ms) of above-mentioned metallic compound is measured relative to main metallic element (such as Zn).

The combined amount of (3-2) acyl group:

The above-mentioned powder sample of 1g quantity is added in 0.1N sodium hydrate aqueous solution, is then stirred for 24 hours.Hereafter, with ion chromatography acyl group and quantitative to the quantity of combination.

The chemical valence evaluation for the metallic element that (3-3) is added:

If desired, the chemical valence for the metallic element (such as Cu, Ag) being added in metal oxide particle is evaluated using the following method.That is, about above-mentioned powder sample, with the 2p of the metallic element (such as Cu, Ag) of contained addition in x-ray photoelectron spectroscopy (XPS) the measurement metal oxide particle of light electrospectrograph (Nippon Denshi K.K. production, ProductName: JPS-90 type)_3/2Spectrum, and measured from peak position and combine energy numerical value, to judge the chemical valence for the metallic element (such as Cu, Ag) being added.

By the way, numerical error is measured in order to reduce caused by the energy for example generated due to electrical property is displaced, the measurement of energy numerical value will be combined to correct on the basis of the Cls peak position of surface hydro carbons.

In addition, as shown in " The Handbook of X-rayPhotoelectron Spectroscopy " (1991) delivered by Nippon Denshi K.K., the 2p of the compound of various metallic elements_3/2The peak position of spectrum is as known relatively data.

(4) optical property of metal oxide particle:

(4-1) absorbent properties (1):

It is used as sample by the dilution that fine particle concentration prepared by the reaction solution for using n-butyl alcohol to generate as retarder thinner dilution is 0.1wt%, and about this sample, the transmitted spectrum of ultraviolet light and visible-range is measured with there is the spectrophotometer (" UV-3100 " of ShimadzuCorporation production) of integrating sphere noted down automatically.

Ultraviolet light blocking ability: it is evaluated with the transmissivity under 380nm, 400nm, 420nm.

Visible transmission property: it is evaluated with the transmissivity under 600nm.

By the way, the transmitted spectrum about film forming product, similar to the above, the transmission spectrum in ultraviolet light and visible-range has the automatic record spectrophotometer (" UV-3100 " of ShimadzuCorporation production) of integrating sphere to measure.

(4-2) absorbent properties (2):

The diffusing reflection spectrum of powder sample identical automatic record spectrophotometer with integrating sphere used in above-mentioned (4-1) measures.

The evaluation of (4-3) transparency and tone:

Form and evaluate the film of fine grained dispersion.Specifically, heated solvent displacement is carried out by the reaction solution that the reaction of formation metal oxide particle generates, so that such a dispersion is made, so that metal oxide particle is dispersed in n-butyl alcohol, granule density 20wt%.The dispersion that 100 parts are generated and 20 parts of silicate adhesives are (with SiO₂Meter solid component content is 51wt%) and 0.5 part of catalyst (n-butylamine) mixing, so that a kind of coating be made.By the way, it about above-mentioned granule density, is calculated with such a method, so that the quantity for the solid component that the dispersion of generation is used to vacuum desiccator vacuum drying 1h at 120 DEG C and is generated is as particle weight.

The coating of generation is coated on alkali-free glass (being produced by CorningInternational Corporation, barium borosilicate glass, glass code 7059, thickness: 0.6mm) with stick coating machine, makes 24 μm of wet-film thickness.Hereafter, they are normally dried at 25 DEG C, so that the glass for forming metal oxide particle dispersion membrane on the surface thereof be made.

Then, the glass by the coating of above-mentioned dispersion film is used as sample, and is evaluated with transparency and tone.Transparency is evaluated with the haze values of nephelometer (" the NDH-1001 DP " of the production of Nippon Denshoku Kogyo Co., Ltd.) measurement.About tone, appearance is with the naked eye observed.

It by the way, is 0% as the turbidity value of the alkali-free glass of substrate.

By the way, it is similar above-mentioned about the transparency and tone of film-forming products, with nephelometer (Nippon Denshoku Kogyo Co., Ltd. " the NDH-1001 DP " that produces) turbidity value of measurement evaluates transparency, and observe appearance with the naked eye to evaluate tone.

(5) tone of powder sample:

Observe the appearance of powder sample with the naked eye to evaluate tone.

(6) fine grain concentration:

The fine particle concentration of reaction solution or dispersion is calculated with following steps: being weighed up 0.5g reaction solution or dispersion in fusing crucible, is then dried in vacuo it 1 hour at 120 DEG C, then measure the weight of the dry powder of generation.

(7) refractive index of film-forming products:

With reflectance spectrum film thickness meter (Ohtsuka Electronics Co., Ltd. " FE-3000 " produced) within the scope of 230-760nm measure film (membrane) (having been formed on film (film)) reflection, then the dispersion formula of nkCauchy is used to determine unknown parameter from the actual measured value of the spectrum of absolute reflection with non-linear least square method as the representative approximate formula of the wavelength dispersion of refractive index.

[embodiment A1-1]:

Prepare such a consersion unit, it includes can pressure-resistant glass reactor external heating and that mouth is sent into equipped with blender, addition entrance (being directly connected with addition tank), thermometer, retort gas outlet and nitrogen；The addition tank being connected with above-mentioned addition entrance and the condenser (being directly connected with trap) being connected with the outlet of above-mentioned retort gas.

Mixture containing 183 parts of anhydrous zinc acetate (zinc acetate anhydride) powder, 0.13 part of anhydrous cupric acetate (I) (zine acetate anhydride) powder and 3885 parts of n-butyl alcohols is packed into above-mentioned reactor, then purges its gas phase portion with nitrogen.Hereafter, the temperature of mixture is increased from 20 DEG C under stiring, and heating is kept for 10 hours at 150 DEG C ± 1 DEG C, to be reacted, generate metal oxide particle, then it cools down, so that the reaction solution (1-1) containing bright grey fine grained (metal oxide particle of the invention), concentration 2wt% be made.

Metal oxide particle in reaction solution (1-1) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 2.

[embodiment A1-2 to A1-13 and comparative example A 1-1 to A1-2]:

Reaction solution (1-2) to (1-13), (c1-1) and (c1-2) of the fine grained (metal oxide particle) containing concentration as listed in table 2 (as listed in table 2) are made with the identical method of embodiment A1-1, unlike, as shown in table 1, for example, change loading raw material type and dosage and reaction condition.

Metal oxide particle in each of reaction solution (1-2) to (1-13), (c1-1) and (c1-2) is carried out to above-mentioned various measurements and evaluation.Its result is included in table 2.

By the way, about the particle as made from embodiment A1-2, A1-5, A1-9 and A1-12, it was demonstrated that the Si compound or Ti compound that the metallic compound as surface treatment is added are integrated on the surface of particle.

Table 1

	The parts by weight of raw materials of metal oxide	Compound by weight part of the metallic element of addition	The parts by weight of raw materials of other metals	Surface-treated metal compound by weight part	Weight of solvent part	Reaction condition
						Reaction condition		Temperature (DEG C)	Residence time (h)
						Embodiment A1-1	Anhydrous zinc acetate 183	Temperature (DEG C)	Residence time (h)	Anhydrous cupric acetate (I) 0.13	- 0	- 0	N-butyl alcohol 3885	150	10
Embodiment A1-2	Anhydrous zn formate 155	Anhydrous cupric acetate (II) 3.7	- 0	Tetramethoxy-silicane 1.5	Methanol 1875	Embodiment A1-1	Anhydrous zinc acetate 183	120	5	Anhydrous cupric acetate (I) 0.13	- 0	- 0	N-butyl alcohol 3885	150	10
Embodiment A1-2	Anhydrous zn formate 155	Anhydrous cupric acetate (II) 3.7	- 0	Tetramethoxy-silicane 1.5	Methanol 1875	Embodiment A1-3	Anhydrous zinc propionate 258	120	5	Anhydrous acetic acid silver (I) 1.7	- 0	- 0	1- propyl alcohol 1096	180	5
Embodiment A1-4	Anhydrous zinc acetate 183	Anhydrous cupric acetate (I) 1.9 anhydrous acetic acid silver (I) 0.8	- 0	- 0	1- propyl alcohol 7670	Embodiment A1-3	Anhydrous zinc propionate 258	180	5	Anhydrous acetic acid silver (I) 1.7	- 0	- 0	1- propyl alcohol 1096	180	5
Embodiment A1-4	Anhydrous zinc acetate 183		- 0	- 0	1- propyl alcohol 7670	Embodiment A1-5	Anhydrous zinc acetate 183	180	5	Anhydrous cupric acetate (II) 0.9	Anhydrous acetic acid indium 3	Four butoxy silanes 16	2- propyl alcohol 1847	150	6
Embodiment A1-6	Anhydrous zinc acetate 183	Anhydrous acetic acid silver (I) 0.9	Anhydrous acetic acid tin (IV) 4	- 0	1- propyl alcohol 3880	Embodiment A1-5	Anhydrous zinc acetate 183	160	5	Anhydrous cupric acetate (II) 0.9	Anhydrous acetic acid indium 3	Four butoxy silanes 16	2- propyl alcohol 1847	150	6
Embodiment A1-6	Anhydrous zinc acetate 183	Anhydrous acetic acid silver (I) 0.9	Anhydrous acetic acid tin (IV) 4	- 0	1- propyl alcohol 3880	Embodiment A1-7	Anhydrous zinc acetate 183	160	5	Anhydrous acetic acid silver (I) 0.9	Bismuth acetate oxide 3	- 0	Ethyl alcohol 3880	160	6
Embodiment A1-8	Anhydrous zinc acetate 183	Four acetate hydrate manganese (II) 5	Anhydrous acetic acid indium 3	- 0	N-butyl alcohol 3900	Embodiment A1-7	Anhydrous zinc acetate 183	180	5	Anhydrous acetic acid silver (I) 0.9	Bismuth acetate oxide 3	- 0	Ethyl alcohol 3880	160	6
Embodiment A1-8	Anhydrous zinc acetate 183	Four acetate hydrate manganese (II) 5	Anhydrous acetic acid indium 3	- 0	N-butyl alcohol 3900	Embodiment A1-9	Anhydrous zinc acetate 183	180	5	Four acetate hydrate manganese (II) 10	Anhydrous acetic acid indium 3	Four titanium butoxides (IV) tetramer 19	Methanol 4000	180	5
Embodiment A1-10	Anhydrous zinc acetate 183	Four acetate hydrate manganese (II) 20	Anhydrous acetic acid indium 3	- 0	2- propyl alcohol 4150	Embodiment A1-9	Anhydrous zinc acetate 183	180	5	Four acetate hydrate manganese (II) 10	Anhydrous acetic acid indium 3	Four titanium butoxides (IV) tetramer 19	Methanol 4000	180	5
Embodiment A1-10	Anhydrous zinc acetate 183	Four acetate hydrate manganese (II) 20	Anhydrous acetic acid indium 3	- 0	2- propyl alcohol 4150	Embodiment A1-11	Anhydrous zinc acetate 183	180	5	Four acetate hydrate manganese (II) 20	- 0	- 0	2- propyl alcohol 4150	180	5
Embodiment A1-12	Anhydrous zinc acetate 183	Four acetate hydrate manganese (II) 40	Anhydrous acetic acid indium 3	Tetramethoxy-silicane 1.6	Methanol 4420	Embodiment A1-11	Anhydrous zinc acetate 183	180	5	Four acetate hydrate manganese (II) 20	- 0	- 0	2- propyl alcohol 4150	180	5
Embodiment A1-12	Anhydrous zinc acetate 183	Four acetate hydrate manganese (II) 40	Anhydrous acetic acid indium 3	Tetramethoxy-silicane 1.6	Methanol 4420	Embodiment A1-13	Anhydrous zinc acetate 183	180	5	Four acetate hydrate manganese (II) 40	- 0	- 0	2- propyl alcohol 4420	180	5
Comparative example A 1-1	Anhydrous zinc acetate 183	- 0	- 0	Tetramethoxy-silicane 6	Methanol 1850	Embodiment A1-13	Anhydrous zinc acetate 183	150	5	Four acetate hydrate manganese (II) 40	- 0	- 0	2- propyl alcohol 4420	180	5
Comparative example A 1-1	Anhydrous zinc acetate 183	- 0	- 0	Tetramethoxy-silicane 6	Methanol 1850	Comparative example A 1-2	Anhydrous zinc acetate 183	150	5	- 0	Anhydrous acetic acid indium 3	- 0	2- propyl alcohol 3900	160	5

Table 2

	Granule density (wt%)	X-ray diffractogram	Crystal grain diameter Dw (nm)	Discrete particles diameter	Dispersion and aggregation state	The color of powder	The binding capacity of acyl group		The content of the metallic element (M ') of addition		The content of surface-treated metal (Ms)		Transparency turbidity (%)	Tone	Ultraviolet transmittance (%)		Transmission of visible light (%)
							The binding capacity of acyl group											Identify	Binding capacity mol%/Zn
							M’	Atom %/Zn												Ms	Atom %/Zn	380 nm	420 nm	600nm
							M’	Atom %/Zn	Embodiment A1-1	2	It is equivalent to ZnO	18			○	B	Grey			Ms	Atom %/Zn	380 nm	420 nm	600nm	Acetyl group	4	Cu	0.1	-	0	8	It is colourless	15	72	82
Embodiment A1-2	4	It is equivalent to ZnO	11	●	A	Grey	Formoxyl		Embodiment A1-1	2	It is equivalent to ZnO	18	8	Cu	○	B	Grey	2	Si	1	0.4	It is colourless	13	69	Acetyl group	4	Cu	0.1	-	0	8	It is colourless	15	72	82	90
Embodiment A1-2	4	It is equivalent to ZnO	11	●	A	Grey	Formoxyl		Embodiment A1-3	6	It is equivalent to ZnO	14	8	Cu	○	A	Yellow	2	Si	1	0.4	It is colourless	13	69	Propiono	0.8	Ag	1	-	0	0.8	Yellow	2	1	62	90
Embodiment A1-4	1	It is equivalent to ZnO	6	○	A	Brown	Acetyl group	0.5	Embodiment A1-3	6	It is equivalent to ZnO	14	Cu Ag	0.9 0.5	○	A	Yellow	-	0	0.3	Brown	3	19	36	Propiono	0.8	Ag	1	-	0	0.8	Yellow	2	1	62
Embodiment A1-4	1	It is equivalent to ZnO	6	○	A	Brown	Acetyl group	0.5	Embodiment A1-5	4	It is equivalent to ZnO	14	Cu Ag	0.9 0.5	●	A	Pewter	-	0	0.3	Brown	3	19	36	Acetyl group	3.1	Cu In	0.4 0.9	Si	5	0.2	Yellow	6	59	85
Embodiment A1-6	2	It is equivalent to ZnO	15	○	A	Yellow	Acetyl group	1.8	Embodiment A1-5	4	It is equivalent to ZnO	14	Ag Sn	0.6 1.2	●	A	Pewter	-	0	0.5	Yellow	3	1	77	Acetyl group	3.1	Cu In	0.4 0.9	Si	5	0.2	Yellow	6	59	85
Embodiment A1-6	2	It is equivalent to ZnO	15	○	A	Yellow	Acetyl group	1.8	Embodiment A1-7	2	It is equivalent to ZnO	12	Ag Sn	0.6 1.2	○	A	Yellow	-	0	0.5	Yellow	3	1	77	Acetyl group	2.3	Ag Bi	0.5 1	-	0	0.4	Yellow	5	3	77
Embodiment A1-8	2	It is equivalent to ZnO	14	○	A	It is yellowish	Acetyl group	1.6	Embodiment A1-7	2	It is equivalent to ZnO	12	Mn In	1.8 1	○	A	Yellow	-	0	1.5	It is yellowish	4	41	89	Acetyl group	2.3	Ag Bi	0.5 1	-	0	0.4	Yellow	5	3	77
Embodiment A1-8	2	It is equivalent to ZnO	14	○	A	It is yellowish	Acetyl group	1.6	Embodiment A1-9	2	It is equivalent to ZnO	15	Mn In	1.8 1	◎	A	It is yellowish	-	0	1.5	It is yellowish	4	41	89	Acetyl group	1.5	Mn In	3.2 1	Ti	2	0.3	It is yellowish	4	33	85
Embodiment A1-10	2	It is equivalent to ZnO	15	○	A	It is light yellow	Acetyl group	1.8	Embodiment A1-9	2	It is equivalent to ZnO	15	Mn In	6.4 1	◎	A	It is yellowish	-	0	0.7	It is light yellow	3	19	77	Acetyl group	1.5	Mn In	3.2 1	Ti	2	0.3	It is yellowish	4	33	85
Embodiment A1-10	2	It is equivalent to ZnO	15	○	A	It is light yellow	Acetyl group	1.8	Embodiment A1-11	2	It is equivalent to ZnO	16	Mn In	6.4 1	○	A	Buff	-	0	0.7	It is light yellow	3	19	77	Acetyl group	1.5	Mn	6.3	-	0	1.2	Buff	10	34	70
Embodiment A1-12	2	It is equivalent to ZnO	13	●	A	It is light yellow	Acetyl group	3	Embodiment A1-11	2	It is equivalent to ZnO	16	Mn In	13 1	○	A	Buff	Si	1	0.2	It is light yellow	3	17	75	Acetyl group	1.5	Mn	6.3	-	0	1.2	Buff	10	34	70
Embodiment A1-12	2	It is equivalent to ZnO	13	●	A	It is light yellow	Acetyl group	3	Embodiment A1-13	2	It is equivalent to ZnO	15	Mn In	13 1	○	B	Buff	Si	1	0.2	It is light yellow	3	17	75	Acetyl group	1.5	Mn	13	-	0	3	Buff	8	26	64
Comparative example A 1-1	4	It is equivalent to ZnO	12	◎	A	White	Acetyl group	3	Embodiment A1-13	2	It is equivalent to ZnO	15	-	0	○	B	Buff	Si	4	0.6	It is colourless	36	70	91	Acetyl group	1.5	Mn	13	-	0	3	Buff	8	26	64
Comparative example A 1-1	4	It is equivalent to ZnO	12	◎	A	White	Acetyl group	3	Comparative example A 1-2	2	It is equivalent to ZnO	15	-	0	○	A	Blue	Si	4	0.6	It is colourless	36	70	91	Acetyl group	3	In	1	-	0	1.2	It is colourless	20	70	87

Fig. 1, which is shown, measures the transmitted spectrum that dilution obtains according to above-mentioned evaluation method (4-1), and the reaction solution (1-2), (1-3), (1-5), (1-10) and (c1-1) that wherein dilution is respectively obtained with embodiment A1-2, A1-3, A1-5, A1-10 and comparative example A 1-1 is diluted to the method that granule density is 0.1wt% and is made.

Result from embodiment A1-8 to A1-13 can be appreciated that in the present invention, if the Mn amount being added increases, ultraviolet light blocking ability is improved, so that the hyaline membrane for having fabulous ultraviolet light blocking ability is made.Itself the reason is as follows that: crystal grain diameter is not more than 20nm, so even if particle Second Aggregation in the stage of reaction solution, aggregation force be also it is so weak so that the particle of aggregation is easily dispersed due to the addition of adhesive.On the other hand, if the quantity of Mn increases, ultraviolet light blocking ability is improved, and the compromised transmissivity of visible light.In particular, jaundice becomes serious, and transmission of visible light is low if the quantity of Mn is more than 10% (embodiment A1-13).If it is considered that this point, it so will now be appreciated that in the present invention, in order to reach higher ultraviolet light blocking ability, higher transmission of visible light and low coloring degree, in the case where Mn, its content is preferably Mn/Zn=3-10 atom %, as in embodiment A1-9 and A1-10.But, as in embodiment A1-12, it is also clear that, if Si compound or Ti compound (as surface-treated metal compound) are integrated on the surface of particle, even in the case where the quantity of Mn is more than 10%, it is also possible to not only make ultraviolet light blocking ability but also improve transmission of visible light.

[embodiment A1-14]:

Use consersion unit identical with embodiment A1-1, in stirring and at room temperature, mixture containing 3000 parts of pure water, 50 part of one cerium acetate hydrate (III) and 0.6 part of anhydrous cupric acetate (II) is packed into reactor, 50 part of 30% aqueous hydrogen peroxide solution is then added.Then, the temperature of mixture is increased from room temperature under stiring, then heating is kept for 5 hours at 90 DEG C ± 2 DEG C, and 30% aqueous hydrogen peroxide solution is then added.Hereafter, temperature is reheated to 1 hour for keeping other at above-mentioned identical temperature, to be reacted, to generate metal oxide particle, then it cools down, to which the reaction solution (1-14) for the fine grained (metal oxide particle of the invention) felt containing micro- yellow and high transparency, fine particle concentration 0.8wt% be made.

Then, the reaction solution of generation (1-14) is filtered with ultrafiltration membrane, to remove foreign ion and remaining hydrogen peroxide, and is concentrated through, so that the aqueous dispersions (1-14) that fine particle concentration is 7wt% be made.

Metal oxide particle in aqueous dispersions (1-14) is subjected to powder x-ray diffraction.To obtain, diffraction maximum is wide, but shows to be equivalent to CeO₂Diffraction pattern.In addition, measurement primary particle diameter is schemed by TEM, because diffraction maximum is wide about crystal grain diameter.Ultraviolet radiation absorption property and visible transmission property are had rated with above-mentioned evaluation method (4-1).By the way, in the measurements, ion exchange water is used as dilution solvent.The above results are included in table 3.

[comparative example A 1-3]:

The aqueous dispersion (c1-3) that fine particle concentration is 7% is made with the same procedure of embodiment A1-14, the difference is that anhydrous cupric acetate (II) is not used.

The metal oxide particle in aqueous dispersion (c1-3) is had rated with the same procedure of embodiment A1-14.Its result is included in table 3.

Table 3

	The content of the metallic element (M ') of addition		X-ray diffractogram	Primary particle diameter (nm)	Ultraviolet transmittance (%)		Transmission of visible light (%)
	The content of the metallic element (M ') of addition				Ultraviolet transmittance (%)		Transmission of visible light (%)	M’	Atom %/Ce	380nm	400nm	600nm
	Embodiment A1-14	Cu			2	It is equivalent to CeO₂	2-4	M’	Atom %/Ce	380nm	400nm	600nm	4	70	99
Comparative example A 1-3	Embodiment A1-14	Cu	-	-	2	It is equivalent to CeO₂	2-4	It is equivalent to CeO₂	2-4	29	75	99	4	70	99

[embodiment A1-15]:

Use consersion unit identical with embodiment A1-1, it will be packed into reactor containing the mixture of 2400 parts of glycol dimethyl ethers (as reaction dissolvent), 303 parts of titanium methoxy propyl oxides, 2.8 parts of silver acetates (I) and 270 parts of acetic acid, and then use the gas phase portion of nitrogen purge.Then, the temperature of mixture is increased from 20 DEG C under stiring, then heating is kept for 5 hours at 180 DEG C ± 1 DEG C, to be reacted, generate metal oxide particle, then it cools down, so that the reaction solution (1-15) containing fine grained (metal oxide particle of the invention), fine particle concentration 2wt% be made.

Metal oxide particle in reaction solution (1-15) is subjected to powder x-ray diffraction.To obtain, show the diffraction pattern for being equivalent to anatase-type titanium oxide, crystal grain diameter 6nm.In addition, having rated ultraviolet radiation absorption property and visible transmission property with above-mentioned evaluation method (4-1).The above results are included in table 4.

[embodiment A1-16]:

The reaction solution (1-16) for the fine grained (metal oxide particle of the invention) for being 2wt% containing fine particle concentration is made with the identical method of embodiment A1-15, the difference is that replacing silver acetate (I) with 6.5 parts of manganese acetates (II).

Powder x-ray diffraction will be carried out in the metal oxide particle in reaction solution (1-16).To obtain, show the diffraction pattern for being equivalent to anatase-type titanium oxide, crystal grain diameter 6nm.In addition, having rated ultraviolet radiation absorption property and visible transmission property with above-mentioned evaluation method (4-1).The above results are included in table 4.

[comparative example A 1-4]:

The fine grain reaction solution (c1-4) for being 2wt% containing fine particle concentration is made with the identical method of embodiment A1-15, the difference is that silver acetate (I) is not used.

The identical method of metal oxide particle embodiment A1-15 in reaction solution (c1-4) is evaluated.Its result is included in table 4.

Table 4

	The content of the metallic element (M ') of addition		X-ray diffractogram	Crystal grain diameter Dw (nm)	Ultraviolet transmittance (%)		Transmission of visible light (%)
	The content of the metallic element (M ') of addition				Ultraviolet transmittance (%)		Transmission of visible light (%)	M’	Atom %/Ti	380nm	400nm	600nm
	Embodiment A1-15	Ag			2	It is equivalent to TiO₂	6	M’	Atom %/Ti	380nm	400nm	600nm	3	4	60
Embodiment A1-16	Embodiment A1-15	Ag	Mn	5	2	It is equivalent to TiO₂	6	It is equivalent to TiO₂	6	30	20	75	3	4	60
Embodiment A1-16	Comparative example A 1-4	-	Mn	5	-	It is equivalent to TiO ₂	8	It is equivalent to TiO₂	6	30	20	75	40	60	78

[embodiment A1-17]:

Firstly, acetic acid zinc powder of the synthesis containing Bi.Specifically, the mixture of 250 part of 80% acetic acid aqueous solution, 36.7 parts of zinc acetates and 2.84 parts of bismuth acetate (III) oxides (bismuth (III) acetate oxide) is packed into glass reactor, the reactor external can heat and equipped with blender, addition entrance and thermometer.Hereafter, it increases its temperature mixture heating under stiring, is then stirred 5 hours at 100 DEG C, so that the solution of homogeneous transparent be made.Hereafter, internal temperature is risen to 120 DEG C, then cooled down, so that white slurry be made.Solvent composition is removed from the slurry of generation with evaporator under reduced pressure under 50 DEG C of bath temperature.In addition, the white powder of generation is used vacuum desiccator heat drying 10 hours at 40 DEG C, so that powder (1) be made.The powder (1) of generation is subjected to elemental analysis with x-ray fluorescence analysis and carries out crystal analysis with powder X-ray RD.To be found to be the zinc acetate containing Bi, Bi relative to ratio Zn be 5 atom %.

Secondly, the mixture containing 18 parts of powder (1) obtained above and 180 parts of methanol is packed into reactor, then uses the gas phase portion of nitrogen purge using consersion unit identical with embodiment A1-1.Then, the temperature of mixture is increased to 150 DEG C from 20 DEG C under stiring, is then kept for 5 hours at 150 DEG C ± 1 DEG C, is then cooled down, contain the fine grain reaction solution of yellow (1-17) to be made.It was found that reaction solution (1-17) is such a material, wherein fine grained (average grain diameter: 10nm) contains ZnO crystal, the Bi (III) for being 5 atom % containing the ratio relative to Zn being present in solid solution in ZnO crystal, and fine grained is dispersed with the concentration of 4wt%.

The fine grain diffusing reflection spectrum evaluation result from reaction solution (1-17) finds that it includes and has the absorption based on the absorption maximum value containing Bi at 422nm；And the band edge based on ZnO crystal absorbs and (has longer wavelength side to absorb the absorption of limit at 400nm).It is found furthermore that: when compared with the diffusing reflection spectrum of the ZnO without Bi, above-mentioned fine grained has absorption (although absorbability is weak) from nearly 650nm to longer wavelength side (infrared wavelength range) and its ultraviolet radiation absorption notch long (in shorter wavelength side) is blue shift (absorbing limit in shorter wavelength side).Therefore, trivalent Bi ion is supported to be present in solid solution indirectly.

The fine grain diffusing reflection spectrum measurement result that embodiment A1-17 and comparative example A 1-1 is obtained is shown in Fig. 5 together.

The reaction solution (1-17) of generation is subjected to heated solvent displacement, so that dispersion (1-17) is made, so that above-mentioned fine grained is contained in and is dispersed in 2- propyl alcohol, concentration 20wt%.

[embodiment A1-18]:

Using consersion unit identical with embodiment A1-1, by 10 parts of ultra-fine CeO₂Particle (average grain diameter: 8nm) is dispersed in the dispersion in 190 parts of n-butanols and is packed into reactor, then stirs this dispersion.On the other hand, 44 parts of solution are prepared by the way that bismuth acetate (III) oxide is dissolved in the in the mixed solvent of propionic acid and n-butanol, so that concentration is 20wt%, the solution of this preparation is then packed into addition tank.Under stiring, the temperature of the dispersion liquid of above-mentioned ultra-fine CeO particle is increased, and is kept at 200 DEG C.Bismuth acetate (III) oxide solution is added to it from addition tank.After this addition terminates, the mixture of generation is kept for 5 hours at 200 DEG C, is then cooled down, contains the fine grain reaction solution of yellow (1-18) to be made.

It was found that reaction solution (1-18) are as follows: be coated with the Bi oxide (Bi of about 1nm thickness containing surface₂O₃) layer ultra-fine CeO₂The fine grained (average grain diameter: 10nm) of particle is dispersed in and is contained in solvent (its primary solvent: n-butanol), concentration 7wt%.It moreover has been found that above-mentioned fine grain average metal group becomes Bi/Ce=0.53/1 (atomic ratio).

The reaction solution (1-18) of generation is subjected to heated solvent displacement, so that such a dispersion (1-18) is made, so that above-mentioned fine grained is contained in and is dispersed in acetic acid butyl ester, concentration 20wt%.

[embodiment A1-19]:

It is made with the identical method of embodiment A1-18 and contains the fine grain reaction solution of yellow (1-19), the difference is that superfine Ti O₂Particle (average grain diameter: 12nm) replaces ultra-fine CeO₂Particle, and whole n-butanols are replaced with ethyl alcohol.

It was found that reaction solution (1-19) are as follows: be coated with the Bi oxide (Bi of about 1nm thickness containing surface₂O₃) fine grained (average grain diameter: 14nm) of superfine Ti O particle of layer is dispersed in and is contained in solvent (its primary solvent: ethyl alcohol), concentration 7wt%.It moreover has been found that above-mentioned fine grain average metal group becomes Bi/Ti=0.25/1 (atomic ratio).

The reaction solution (1-19) of generation is subjected to heated solvent displacement, so that such a dispersion (1-19) is made, so that above-mentioned fine grained is contained in and is dispersed in water, concentration 20wt%.

[embodiment A1-20]:

Mixture containing 18 parts of anhydrous acetic acid zinc powders, 0.9 part of anhydrous acetic acid indium powder and 160 parts of butoxy ethanols is packed into reactor identical with embodiment A1-17, then uses the gas phase portion of nitrogen purge.Then, the temperature of mixture is increased under stiring, 3 hours (at this point, forming ultra-fine ZnO particle, wherein In is present in solid solution) is then kept at 200 DEG C DEG C.Hereafter, suspended substance is added from addition tank (18 parts of powder as made from embodiment A1-17 (1) are dispersed in 18 parts of butoxy ethanols).After addition terminates, the mixture of generation is kept for 3 hours at 200 DEG C, is then cooled down, contains fine grain reaction solution (1-20) to be made.

It was found that this reaction solution (1-20) is such a material, wherein contain and be dispersed with the fine grained (average grain diameter: 18nm) containing ZnO crystal, its concentration is 7.4wt%, is contained in the ZnO crystal to be respectively the Bi (III) and In (III) of 2.5 atom % and 1.5 atom % relative to Zn existing for solid solution (wherein Bi (III) is in fine grain surface ZnO layer locally with solid solution presence).

The evaluation of fine grain diffusing reflection spectrum as a result, discovery has the absorption based on the absorption maximum value containing Bi at 422nm from reaction solution (1-20)；And absorbing with limit and (thering is longer wavelength side to absorb the absorption of limit at 400nm) based on ZnO crystal；In addition, the strong absorption near infra red region is considered as caused by plasma absorption mainly due to the solid solution of In.

The reaction solution (1-20) of generation is subjected to heating concentration with evaporator under reduced pressure, so that dispersion (1-20) be made, above-mentioned fine grain concentration is 20wt%.

[embodiment A1-21]:

Firstly, acetic acid zinc powder of the synthesis containing Bi and In.Specifically, powder (2) are made with the identical method of zinc acetate containing Bi is synthesized in embodiment A1-17, the difference is that the quantity of bismuth acetate (III) oxide used becomes 1.7 parts, and 1.8 parts of anhydrous acetic acid indiums are also used.The powder (2) of generation is subjected to elemental analysis with x-ray fluorescence analysis and carries out crystal analysis with powder X-ray RD.To be found to be the zinc acetate containing Bi and In, the content relative to Zn is all 3 atom %.

Secondly, the mixture containing 18 parts of powder (2) obtained above and 160 parts of butoxy ethanols is packed into reactor identical with embodiment A1-17, the gas phase portion of nitrogen purge is then used.Then, the temperature of mixture is increased under stiring, 3h is then kept at 200 DEG C, is then cooled down, contain fine grain reaction solution (1-21) to be made.

It was found that this reaction solution (1-21) is such a material, wherein contain and be dispersed with the fine grained (average grain diameter: 8nm) containing ZnO crystal, its concentration is 4.5wt%, is contained in ZnO crystal with Bi existing for solid solution (III) and In (III) (wherein relative to Zn, its content is 3 atom %).

The reaction solution (1-21) of generation is subjected to heating concentration with evaporator under reduced pressure, so that dispersion (1-21) is made, so that above-mentioned fine grain concentration is 20wt%.

[embodiment A1-22]:

Reaction solution (1-22) is made with the same procedure of embodiment A1-1, the difference is that 0.1 part of acetic acid dihydrate lithium is used as another raw material.

The reaction solution (1-22) generated with the same procedure evaluation of embodiment A1-1.As a result, the fine grained that the crystal grain diameter that metal oxide particle in reaction solution (1-22) is is 18nm, the metal oxide particle contains the ZnO crystal containing Cu and Li, relative to Zn, the ratio of Cu and Li is respectively 0.1 atom % and 0.08 atom %, and the ultraviolet transmittance at 380nm is 10%, and the transmissivity of visible light is 82%.

[embodiment A1-23]:

Reaction solution (1-23) is made with the same procedure of embodiment A1-11, the difference is that 0.3 part of cerium hydroxide is used as another raw material.

The reaction solution (1-23) generated with the same procedure evaluation of embodiment A1-11.As a result, the fine grained that the crystal grain diameter that metal oxide particle in reaction solution (1-23) is is 16nm, the metal oxide particle contains the ZnO crystal containing Mn and Cs, relative to Zn, the ratio of Mn and Ce is respectively 6.3 atom % and 0.2 atom %, and the ultraviolet transmittance at 380nm is 7%, and the transmissivity of visible light is 70%.

[embodiment A1-24]:

Reaction solution (1-24) is made with the same procedure of embodiment A1-7, the difference is that 2 part of one acetate hydrate calcium is used as another raw material.

The reaction solution (1-24) generated with the same procedure evaluation of embodiment A1-7.As a result, the fine grained that the crystal grain diameter that metal oxide particle in reaction solution (1-24) is is 12nm, the metal oxide particle contains the ZnO crystal containing Ag, Bi and Ca, relative to Zn, the ratio of Ag, Bi and Ca are respectively 0.5 atom %, 1 atom % and 1.1 atom %, and the ultraviolet transmittance at 380nm is 3%, and the transmissivity of visible light is 78%.

[embodiment A1-25]:

Reaction solution (1-25) is made with the same procedure of embodiment A1-15, the difference is that 0.3 part of four acetate hydrate magnesium is used as another raw material.

The reaction solution (1-25) generated with the same procedure evaluation of embodiment A1-15.As a result, the fine grained that the crystal grain diameter that the metal oxide particle in reaction solution (1-25) is is 6nm, the metal oxide particle contains the Detitanium-ore-type TiO containing Ag and Mg₂Crystal, the ratio relative to Ti, Ag and Mg are respectively 2 atom % and 0.1 atom %, and the ultraviolet transmittance at 380nm is 1%, and the transmissivity of visible light is 62%.

[embodiment A2-1]:

It is heated with 1000 parts of reaction solutions (1-1) that evaporator obtains embodiment A1-1, to be concentrated to 100 parts.Hereafter, when methyl proxitol acetate is added as substitution solvent, while solvent composition is steamed, contains dispersion of the propylene glycol methyl ether acetate as solvent composition to be made.Then, this dispersion is heated and is concentrated, then cools down, adds 0.2 part of four titanium butoxide (IV) tetramer (Wako Pure Chemical Industries, Ltd. produce) as dispersing agent, so that dispersion (2-1) be made.The granule density and discrete particles diameter of the dispersion of generation are included in table 5.

[embodiment A2-2 to A2-10]:

Dispersion (2-2) to (2-10) is made with the identical method of embodiment A2-1, the difference is that using reaction solution listed by table 5 and using substitution solvent and dispersing agent listed by table 5.The granule density and discrete particles diameter of the dispersion of generation are included in table 5.

Table 5

	Reaction solution	Substitute solvent	Dispersing agent		Granule density (wt%)	Discrete particles diameter (μm)
			Dispersing agent				Type	Additional amount (wt%/particle)
			Embodiment A2-1	(1-1)			Type	Additional amount (wt%/particle)	Methyl proxitol acetate	Four titanium butoxides (IV) tetramer	1	20	0.08
Embodiment A2-2	(1-2)	1- propyl alcohol	Embodiment A2-1	(1-1)	-	0	20	0.03	Methyl proxitol acetate	Four titanium butoxides (IV) tetramer	1	20	0.08
Embodiment A2-2	(1-2)	1- propyl alcohol	Embodiment A2-3	(1-3)	-	0	20	0.03	Methyl iso-butyl ketone (MIBK)	Four titanium butoxides (IV) tetramer	10	20	0.04
Embodiment A2-4	(1-4)	Dimethylbenzene	Embodiment A2-3	(1-3)	-	0	30	0.09	Methyl iso-butyl ketone (MIBK)	Four titanium butoxides (IV) tetramer	10	20	0.04
Embodiment A2-4	(1-4)	Dimethylbenzene	Embodiment A2-5	(1-5)	-	0	30	0.09	N-butyl alcohol	-	0	25	0.04
Embodiment A2-6	(1-6)	Water	Embodiment A2-5	(1-5)	-	0	16	0.05	N-butyl alcohol	-	0	25	0.04
Embodiment A2-6	(1-6)	Water	Embodiment A2-7	(1-7)	-	0	16	0.05	Methyl ethyl ketone	-	0	22	0.21
Embodiment A2-8	(1-9)	N-butyl alcohol	Embodiment A2-7	(1-7)	-	0	20	0.05	Methyl ethyl ketone	-	0	22	0.21
Embodiment A2-8	(1-9)	N-butyl alcohol	Embodiment A2-9	(1-10)	-	0	20	0.05	Propylene glycol monomethyl ether	Partial hydrolysis-condensation product (trimer to pentamer) of tetramethoxy-silicane	5	30	0.03
Embodiment A2-10	(1-12)	N-butyl alcohol	Embodiment A2-9	(1-10)	-	0	30	0.03	Propylene glycol monomethyl ether		5	30	0.03

[embodiment A3-1]:

36 parts of silicate adhesives (" the MKC Silicate MS56 " of Mitsubishi Chemical Corporation production) and 1 part of n-butylamine (as catalyst) are added in 100 parts of dispersions (2-1) (as made from embodiment A2-1), then they are bound together, so that a kind of coating (3-1) be made.Fine grain discrete particles diameter in this coating is 0.04 μm.

Secondly, alkali glass is used as substrate, repeats the operation that coating (3-1) is repeatedly coated to above-mentioned substrate with stick coating machine, then at normal temperature dry them, then heated 60 minutes at 200 DEG C.To which the substrate (3-1-B) that the fine grained dispersion membrane of substrate (3-1-A) and a kind of fine grained dispersion membrane for being 4 μm with thickness of dry film that a kind of fine grained dispersion membrane of fine grained dispersion membrane for being 2 μm with thickness of dry film coats coats be made.

The substrate (3-1-A) of fine grained dispersion membrane coating and the transmitted spectrum of (3-1-B) of generation are shown in Fig. 2 together with the alkali glass of primary substrate.

In addition, having rated the substrate (3-1-A) of the fine grained dispersion membrane coating of generation and the transparency and tone of (3-1-B).Accordingly, with respect to the two, transparency is turbidity 0.3%, and tone is colourless.

[embodiment A3-2]:

36 parts of silicate adhesives (" the MKC Silicate MS56 " of Mitsubishi Chemical Corporation production) and 1 part of n-butylamine (as catalyst) are added in 100 parts of dispersions (2-3) (as made from embodiment A2-3), then they are bound together, so that a kind of coating (3-2) be made.Fine grain discrete particles diameter in this coating is 0.05 μm.

Secondly, alkali glass is used as substrate, repeats the operation that coating (3-2) is repeatedly coated to above-mentioned substrate with stick coating machine, then they are dried at normal temperature, then heats 60min at 200 DEG C.To which the substrate (3-2) that a kind of fine grained dispersion membrane of fine grained dispersion membrane for being 3 μm with thickness of dry film coats be made.

The transmitted spectrum of the substrate (3-2) of the fine grained dispersion membrane coating of generation is shown in Fig. 3 together with the alkali glass of primary substrate.

In addition, having rated the transparency and tone of the substrate (3-2) of the fine grained dispersion membrane coating of generation.As a result, transparency is turbidity 0.5%, and tone is yellow.

[embodiment A3-3]:

The mixed solvent (as retarder thinner) of 60 parts of acrylic resin solns (concentration of solid component: 50wt%) and 20 parts of toluene/methyl ethyl ketone=1/1 (weight ratio) is added in 100 parts of dispersions (2-9) (as made from embodiment A2-9), then they are bound together, so that a kind of coating (3-3) be made.Fine grain discrete particles diameter in this coating is 0.06 μm.

Secondly, polymer PET is used as substrate, coating (3-3) is coated on above-mentioned substrate with stick coating machine, to make 24 μm of wet-film thickness.Hereafter they are heated into 10min at 100 DEG C, so that a kind of substrate (3-3) of fine grained dispersion membrane coating for having fine grained dispersion membrane be made.

The transmitted spectrum of the substrate (3-3) of the fine grained dispersion membrane coating of generation is shown in Fig. 4.

In addition, having rated the transparency and tone of the substrate (3-3) of the fine grained dispersion membrane coating of generation.As a result, transparency is turbidity 0.5%, and tone is yellowish.

[embodiment A3-4]:

By 20 parts of ultraviolet-curable coating agents (" HIC2000 " of KYOEISHA CHEMICAL Co., LTD. production；Solid component content: 50wt%；Refractive index: 1.58) being added in 100 parts of dispersions (2-2) (as made from embodiment A2-2), be then bound together them, so that a kind of coating (3-4) be made.

Secondly, the polyethylene terephthalate film of highly transparent is used as substrate, coating (3-4) is coated on this substrate with stick coating machine.Hereafter they are heated into 10min at 100 DEG C, irradiates 10min with the ultraviolet light of high-pressure sodium lamp, so that a kind of substrate (3-4) of fine grained dispersion membrane coating for having fine grained dispersion membrane for being 5 μm with thickness of dry film be made.

Similar with embodiment A3-1, the substrate (3-4) of the fine grained dispersion membrane coating of generation is a kind of ultraviolet blocking-up and the material with high visible transmission property.

In addition, having rated the transparency and tone of the substrate (3-4) of the fine grained dispersion membrane coating of generation.To obtain, transparency is turbidity 0.5%, and tone is colourless, and the refractive index of film is 1.7.

[embodiment A3-5]:

By 100 parts of dispersions (1-17) (being made by embodiment A1-17), 40 parts of silicate adhesive (hydrolysis-condensation products of tetramethoxy-silicane；Concentration=50wt% using in terms of silica) and 1 part of n-butylamine (as catalyst) mix, so that a kind of composition (3-5) for film forming be made.

Use stick coating machine that composition (3-5) is coated on glass plate (as substrate), then moisturecuring at normal temperature, it is heated with the heating rate of 2 DEG C/min from room temperature in heating furnace and is kept for 2 hours at 300 DEG C again, to form the film that film thickness is 4 μm on the surface of glass plate.

The film of formation is such a film, the ultra-fine ZnO particle dispersed and be present in solid solution containing wherein Bi in amorphous oxide silicon fiml.

Have rated the spectral property for forming the glass plate (glass plate of film coating) of film on the surface thereof.It is obtained from result, it was found that this glass plate absorbs the ultraviolet light in wide scope, specifically, it blocks the ultraviolet light for being not more than 370nm by the absorption (first absorbs) based on ZnO band gap, and has on longer wavelength side (thering is it to absorb limit at 416nm) and absorb (based on containing Bi) (second absorbs).The transmissivity for the light that wavelength is 600nm is 84%, and the transmissivity for the light that wavelength is 500nm is 77%, and the transmissivity for the light that the transmissivity for the light that wavelength is 410nm is 37% and wavelength is 370nm is 1.5%.

The visible transparency of the glass plate of film coating is "○", and colours and be also at imperceptible degree.

[embodiment A3-6]:

24 parts of dispersions (1-17) (being made by embodiment A1-17), 16 parts of acrylic resin adhesives (containing polyisocyanate curing agent) and 50 parts of acetic acid butyl esters-toluene (as solvent) are mixed, so that a kind of composition (3-6) for film forming be made.

It uses stick coating machine that composition (3-6) is coated on PET film (as substrate), makes 8 μm of thickness of dry film, then kept for 5 minutes at 100 DEG C, to form the film that film thickness is 8m on the surface of PET film.

The film of formation is such a film, the ultra-fine ZnO particle dispersed and be present in solid solution containing wherein Bi in acrylic resin film.

Have rated the spectral property for forming the PET film (PET film of film coating) of film on the surface thereof.It is obtained from result, it is found that the glass plate for the film that this PET film is similar embodiment A3-5 coats has first to absorb the film absorbed with second, so cutting off property with fabulous ultraviolet light.

The visible transparency of the PET film of film coating is "○", and colours and be also at imperceptible degree.

[embodiment A3-7]:

By 100 parts of dispersions (1-18) (being made by embodiment A1-18) and 100 parts of silica solution (solvents: IPA, concentration=20wt% of silica) it is mixed (as adhesive), so that a kind of composition (3-7) for film forming be made.

Composition (3-7) is coated on the identical glass plate of embodiment A3-5 with stick coating machine, is then heated at 300 DEG C, to form the film that film thickness is 2 μm on the surface of glass plate.

It is such a film by the film that composition (3-7) is formed, disperses and contain useful Bi in amorphous oxide silicon fiml₂O₃The ultra-fine CeO of coating₂Particle.

Have rated the spectral property for forming the glass plate (glass plate of film coating) of film on the surface thereof.It is obtained from result, it is found that this glass plate absorbs the ultraviolet light for being not more than 360nm, due also to having absorption in the case where being not more than 420nm wavelength containing Bi.

[embodiment A3-8]:

By 100 parts of dispersions (1-19) (being made by embodiment A1-19) and 100 parts of silica solution (solvents: IPA, concentration=20wt% of silica) it is mixed (as adhesive), so that a kind of composition (3-8) for film forming be made.

Composition (3-8) is coated on the identical glass plate of embodiment A3-5 with stick coating machine, is then heated at 300 DEG C, to form the film that film thickness is 2 μm on the surface of glass plate.

The film formed by composition (3-8) is such a film, the dispersion and containing using Bi in amorphous oxide silicon fiml₂O₃The superfine Ti O of coating₂Particle.

Have rated the spectral property for forming the glass plate (glass plate of film coating) of film on the surface thereof.It is obtained from result, it is found that this glass plate absorbs the ultraviolet light for being not more than 360nm, due also to containing Bi no more than having absorption at 420nm wavelength.

[embodiment A3-9]:

Use stick coating machine that dispersion (1-17) (as made from embodiment A1-17) is coated on glass plate (as substrate), then in heating furnace at 100 DEG C heat drying, then its temperature is increased and is kept for 2 hours after reaching 350 DEG C, to form the film that film thickness is 2 μm in glass pane surface.

The film of formation is ZnO crystal film, wherein containing the Bi of 5 atom % relative to Zn.

Have rated the spectral property for forming the glass plate (glass plate of film coating) of film on the surface thereof.It is obtained from result, it was found that this glass plate absorbs the ultraviolet light of wide scope, specifically, it blocks the ultraviolet light for being not more than 370nm by the absorption (first absorbs) based on ZnO band gap, and has on longer wavelength side (thering is it to absorb limit at 416nm) and absorb (based on containing Bi) (second absorbs).

The transparency of the glass plate of film coating is 0.6% turbidity.

[embodiment A3-10]:

The film that film thickness is 2 μm is formed in glass pane surface with the identical method of embodiment A3-9, the difference is that dispersion (1-21) (as made from embodiment A1-21) replaces dispersion (1-17) and heat drying temperature to become 200 DEG C.

The film of formation is the ZnO crystal film containing Bi and In, and wherein the content relative to Zn of Bi and In is about 3 atom %.

Have rated the spectral property for forming the glass plate (glass plate of film coating) of film on the surface thereof.It is obtained from result, it is found that this glass plate absorbs the ultraviolet light of wide scope, specifically, there is the first absorption and second of similar embodiment A3-9 to absorb, also have blocking property to the light of near infra red region.

The transparency of the glass plate of film coating is 1.2% turbidity.

[embodiment A3-11]:

The film that film thickness is 2 μm is formed in glass pane surface with the identical method of embodiment A3-9, the difference is that dispersion (1-19) (as made from embodiment A1-19) replaces dispersion (1-17) and heat drying temperature to become 500 DEG C.

The film of formation is a kind of crystalliferous crystal film, wherein containing the Bi of 25 atom % relative to Ti.

Have rated the spectral property for forming the glass plate (glass plate of film coating) of film on the surface thereof.It is obtained from result, it is found that this film is a kind of film for having fabulous reflectivity properties.

[embodiment A3-12]:

The film that film thickness is 2 μm is formed in glass pane surface with the identical method of embodiment A3-9, the difference is that replacing dispersion (1-17) and heat drying temperature to become 200 DEG C as the 2- propyl alcohol dispersion (1-3) to concentration 20wt% made from the displacement of reaction solution (1-3) (as made from embodiment A1-3) heated solvent.

The film of formation is a kind of ZnO crystal film, wherein containing the Ag of 1 atom % relative to Zn.

Have rated the spectral property for forming the glass plate (glass plate of film coating) of film on the surface thereof.It is obtained from result, it is found that this glass plate absorbs the ultraviolet light of wide scope, specifically, having blocking property to the ultraviolet light no more than 430nm.

The transparency of the glass plate of film coating is 0.8% turbidity.

[embodiment A3-13]:

The film that film thickness is 2 μm is formed in glass pane surface with the identical method of embodiment A3-9, the difference is that as replacing dispersion (1-17) and heat drying temperature to become 350 DEG C the 2- propyl alcohol dispersion (1-2) of concentration 20wt% made from the displacement of reaction solution (1-2) (as made from embodiment A1-2) heated solvent.

The film of formation is a kind of ZnO crystal film, wherein containing the Cu of 2 atom % relative to Zn.

Have rated the spectral property for forming the glass plate (glass plate of film) of film on the surface thereof.It is obtained from result, it is found that this glass plate absorbs the ultraviolet light of wide scope, specifically, having blocking property to the ultraviolet light no more than 380nm.

The transmissivity of the glass plate of film coating is 0.2% turbidity.

[second of metal oxide particle]:

Unless separately plus illustrating in each for the embodiment and comparative example mentioned below, measures and evaluate using the following method in these embodiment and comparative examples.

<evaluation of metal oxide particle>:

(1) the crystal identification of metal oxide particle:

X-ray: 1 ray of CuK α (wavelength: 1.54056)/40kV/200mA

Scanning range: 2 θ=20-80 °

Scanning speed: 5 °/min

For example, in the case where metal oxide particle contains Zn as main metal component, by whether observing that the three strong ray peak of ZnO of characterization hexagonal crystal system judges whether metal oxide particle has crystallographic system identical with ZnO and crystal structure.Specifically, judging the metal oxide particle and ZnO crystallographic system having the same and crystal structure if having diffraction maximum in all positions following three angle of diffraction (a)-(c).

(d) 2 θ=31.65-31.95 °

(e) 2 θ=34.30-34.60 °

(f) 2 θ=36.10-36.40 °

By the way, diffraction maximum existing at the position of above-mentioned (a) is judged as the diffracted ray in (100) face based on ZnO crystal, and at the position of above-mentioned (b) existing for diffraction maximum be judged as the diffracted ray in (002) face based on ZnO crystal, and at the position of above-mentioned (c) existing for diffraction maximum be judged as the diffracted ray in (101) face based on ZnO crystal.

Similar, containing the metallic element different from Zn as main metal component in metal oxide particle, whether metal oxide particle with the oxide of above-mentioned metallic element has identical crystallographic system and crystal structure by whether observing that characterizing the three strong ray peak of the oxide crystal of above-mentioned metallic element judges.

(2) particle diameter (Ds) and (Dw) of metal oxide particle:

About above-mentioned powder sample, the crystal grain diameter (Ds) of metal oxide particle is evaluated with the powder X-ray diffractometry of powder x-ray diffraction (Rigaku Denki K.K. production, ProductName: RINT 2400).

Specifically, about crystal grain diameter Ds, crystal grain diameter Ds (hkl) (wherein hkl indicate Miller index: Ds (hkl) be perpendicular to Miller index (hkl) lattice plane direction crystallite dimension (by the way, Miller index (hkl) is different with embodiment and comparative example and shows in table, shows its respective result)) it is measured with Scherrer equation (analysis) by the width of the diffracted ray in obtained X-ray diffractogram.

About crystal grain diameter (Dw), the average value of the strong respective Ds numerical value of ray of three measured in aforementioned manners is as Dw.That is, unless otherwise noted, crystal grain diameter (Dw) usually calculates using the following method.Measure the x-ray diffractogram of powder of metal oxide particle, about three of them strong ray (the third-largest peak (3) of the maximum peak (1) of diffracted ray, the second largest peak (2) of diffracted ray and diffracted ray), vertically crystal grain diameter Ds1, Ds2 and Ds3 for being belonging respectively in the direction of diffracted ray (1)-(3) diffraction surfaces by respective maximum intensity half overall with or integral breadth measured according to Scherrer equation, then regard its average value ((Ds1+Ds2+Ds3)/3) as crystal grain diameter (Dw).

(3) composition (average composition of metallic element) of metal oxide particle:

The quantitative analysis of metallic element is carried out to above-mentioned powder sample with x-ray fluorescence analysis, content to measurement relative at least two miscellaneous metallic elements (M ') (hereinafter referred to as M1, M2) of main metal element (M), and for during particle is formed, in the case that metallic compound is used as additive, the content of the metallic element (Ms) relative to main metal element (M) above-mentioned metallic compound is measured.

Furthermore, when observing each particle in above-mentioned powder sample with the FE-TEM (Flied emission transmission electron microscope) equipped with resolution ratio 1nm φ XMA equipment (X-ray microanalysis instrument), the any part of central part by the superficial layer of particle to it carries out local elemental analysis, the deviation of the intensity ratio of the peak intensity of every kind of metallic element peak intensity and main metal element (M) is evaluated, to judge whether every kind of metallic element is uniformly distributed contained in particle (uniformity for namely judging distribution).In addition, also evaluating the miscellaneous metallic element (M1, M2) of metallic compound when carrying out local elemental analysis to every kind of metallic element or whether metallic element (Ms) being segregated.

Zero: uniformly containing the metallic element (M1, M2, Ms) different from main metal element (M).

×: it is uneven to contain the metallic element (M1, M2, Ms) different from main metal element (M) and/or see its metal or compound segregation.

(4) chemical valence of contained miscellaneous metallic element is evaluated in metal oxide particle:

About above-mentioned powder sample, the 2p of contained miscellaneous metallic element (especially Co and Fe) in metal oxide particle is measured by x-ray photoelectron spectroscopy (XPS) with photoelectron spectroscopy (Nippon Denshi K.K. production, ProductName: JPS-90 type)_3/2Spectrum, and measured from peak position and combine energy numerical value, to judge the chemical valence of miscellaneous metallic element.

(5) performance of metal oxide particle:

(5-1):

Performance in the membrane stage of evaluation metal oxide particle dispersion using the following method.That is, heated solvent displacement is carried out by the reaction solution (dispersion) that the reaction of generation metal oxide particle generates, to which such a dispersion be made, metal oxide particle is dispersed in n-butyl alcohol, granule density is 20wt% (in the case that the boiling point of the solvent in reaction solution is higher than n-butyl alcohol, 20wt% dispersion is made by heating concentration of reaction solution (dispersion) and uses this dispersion).The dispersion that 100 parts are generated (presses SiO with 20 parts of silicate adhesives₂Meter solid component content is 51wt%) and 0.5 part of catalyst (n-butylamine) mixing, so that a kind of coating be made.By the way, about above-mentioned granule density, the dispersion of generation is used vacuum desiccator to be dried in vacuo 1 hour obtained solid component quantity at 120 DEG C and is calculated as particle weight.

The coating of generation is coated on alkali-free glass (being produced by CorningInternational Corporation, barium borosilicate glass, glass code 7059, thickness: 0.6mm) with stick coating machine, wet film with a thickness of 24 μm.Hereafter, they are normally dried at 25 DEG C, so that the glass for forming metal oxide particle dispersion membrane on the surface thereof be made.Then, with the only membrane part for evaluating this dispersion-film coating glass based on the visible transmission property of transmitted spectrum, ultraviolet radiation absorption property and visible light long wavelength absorbent properties.By the way, it because the transmitted spectrum of above-mentioned dispersion membrane is also influenced by the dispersity of particle, requires herein: should only evaluate the dispersion membrane of turbidity < 3% in terms of meeting transparency.So, in the case where particle is difficult to disperse, decentralized processing carries out (result for referring to following evaluations (6)) for a long time, if it is desired, also uses other dispersing methods when coating is made.

The glass of each dispersion film coating and the transmitted spectrum of above-mentioned alkali-free glass are measured using the automatic record spectrophotometer (" UV-3100 " of Shimadzu Corporation production) for having integrating sphere.

Glass and alkali-free glass about the coating of each dispersion film, by obtained transmitted spectrum, with transmission of visible light (transmissivity (%) of wavelength 500-600nm light) (embodiment B4-1, the transmissivity (%) of B4-2 and comparative example B4-1 in the transmissivity (%) and other embodiments and comparative example into B4-3 under 600nm under 500nm) have rated the transmission property of visible light, and with transmissivity (the wavelength 380nm within the scope of visible light to short-wavelength visible light, 400nm, transmissivity under 420nm) have rated ultraviolet radiation absorption property (still, in some embodiments and comparative example, transmissivity under the 380nm being used only in above-mentioned wavelength or 380 and 400nm has rated ultraviolet radiation absorption property).In addition, having rated the absorbent properties of wavelength visible using the following method: about the absorbent properties within the scope of 550-700nm, Δ (%) is measured with following equation:

Δ (%)=[| T⁵⁰⁰-T¹|/T⁵⁰⁰]×100

(wherein T¹For the minimum value of 550-700nm range internal transmission factor (%)；And T⁵⁰⁰For the transmissivity (%) under 500nm, value is evaluated by following standard:

A: Δ (%) < 10%

B:10≤Δ (%)

By the way, with the above-mentioned transmissivity under following equation measurement only each wavelength of membrane part:

The only transmissivity under each wavelength of membrane part=[transmissivity (%) under transmissivity (%)/each wavelength of alkali-free glass under each wavelength of glass of dispersion film coating] × 100

(wherein: about the transmissivity (%) under each wavelength of the alkali-free glass measured with above-mentioned evaluation method, 91%) any transmissivity at 380nm, 400nm, 420nm and 500nm and the transmissivity within the scope of 550-700nm are.

(5-2):

Identical evaluation is carried out with the identical method of above-mentioned evaluation method (5-1), the difference is that the glass of dispersion film coating is made with the method that the coating wet-film thickness that stick coating machine obtains is 66 μm.By the way, the metal oxide particle pointed out in embodiment carries out this evaluation.

(5-3):

The dilution prepared by using n-butyl alcohol that the reaction solution (dispersion) of generation is diluted to 0.1wt% fine particle concentration as retarder thinner, and the dilution is used as sample, the transmitted spectrum in ultraviolet light and visible-range then is measured with the automatic record spectrophotometer (" UV-3100 " of Shimadzu Corporation production) for having integrating sphere for this sample.

The transmission property of visible light: it is evaluated with the transmissivity under 600nm.

By the way, similar above-mentioned about the transmitted spectrum of film-forming products, the transmitted spectrum in ultraviolet light and visible-range is measured with the automatic record spectrophotometer (" UV-3100 " of Shimadzu Corporation production) for having integrating sphere.

The evaluation of (5-4) transparency and tone:

Form and evaluate the film of fine grained dispersion.

The glass of the coating of dispersion film made from above-mentioned (5-1) is used as sample, and is evaluated with transparency and tone.That is, evaluating transparency with the turbidity value of nephelometer (" the NDH-1001 DP " of the production of Nippon Denshoku Kogyo Co., Ltd.) measurement.About tone, appearance is with the naked eye observed.By the way, the turbidity value of alkali-free glass is 0%.

By the way, it is similar above-mentioned about the transparency and tone of film-forming products, with nephelometer (Nippon Denshoku Kogyo Co., Ltd. " NDH-1001DP " that produces) turbidity value of measurement evaluates transparency, and observe appearance with the naked eye to evaluate tone.

(6) (dispersing-ease) (dispersibility) is easily spent in the dispersion of metal oxide particle:

Dispersion condition of the turbidity value of the glass coated by dispersion film less than 3% is easily spent to evaluate the dispersion of metal oxide particle, at this time, with above-mentioned (5) identical method, the coating of containing metal oxide particle is prepared, and the glass for forming metal oxide particle dispersion membrane on its surface is made.Specifically, when uncoated coating ultrasonic homogenizer decentralized processing, with following standard, it is evaluated as the decentralized processing time (Ultrasonic Radiation time) how grown needed for obtaining the glass of the dispersion film for meeting above-mentioned turbidity value (< 3%) coating.

Zero: less than 5 minute

△: 5-10 minute (but not including 10 minutes)

×: it is not less than 10 minutes

(7) identification of acyl group and binding capacity:

1g powder sample is added in 0.1N sodium hydrate aqueous solution, is then stirred 24 hours.Hereafter, acyl group is identified with ion chromatography and the quantity of combination is quantified.

<evaluation of film-forming composition>:

(1) dispersion stabilization:

The dispersion stabilization of the dispersion generated is evaluated with following standard:

A: it from dispersion is placed not disturbedly, was also had not seen even across 1 week and is separated into two layers or deposit.

B: occurs a small amount of deposit in 1 week after not placing dispersion not disturbedly.

C: occur a large amount of deposits in 1 week after not placing dispersion not disturbedly.

(2) transparency:

The dispersion of generation is coated on transparency glass plate in membrane form, is then detected by an unaided eye in the wet state, to evaluate it with following standard:

A: transparency feels high.

B: transparency feels high.

C: transparency feels low.

(3) discrete particles diameter:

Its median diameter is measured with dynamic light scattering type particle diameter distribution analyzer (" LB-500 " that is produced by Horiba Seisakusho), and as discrete particles diameter.

<evaluation of film (or substrate of film coating)>:

(1) visible transmission property and ultraviolet radiation absorption property based on transmitted spectrum:

The substrate that film by being evaluated generation based on the visible transmission property of its transmitted spectrum and ultraviolet radiation absorption property is coated.

The transmitted spectrum of the substrate of film coating is measured using the automatic record spectrophotometer (Shimadzu Corporation production, ProductName: UV-3100) for having integrating sphere.

Substrate about film coating, by obtained transmitted spectrum, visible transmission property is evaluated by the transmissivity (in the transmissivity (%) under 500nm) of visible light and ultraviolet radiation absorption property is evaluated by the transmissivity (transmissivity at 380nm, 400nm and 420nm) within the scope of from visible light to short-wavelength visible light.

By the way, only about the substrate for film coating substrate, the transmissivity under each wavelength is measured with above-mentioned identical method.

(2) visible transparency:

With nephelometer (Nippon Denshoku Kogyo Co., Ltd. " NDH-1001DP " produced) substrate and independent substrate of each film coating are measured by whole radiant transmittances, diffusion radiant transmittance, infinite ray transmissivity and turbidity, so as to the transparency with following standard from the turbidity value evaluated for film of measurement.By the way, the turbidity value of film is obtained by the turbidity value that the turbidity value of the substrate of film coating subtracts independent substrate.

Zero: turbidity < 3%

×: turbidity >=3%

(3) coloring degree:

About the film (substrate of film coating) of generation, detect by an unaided eye its appearance, to evaluate coloring degree with following standard:

×: coloring is obvious.

Zero: not changing, even if having, colour also unobvious.

(4) refractive index:

By with reflectance spectrum film thickness meter (Ohtsuka Electronics Co., Ltd. " FE-3000 " produced) within the scope of 230-760nm measure film (formed on the substrate) reflection, then use the dispersion formula of nkCauchy as the representative approximate formula of refractive index, to determine unknown parameter by the actual measured value of the spectrum of absolute reflection by non-linear least square method, to measure the refractive index under 550nm wavelength.

(5) thickness of dry film:

With reflection-spectro-film thickness gauge (" FE-3000 " of the production of Ohtsuka Electronics Co., Ltd.) measurement.

[embodiment B1-1]:

Prepare such a consersion unit, it includes: can pressure-resistant glass reactor external heating and that mouth is sent into equipped with blender, addition entrance (being directly connected with addition tank), thermometer, retort gas outlet and nitrogen；The addition tank being connected with above-mentioned addition entrance and the condenser (being directly connected with trap) being connected with the outlet of above-mentioned retort gas.

Mixture containing 183 parts of anhydrous zinc acetates, 3.8 parts of ferric acetate (III) hydroxide powders, 7.1 parts of tin acetates (IV) and 1700 parts of methanol is packed into above-mentioned reactor, then purges its gas phase portion with nitrogen.Hereafter, the temperature of mixture (from 20 DEG C) is risen to 150 DEG C under stiring, and heating is kept for 5 hours at 150 DEG C ± 1 DEG C, to be reacted, generate metal oxide particle, then it cools down, so that the reaction solution (11) containing yellow fine grained (metal oxide particle) be made.In addition, the reaction solution of generation is subjected to heated solvent displacement, so that the dispersion (11) that above-mentioned metal oxide particle is dispersed in n-butyl alcohol is made, granule density 20wt%.

Metal oxide particle in reaction solution (11) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 7.By the way, the chemical valence of the Fe contained in the metal oxide particle in reaction solution (11), by the 2p for measuring Fe in aforementioned manners_3/2Spectrum is evaluated.As a result, judging from its peak position, the Fe (Fe (III)) containing trivalent.

In addition, the transmitted spectrum of the glass of dispersion film obtained coating is shown in Fig. 6 with comparative example B1-1 cited below together in above-mentioned various measurements and evaluation.

[comparative example B1-1]:

Preparation and embodiment B1-1 same reaction equipment, it is for example comprising pressure-resistant glass reactor.

Mixture containing 183 parts of anhydrous acetic acid zinc powders, 3.8 parts of ferric acetate (III) hydroxide powders and 1700 parts of methanol is packed into above-mentioned reactor, then purges its gas phase portion with nitrogen.Hereafter, the temperature of mixture (from 20 DEG C) is risen to 180 DEG C under stiring, and heating is kept for 5 hours at 180 DEG C ± 1 DEG C, to be reacted, generate metal oxide particle, then it cools down, so that the reaction solution (c11) containing yellow fine grained (metal oxide particle) be made.In addition, the reaction solution of generation is subjected to heated solvent displacement, so that the dispersion (c11) that above-mentioned metal oxide particle is dispersed in n-butyl alcohol is made, granule density 20wt%.

Metal oxide particle in reaction solution (c11) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 7.

In addition, the transmitted spectrum of the glass of dispersion film obtained coating is shown in Fig. 6 with comparative example B1-1 above-mentioned together in above-mentioned various measurements and evaluation.

[embodiment B1-2 to B1-4]:

Reaction solution (12) to (14) and dispersion (12) to (14) containing yellow fine grained (metal oxide particle) is made with the identical method of embodiment B1-1, unlike as shown in table 6, change the raw material type and dosage and reaction condition of loading.

Metal oxide particle of the reaction solution (12) into (14) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 7.By the way, the chemical valence about the Co contained in metal oxide particle of the reaction solution (12) to (14), by the 2p for measuring Co in aforementioned manners_3/2Spectrum is evaluated.As a result, judging from its peak position, the Co (Co (II)) containing divalent.

About the metal oxide particle in reaction solution (12), the evaluation (5-2) in the evaluation of above-mentioned metal oxide particle is also carried out.Therefore it obtains, the transmissivity at 380nm is less than 1%, and the transmissivity at 500nm is 80%, and Δ (%) is 4%.

In addition, about the metal oxide particle in reaction solution (12), the transmitted spectrum of the glass of dispersion film coating obtained is shown in Fig. 7 with comparative example B1-2 cited below together in above-mentioned various measurements and evaluation.

By the way, the particle in the dispersion made from embodiment B1-3, with the chemical valence of XPS measuring trace metal element.Therefore it obtains, Cu (II) and Cu (I) are mixed.

[embodiment B1-5 to B1-8]:

Reaction solution (15) to (18) and dispersion (15) to (18) containing yellow fine grained (metal oxide particle) is made with the identical method of embodiment B1-1, the difference is that as shown in table 6, change the raw material type being packed into and dosage and reaction condition (as raw material is packed into, additive shown in table 6 also includes wherein).

By reaction solution (15), into (18), the metal oxide particle of each carries out above-mentioned various measurements and evaluation.Its result is included in table 7.By the way, the chemical valence of the Co contained in the metal oxide particle in reaction solution (17), by the 2p for measuring Co in aforementioned manners_3/2Spectrum is evaluated.As a result, judging from its peak position, the Co (Co (II)) containing divalent.

[comparative example B1-2 to B1-3]:

Reaction solution (c12) to (c13) and dispersion (c12) to (c13) containing yellow fine grained (metal oxide particle) is made with the identical method of embodiment B1-1, unlike as shown in table 6, change the raw material type and dosage and reaction condition of loading.

By reaction solution (c12), into (c13), the metal oxide particle of each carries out above-mentioned various measurements and evaluation.Its result is included in table 7.In addition, about the metal oxide particle in reaction solution (c12), the transmitted spectrum of the glass of dispersion film coating obtained is shown in Fig. 7 with above-described embodiment B1-2 together in above-mentioned various measurements and evaluation.

Table 6

	Zinc compound parts by weight	M1 compound by weight part	M2 compound by weight part	Additive parts by weight	Weight of solvent part	Reaction condition
						Reaction condition		Temperature (DEG C)	Residence time (h)
						Embodiment B1-1	Zinc acetate 183	Temperature (DEG C)	Residence time (h)	Ferric acetate (III) hydroxide 3.8	Tin acetate (IV) 7.1	- 0	Methanol 1700	150	5
Embodiment B1-2	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	Anhydrous acetic acid indium (III) 2.9	- 0	1- propyl alcohol 1700	Embodiment B1-1	Zinc acetate 183	150	5	Ferric acetate (III) hydroxide 3.8	Tin acetate (IV) 7.1	- 0	Methanol 1700	150	5
Embodiment B1-2	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	Anhydrous acetic acid indium (III) 2.9	- 0	1- propyl alcohol 1700	Embodiment B1-3	Zinc acetate 183	150	5	Anhydrous cupric acetate (II) 3.6	Aluminium-sec-butylate (III) 0.49	- 0	Ethyl alcohol 1700	150	5
Embodiment B1-4	Zinc acetate 183	Anhydrous cobalt acetate (II) 7.1	Titanium (IV) methoxy propyl oxide 8.1	- 0	1- propyl alcohol 1700	Embodiment B1-3	Zinc acetate 183	180	5	Anhydrous cupric acetate (II) 3.6	Aluminium-sec-butylate (III) 0.49	- 0	Ethyl alcohol 1700	150	5
Embodiment B1-4	Zinc acetate 183	Anhydrous cobalt acetate (II) 7.1	Titanium (IV) methoxy propyl oxide 8.1	- 0	1- propyl alcohol 1700	Embodiment B1-5	Zinc acetate 183	180	5	Anhydrous cobalt acetate (II) 1.8	Ethyoxyl gallium (III) 2.0	Methyltrimethoxysilane 2.7	Ethyl alcohol 1700	160	5
Embodiment B1-6	Zinc acetate 183	Isopropoxy iron (III) 1.2	The tertiary pentoxide 9.4 of bismuth (III)	Partial hydrolysis-condensation product (trimer to pentamer) 11.0 of tetramethoxy-silicane	1- propyl alcohol 1700	Embodiment B1-5	Zinc acetate 183	150	5	Anhydrous cobalt acetate (II) 1.8	Ethyoxyl gallium (III) 2.0	Methyltrimethoxysilane 2.7	Ethyl alcohol 1700	160	5
Embodiment B1-6	Zinc acetate 183	Isopropoxy iron (III) 1.2	The tertiary pentoxide 9.4 of bismuth (III)		1- propyl alcohol 1700	Embodiment B1-7	Zinc acetate 183	150	5	Anhydrous cobalt acetate (II) 3.5	Bismuth acetate (III) 0.77	N-butoxy aluminium (III) trimer 1.0	Ethyl alcohol 1700	160	5
Embodiment B1-8	Zinc acetate 183	Anhydrous cobalt acetate (II) 0.88	2.9 bismuth acetate (III) 5.7 of anhydrous acetic acid indium (III)	Four titanium n-butoxides (IV) tetramer 12.1	1- propyl alcohol 1700	Embodiment B1-7	Zinc acetate 183	180	5	Anhydrous cobalt acetate (II) 3.5	Bismuth acetate (III) 0.77	N-butoxy aluminium (III) trimer 1.0	Ethyl alcohol 1700	160	5
Embodiment B1-8	Zinc acetate 183	Anhydrous cobalt acetate (II) 0.88		Four titanium n-butoxides (IV) tetramer 12.1	1- propyl alcohol 1700	Comparative example B1-1	Zinc acetate 183	180	5	Ferric acetate (III) hydroxide 3.8	- 0	- 0	Methanol 1700	180	5
Comparative example B1-2	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	- 0	- 0	1- propyl alcohol 1700	Comparative example B1-1	Zinc acetate 183	150	5	Ferric acetate (III) hydroxide 3.8	- 0	- 0	Methanol 1700	180	5
Comparative example B1-2	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	- 0	- 0	1- propyl alcohol 1700	Comparative example B1-3	Zinc acetate 183	150	5	- 0	Indium acetate (III) 5.8	- 0	Ethyl alcohol 1700	180	5

Table 7

	X-ray diffractogram	Fine grain metal forms (x-ray fluorescence analysis)			Distributing homogeneity	Crystal grain diameter (nm)		Visible transmission property (%) 500nm	Ultraviolet radiation absorption property (%)			Wavelength visible absorbent properties	Dispersibility
		Fine grain metal forms (x-ray fluorescence analysis)				Crystal grain diameter (nm)			Ultraviolet radiation absorption property (%)					M1 atom %/Zn	M2 atom %/Zn	Ms atom %/Zn	Ds(100)	Ds(002)	380 nm	400 nm	420 nm
		Embodiment B1-1	It is equivalent to ZnO	Fe 1.9		Sn 1.9	- < 0.01		○	18	17			M1 atom %/Zn	M2 atom %/Zn	Ms atom %/Zn	Ds(100)	Ds(002)	380 nm	400 nm	420 nm	92	18	60	75	A	△
Embodiment B1-2	It is equivalent to ZnO	Embodiment B1-1	It is equivalent to ZnO	Fe 1.9	Co 1.9	Sn 1.9	- < 0.01	In 1	○	18	17	- < 0.01	○	24	21	91	10	39	65	A	△	92	18	60	75	A	△
Embodiment B1-2	It is equivalent to ZnO	Embodiment B1-3	It is equivalent to ZnO	Cu 1.5	Co 1.9	Al 0.2	- < 0.01	In 1	○	25	24	- < 0.01	○	24	21	91	10	39	65	A	△	93	19	61	75	A	×
Embodiment B1-4	It is equivalent to ZnO	Embodiment B1-3	It is equivalent to ZnO	Cu 1.5	Co 3.8	Al 0.2	- < 0.01	Ti 1.9	○	25	24	- < 0.01	○	15	15	93	14	44	69	A	△	93	19	61	75	A	×
Embodiment B1-4	It is equivalent to ZnO	Embodiment B1-5	It is equivalent to ZnO	Co 0.9	Co 3.8	Ga 1	Si 2	Ti 1.9	○	8	18	- < 0.01	○	15	15	93	14	44	69	A	△	90	9	35	58	A	○
Embodiment B1-6	It is equivalent to ZnO	Embodiment B1-5	It is equivalent to ZnO	Co 0.9	Fe 0.5	Ga 1	Si 2	Bi 1.3	○	8	18	Si 8.8	○	11	16	90	43	57	52	A	○	90	9	35	58	A	○
Embodiment B1-6	It is equivalent to ZnO	Embodiment B1-7	It is equivalent to ZnO	Co 2	Fe 0.5	Bi 0.2	Al 0.6	Bi 1.3	○	8	20	Si 8.8	○	11	16	90	43	57	52	A	○	89	29	48	60	A	○
Embodiment B1-8	It is equivalent to ZnO	Embodiment B1-7	It is equivalent to ZnO	Co 2	Co 0.5	Bi 0.2	Al 0.6	In 0.5 Bi 1.5	○	8	20	Ti 4.9	○	10	12	88	10	27	27	A	○	89	29	48	60	A	○
Embodiment B1-8	It is equivalent to ZnO	Comparative example B1-1	It is equivalent to ZnO	Fe 1.8	Co 0.5	- 0	- < 0.01	In 0.5 Bi 1.5	○	21	21	Ti 4.9	○	10	12	88	10	27	27	A	○	96	46	76	84	A	×
Comparative example B1-2	It is equivalent to ZnO	Comparative example B1-1	It is equivalent to ZnO	Fe 1.8	Co 1.7	- 0	- < 0.01	- 0	○	21	21	- < 0.01	○	26	23	97	30	60	81	A	×	96	46	76	84	A	×
Comparative example B1-2	It is equivalent to ZnO	Comparative example B1-3	It is equivalent to ZnO	- 0	Co 1.7	In 1.9	- < 0.01	- 0	○	20	18	- < 0.01	○	26	23	97	30	60	81	A	×	98	36	87	73	A	△

[embodiment B1-9]:

It will be sent into consersion unit identical with embodiment B1-1 containing the mixture of 183 parts of anhydrous zinc acetates, 0.9 part of anhydrous cupric acetate (II), 3 parts of anhydrous acetic acid indiums, 16 part of four butoxy silane and 1847 parts of 2- propyl alcohol, and then purge its gas phase portion with nitrogen.Hereafter, the temperature of mixture is increased from 20 DEG C under stiring, and heating is kept for 5 hours at 150 DEG C ± 1 DEG C, to be reacted, metal oxide particle is generated, is then cooled down, to which the dispersion (19) containing containing metal oxide particle reaction liquid, concentration 4wt% be made.

It has proven to; fine grained in the dispersion of generation is those particles; they contain ZnO crystal; its crystal grain diameter is 14nm; copper and indium relative to Zn respectively containing 0.4 and 0.9 atom %, and the acetyl group of 3.1 moles of % and Si compound containing Si/Zn=5 atom % are combined relative to its surface Zn.

The metal oxide particle of dispersion (19) is had rated with the method for above-mentioned (5-3) and (5-4).That is, ultraviolet radiation absorption property and visible absorption property are had rated using the following method: as using n-butyl alcohol as the dispersion of retarder thinner dilution generation to cause fine grain concentration to be 0.1wt% dilution come made from, and use the dilution as sample, this a sample is fitted into the quartz cell of thickness 1cm, to measure the transmitted spectrum in its ultraviolet light and visible-range with the automatic record spectrophotometer (" UV-3100 " of Shimadzu Corporation production) for having integrating sphere.Ultraviolet radiation absorption property is evaluated with the transmissivity under 380nm, 400nm, 420nm, and the transmission property of visible light is evaluated with the transmissivity under 600nm.Its result is included in table 9.

[embodiment B1-10 to B1-15 and comparative example B1-4 to B1-6]:

There is the mixture of alcohol come obtained dispersion (110) to (115) and (c14) to (c16) containing reaction solution by heating in the range of 120-200 DEG C with the identical method of embodiment B1-9, wherein metal oxide particle is 4wt% dispersion with granule density, the difference is that as shown in table 8, change the type for the raw material being packed into (as the raw material of addition, additive shown in table 8 also includes wherein).

The dispersion generated with the identical method evaluation of embodiment B1-9.Its result is included in table 9.

The fine grained in dispersion made from embodiment B1-9 to B1-15 is evaluated with the uniformity of distribution.As a result, not seeing including containing the metallic element (M1, M2, M3 of table 4) being added, as (super) thin monometallic particle of main component or the segregation of metal oxide particle, any situation is all chosen as "○".

About by combination can value can determine whether metalliferous chemical valence material, as with the measurement of light electronic electricity tester, these chemical valences are included in table.

Table 8

	Zinc compound	M1 compound	M2 compound	M3 compound	The metallic compound of surface treatment
	Zinc compound	M1 compound	M2 compound	M3 compound	The metallic compound of surface treatment	Embodiment B1-9	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Anhydrous acetic acid indium	-	Four butoxy silanes
Embodiment B1-10	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Cerium acetate hydrate (III)	-	Tetramethoxy-silicane	Embodiment B1-9	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Anhydrous acetic acid indium	-	Four butoxy silanes
Embodiment B1-10	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Cerium acetate hydrate (III)	-	Tetramethoxy-silicane	Embodiment B1-11	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Four titanium n-butoxides (IV)	-	Methyltrimethoxysilane
Embodiment B1-12	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Tin acetate (II)	-	-	Embodiment B1-11	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Four titanium n-butoxides (IV)	-	Methyltrimethoxysilane
Embodiment B1-12	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Tin acetate (II)	-	-	Embodiment B1-13	Anhydrous zinc propionate	Anhydrous cupric acetate (II)	Bismuth acetate (III) oxide	-	-
Embodiment B1-14	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Ferric acetate (III) hydroxide	-	-	Embodiment B1-13	Anhydrous zinc propionate	Anhydrous cupric acetate (II)	Bismuth acetate (III) oxide	-	-
Embodiment B1-14	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Ferric acetate (III) hydroxide	-	-	Embodiment B1-15	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Nickel acetate tetrahydrate (II)	Anhydrous acetic anhydride indium	-
Comparative example B1-4	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	-	-	Tetramethoxy-silicane	Embodiment B1-15	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	Nickel acetate tetrahydrate (II)	Anhydrous acetic anhydride indium	-
Comparative example B1-4	Anhydrous zinc acetate	Anhydrous cupric acetate (II)	-	-	Tetramethoxy-silicane	Comparative example B1-5	Anhydrous zinc acetate	Anhydrous acetic acid indium	-	-	Tetramethoxy-silicane
Comparative example B1-6	Anhydrous zinc acetate	-	-	-	Tetramethoxy-silicane	Comparative example B1-5	Anhydrous zinc acetate	Anhydrous acetic acid indium	-	-	Tetramethoxy-silicane

Table 9

	X-ray diffractogram	Fine grain metal forms (x-ray fluorescence analysis)				Crystal grain diameter Dw (nm)	The binding capacity of acyl group		Transparency turbidity (%)	Tone	Ultraviolet radiation absorption property (%)			Transmission of visible light (%) 600nm
		Fine grain metal forms (x-ray fluorescence analysis)					The binding capacity of acyl group				Ultraviolet radiation absorption property (%)				M1 atom %/Zn	M2 atom %/Zn	M3 atom %/Zn	Ms atom %/Zn	Identification	Binding capacity mol%/Zn	380 nm	400 nm	420 nm
		Embodiment B1-9	It is equivalent to ZnO	Cu 0.4	In 0.8		- -	Si 5			14	Acetyl group	3.1		M1 atom %/Zn	M2 atom %/Zn	M3 atom %/Zn	Ms atom %/Zn	Identification	Binding capacity mol%/Zn	380 nm	400 nm	420 nm	0.2	It is colourless	6	43	59	85
Embodiment B1-10	It is equivalent to ZnO	Embodiment B1-9	It is equivalent to ZnO	Cu 0.4	In 0.8	Cu 0.1	- -	Si 5	Ce(III) 0.2	- -	14	Acetyl group	3.1	Si 1	13	Acetyl group	2	0.3	It is colourless	2	16	31	83	0.2	It is colourless	6	43	59	85
Embodiment B1-10	It is equivalent to ZnO	Embodiment B1-11	It is equivalent to ZnO	Cu 0.5	Ti 0.05	Cu 0.1	- -	Si 2	Ce(III) 0.2	- -	14	Acetyl group	1.5	Si 1	13	Acetyl group	2	0.3	It is colourless	2	16	31	83	0.1	It is colourless	3	19	30	83
Embodiment B1-12	It is equivalent to ZnO	Embodiment B1-11	It is equivalent to ZnO	Cu 0.5	Ti 0.05	Cu 1	- -	Si 2	Sn(II) 0.5	- -	14	Acetyl group	1.5	- -	16	Formoxyl	1.1	0.5	It is colourless	3	18	29	87	0.1	It is colourless	3	19	30	83
Embodiment B1-12	It is equivalent to ZnO	Embodiment B1-13	It is equivalent to ZnO	Cu 1	Bi(III) 0.9	Cu 1	- -	- -	Sn(II) 0.5	- -	15	Propiono	1.4	- -	16	Formoxyl	1.1	0.5	It is colourless	3	18	29	87	0.6	It is colourless	7	11	13	88
Embodiment B1-14	It is equivalent to ZnO	Embodiment B1-13	It is equivalent to ZnO	Cu 1	Bi(III) 0.9	Cu 1.3	- -	- -	Fe(II) 1.5Fe(III)	- -	15	Propiono	1.4	- -	13	Acetyl group	2	0.9	It is yellowish	5	18	28	78	0.6	It is colourless	7	11	13	88
Embodiment B1-14	It is equivalent to ZnO	Embodiment B1-15	It is equivalent to ZnO	Cu 3	Ni(II) 2.5	Cu 1.3	In 0.1	- -	Fe(II) 1.5Fe(III)	- -	16	Acetyl group	10	- -	13	Acetyl group	2	0.9	It is yellowish	5	18	28	78	0.6	It is yellowish	2	16	29	76
Comparative example B1-4	It is equivalent to ZnO	Embodiment B1-15	It is equivalent to ZnO	Cu 3	Ni(II) 2.5	Cu 2	In 0.1	- -	- -	- -	16	Acetyl group	10	Si 1	11	Acetyl group	8	0.4	It is colourless	13	55	69	90	0.6	It is yellowish	2	16	29	76
Comparative example B1-4	It is equivalent to ZnO	Comparative example B1-5	It is equivalent to ZnO	In 1.5	- -	Cu 2	- -	Si 1	- -	- -	15	Acetyl group	3	Si 1	11	Acetyl group	8	0.4	It is colourless	13	55	69	90	1.2	It is colourless	20	57	70	87
Comparative example B1-6	It is equivalent to ZnO	Comparative example B1-5	It is equivalent to ZnO	In 1.5	- -	- -	- -	Si 1	- -	- -	15	Acetyl group	3	Si 4	12	Acetyl group	3	0.6	It is colourless	36	62	70	91	1.2	It is colourless	20	57	70	87

From table 9 it is recognized that the case where absorptance of 380nm ultraviolet light contains a large amount of Cu increases more if also containing In, Sn, Ti or Ce (they are n-type dopant) in addition to Cu；And if also containing Bi in addition to Cu, the absorption of light improves within the scope of 400nm to 420nm；And if especially contain Sn or Bi, it can be seen that the transmission property (transmissivity at 600nm) of light improves.

[embodiment B1-16]:

Use the identical consersion unit of embodiment B1-1, by the mixture feeding reactor containing acetic acid gallium (III), 20 part of four titanium butoxide tetramer and the 3940 parts of 1- propyl alcohol that 183 parts of anhydrous zinc acetates, 5.8 parts of anhydrous acetic acid iron (III), 4.6 part 19 are hydrated, its gas phase portion then is purged with nitrogen.Hereafter, the temperature of mixture is increased from 20 DEG C under stiring, and heating is kept for 5 hours at 140 DEG C ± 1 DEG C, to be reacted, metal oxide particle is generated, is then cooled down, so that the dispersion (116) of the reaction solution containing the metal oxide particle containing 2wt% be made.

The dispersion of generation is evaluated with embodiment B1-9 identical method.Its result is included in table 11.

[embodiment B1-17 to B1-23 and comparative example B1-7]:

The dispersion (117) comprising the reaction solution for being wherein dispersed with the metal oxide particle that granule density is 2wt% is made by being heated mixture together with alcohol within the scope of 120-200 DEG C with the identical method of embodiment B1-16 to (123) and (c17), the difference is that as shown in table 10, change the raw material type being packed into (as the raw material of loading, additive shown in table 10 is also included within wherein).

The dispersion liquid of generation is evaluated with embodiment B1-9 identical method.Its result is included in table 11.

The fine grained in dispersion made from embodiment B1-16 to B1-23 is evaluated with the uniformity of distribution.As a result, any situation is all chosen as "○".

Table 10

	Zinc compound	M1 compound	M2 compound	M3 compound	Surface-treated metal compound
	Zinc compound	M1 compound	M2 compound	M3 compound	Surface-treated metal compound	Embodiment B1-16	Anhydrous zinc acetate	Anhydrous acetic acid iron (III)	Acetate hydrate gallium	-	Four titanium butoxide tetramers
Embodiment B1-17	Anhydrous zinc acetate	Ferric acetate (III) hydroxide	Anhydrous acetic acid silver (I)	Anhydrous acetic acid indium	-	Embodiment B1-16	Anhydrous zinc acetate	Anhydrous acetic acid iron (III)	Acetate hydrate gallium	-	Four titanium butoxide tetramers
Embodiment B1-17	Anhydrous zinc acetate	Ferric acetate (III) hydroxide	Anhydrous acetic acid silver (I)	Anhydrous acetic acid indium	-	Embodiment B1-18	Anhydrous zinc acetate	Ferric acetate (III) hydroxide	Cerium acetate hydrate (III)	-	-
Embodiment B1-19	Anhydrous zinc acetate	Ferric acetate (II)	Tin acetate (IV)	-	-	Embodiment B1-18	Anhydrous zinc acetate	Ferric acetate (III) hydroxide	Cerium acetate hydrate (III)	-	-
Embodiment B1-19	Anhydrous zinc acetate	Ferric acetate (II)	Tin acetate (IV)	-	-	Embodiment B1-20	Anhydrous zinc acetate	Ferric acetate (II)	Anhydrous cupric acetate (II)	-	Tetramethoxy-silicane
Embodiment B1-21	Anhydrous zn formate	Four acetate hydrate cobalts (II)	Anhydrous acetic acid indium	-	Tetrabutyl zirconate oligomer (condensation degree: 6-10)	Embodiment B1-20	Anhydrous zinc acetate	Ferric acetate (II)	Anhydrous cupric acetate (II)	-	Tetramethoxy-silicane
Embodiment B1-21	Anhydrous zn formate	Four acetate hydrate cobalts (II)	Anhydrous acetic acid indium	-	Tetrabutyl zirconate oligomer (condensation degree: 6-10)	Embodiment B1-22	Anhydrous zinc propionate	Nickel acetate tetrahydrate (II)	Anhydrous cupric acetate (II)	Aluminium-sec-butylate (III)	-
Comparative example B1-23	Anhydrous zinc propionate	Nickel acetate tetrahydrate (II)	Four titanium butoxides	-	-	Embodiment B1-22	Anhydrous zinc propionate	Nickel acetate tetrahydrate (II)	Anhydrous cupric acetate (II)	Aluminium-sec-butylate (III)	-
Comparative example B1-23	Anhydrous zinc propionate	Nickel acetate tetrahydrate (II)	Four titanium butoxides	-	-	Comparative example B1-7	Anhydrous zinc acetate	Ferric acetate (III)	-	-	-

Table 11

	X-ray diffractogram	Fine grain metal forms (x-ray fluorescence analysis)				Crystal grain diameter Dw (nm)	The binding capacity of acyl group		Transparency turbidity (%)	Tone	Ultraviolet radiation absorption property (%)			Transmission of visible light (%) 600nm
		Fine grain metal forms (x-ray fluorescence analysis)					The binding capacity of acyl group				Ultraviolet radiation absorption property (%)				M1 atom %/Zn	M2 atom %/Zn	M3 atom %/Zn	Ms atom %/Zn	Identification	Binding capacity mol%/Zn	380 nm	400 nm	420 nm
		Embodiment B1-16	It is equivalent to ZnO	Fe(III) 2.3	Ga 1		- -	Ti 8			15	Acetyl group	4		M1 atom %/Zn	M2 atom %/Zn	M3 atom %/Zn	Ms atom %/Zn	Identification	Binding capacity mol%/Zn	380 nm	400 nm	420 nm	0.2	It is yellowish	3	22	37	86
Embodiment B1-17	It is equivalent to ZnO	Embodiment B1-16	It is equivalent to ZnO	Fe(III) 2.3	Ga 1	Fe(II) 1.1Fe(III)	- -	Ti 8	Ag 0.05	In 1	15	Acetyl group	4	- -	18	Acetyl group	3.3	0.6	It is yellowish	4	16	14	79	0.2	It is yellowish	3	22	37	86
Embodiment B1-17	It is equivalent to ZnO	Embodiment B1-18	It is equivalent to ZnO	Fe(II) 0.2Fe(III)	Ce 0.5	Fe(II) 1.1Fe(III)	- -	- -	Ag 0.05	In 1	18	Acetyl group	0.9	- -	18	Acetyl group	3.3	0.6	It is yellowish	4	16	14	79	0.8	It is yellowish	5	16	28	76
Embodiment B1-19	It is equivalent to ZnO	Embodiment B1-18	It is equivalent to ZnO	Fe(II) 0.2Fe(III)	Ce 0.5	Fe(II) 0.6	- -	- -	Sn 0.5	- -	18	Acetyl group	0.9	- -	15	Acetyl group	1.7	0.5	Micro- green	3	13	29	88	0.8	It is yellowish	5	16	28	76
Embodiment B1-19	It is equivalent to ZnO	Embodiment B1-20	It is equivalent to ZnO	Fe(II) 5.2	Cu 0.1	Fe(II) 0.6	- -	Si 5	Sn 0.5	- -	7	Acetyl group	6	- -	15	Acetyl group	1.7	0.5	Micro- green	3	13	29	88	0.2	Micro- green	2	10	23	82
Embodiment B1-21	It is equivalent to ZnO	Embodiment B1-20	It is equivalent to ZnO	Fe(II) 5.2	Cu 0.1	Co(II) 1.9	- -	Si 5	In 1	- -	7	Acetyl group	6	Zr 0.4	15	Formoxyl	2	0.2	Micro- blue	2	11	27	72	0.2	Micro- green	2	10	23	82
Embodiment B1-21	It is equivalent to ZnO	Embodiment B1-22	It is equivalent to ZnO	Ni(II) 3	Cu 0.5	Co(II) 1.9	Al 1	- -	In 1	- -	20	Propiono	0.6	Zr 0.4	15	Formoxyl	2	0.2	Micro- blue	2	11	27	72	0.9	Micro- green	2	16	29	76
Comparative example B1-23	It is equivalent to ZnO	Embodiment B1-22	It is equivalent to ZnO	Ni(II) 3	Cu 0.5	Ni(II) 0.5	Al 1	- -	Ti 0.5	- -	20	Propiono	0.6	- -	22	Propiono	0.5	1.2	Micro- green	6	20	31	76	0.9	Micro- green	2	16	29	76
Comparative example B1-23	It is equivalent to ZnO	Comparative example B1-7	It is equivalent to ZnO	Fe(III) 2.2	- -	Ni(II) 0.5	- -	- -	Ti 0.5	- -	16	Acetyl group	2	- -	22	Propiono	0.5	1.2	Micro- green	6	20	31	76	3	Yellow	15	24	40	70

[embodiment B1-24]:

Using the identical consersion unit of embodiment B1-1, it will be sent into reactor containing the mixture of 183 parts of anhydrous zinc acetates, 20 part of four acetate hydrate manganese (II), 3 parts of anhydrous acetic acid indiums and 4150 parts of 2- propyl alcohol, and then purge its gas phase portion with nitrogen.Hereafter, the temperature of mixture is increased from 20 DEG C under stiring, and heating is kept for 5 hours at 180 DEG C ± 1 DEG C, to be reacted, metal oxide particle is generated, is then cooled down, so that obtained includes the dispersion (124) of the reaction solution containing 2wt% metal oxide particle.

The dispersion of generation is evaluated with embodiment B1-9 identical method.Its result is included in table 13.

[embodiment B1-25 to B1-33 and comparative example B1-8 to B1-9]:

Be made by being heated mixture together with alcohol within the scope of 120-200 DEG C with the identical method of embodiment B1-24 includes the dispersion (125) to (133) and (c18) to (c19) for being wherein dispersed with the reaction solution for the metal oxide particle that granule density is 2wt%, the difference is that as shown in table 12, change the material type being packed into (as the raw material of addition, additive shown in table 12 is also included within wherein).

The dispersion liquid of generation is evaluated with embodiment B1-9 identical method.Its result is included in table 13.

The fine grained in dispersion liquid made from embodiment B1-24 to B1-33 is evaluated with the uniformity of distribution.As a result, any situation is all chosen as "○".

Table 12

	Zinc compound	M1 compound	M2 compound	M3 compound	The metallic compound of surface treatment
	Zinc compound	M1 compound	M2 compound	M3 compound	The metallic compound of surface treatment	Embodiment B1-24	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Anhydrous acetic acid indium	-
Embodiment B1-25	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Anhydrous acetic acid indium	-	-	Embodiment B1-24	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Anhydrous acetic acid indium	-
Embodiment B1-25	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Anhydrous acetic acid indium	-	-	Embodiment B1-26	Anhydrous zinc acetate	Acetic acid dihydrate manganese (III)	Aluminium-sec-butylate (III)	Ferric acetate (II)	-
Embodiment B1-27	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Anhydrous acetic acid indium	Bismuth acetate (III) oxide	-	Embodiment B1-26	Anhydrous zinc acetate	Acetic acid dihydrate manganese (III)	Aluminium-sec-butylate (III)	Ferric acetate (II)	-
Embodiment B1-27	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Anhydrous acetic acid indium	Bismuth acetate (III) oxide	-	Embodiment B1-28	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Tin acetate (IV)	Anhydrous acetic acid indium	Tetramethoxy-silicane
Embodiment B1-29	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Tin acetate (II)	Anhydrous acetic acid indium	Tetrabutyl zirconate oligomer (condensation degree: 6-10)	Embodiment B1-28	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Tin acetate (IV)	Anhydrous acetic acid indium	Tetramethoxy-silicane
Embodiment B1-29	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Tin acetate (II)	Anhydrous acetic acid indium	Tetrabutyl zirconate oligomer (condensation degree: 6-10)	Embodiment B1-30	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Cerium acetate hydrate (III)	-	Four titanium butoxide tetramers
Embodiment B1-31	Anhydrous zinc acetate	Anhydrous manganese acetate (II)	Four titanium n-butoxides	Anhydrous acetic acid indium	-	Embodiment B1-30	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Cerium acetate hydrate (III)	-	Four titanium butoxide tetramers
Embodiment B1-31	Anhydrous zinc acetate	Anhydrous manganese acetate (II)	Four titanium n-butoxides	Anhydrous acetic acid indium	-	Embodiment B1-32	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Bismuth acetate (III)	-	-
Embodiment B1-33	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Anhydrous cupric acetate (II)	-	-	Embodiment B1-32	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Bismuth acetate (III)	-	-
Embodiment B1-33	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	Anhydrous cupric acetate (II)	-	-	Comparative example B1-8	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	-	-	-
Comparative example B1-9	Anhydrous zinc acetate	Anhydrous acetic acid indium	-	-	-	Comparative example B1-8	Anhydrous zinc acetate	Four acetate hydrate manganese (II)	-	-	-

Table 13

	X-ray diffractogram	Fine grain metal forms (x-ray fluorescence analysis)				Crystal grain diameter Dw (nm)	The binding capacity of acyl group		Transparent turbidity (%)	Tone	Ultraviolet radiation absorption property (%)			600 nm of transmission of visible light (%)
		Fine grain metal forms (x-ray fluorescence analysis)					The binding capacity of acyl group				Ultraviolet radiation absorption property (%)				M1 atom %/Zn	M2 atom %/Zn	M3 atom %/Zn	Ms atom %/Zn	Identification	Binding capacity mol%/Zn	380 nm	400 nm	420 nm
		Embodiment B1-24	It is equivalent to ZnO	Mn(II) 6.4	In 1		- -	- -			15	Acetyl group	1.6		M1 atom %/Zn	M2 atom %/Zn	M3 atom %/Zn	Ms atom %/Zn	Identification	Binding capacity mol%/Zn	380 nm	400 nm	420 nm	0.7	It is light yellow	3	11	19	77
Embodiment B1-25	It is equivalent to ZnO	Embodiment B1-24	It is equivalent to ZnO	Mn(II) 6.4	In 1	Mn(II) 1.8	- -	- -	In 1	- -	15	Acetyl group	1.6	- -	14	Acetyl group	1.6	1.5	It is light yellow	4	26	41	89	0.7	It is light yellow	3	11	19	77
Embodiment B1-25	It is equivalent to ZnO	Embodiment B1-26	It is equivalent to ZnO	Mn(III) 4	Al 0.2	Mn(II) 1.8	Fe(II) 1.2	- -	In 1	- -	15	Acetyl group	1.8	- -	14	Acetyl group	1.6	1.5	It is light yellow	4	26	41	89	0.7	It is light yellow	3	20	36	82
Embodiment B1-27	It is equivalent to ZnO	Embodiment B1-26	It is equivalent to ZnO	Mn(III) 4	Al 0.2	Mn(II) 6.2	Fe(II) 1.2	- -	In 0.8	Bi 1.7	15	Acetyl group	1.8	- -	15	Acetyl group	1.6	0.8	It is light yellow	2	8	15	80	0.7	It is light yellow	3	20	36	82
Embodiment B1-27	It is equivalent to ZnO	Embodiment B1-28	It is equivalent to ZnO	Mn(II) 3.3	Sn 0.2	Mn(II) 6.2	In 1	Si 2	In 0.8	Bi 1.7	10	Acetyl group	2.3	- -	15	Acetyl group	1.6	0.8	It is light yellow	2	8	15	80	0.3	It is light yellow	3	17	29	80
Embodiment B1-29	It is equivalent to ZnO	Embodiment B1-28	It is equivalent to ZnO	Mn(II) 3.3	Sn 0.2	Mn(II) 6.3	In 1	Si 2	Sn(II) 0.4	In 1	10	Acetyl group	2.3	Zr 0.5	14	Acetyl group	3	0.2	It is yellowish	3	18	29	87	0.3	It is light yellow	3	17	29	80
Embodiment B1-29	It is equivalent to ZnO	Embodiment B1-30	It is equivalent to ZnO	Mn(II) 6.2	Ce(III) 1.8	Mn(II) 6.3	- -	Ti 1	Sn(II) 0.4	In 1	14	Acetyl group	3.2	Zr 0.5	14	Acetyl group	3	0.2	It is yellowish	3	18	29	87	0.2	Yellow	4	11	17	72
Embodiment B1-31	It is equivalent to ZnO	Embodiment B1-30	It is equivalent to ZnO	Mn(II) 6.2	Ce(III) 1.8	Mn(II) 6.2	- -	Ti 1	Ti 1	In 1	14	Acetyl group	3.2	- -	15	Acetyl group	4	0.5	It is light yellow	2	9	17	75	0.2	Yellow	4	11	17	72
Embodiment B1-31	It is equivalent to ZnO	Embodiment B1-32	It is equivalent to ZnO	Mn(II) 6.5	Bi 2	Mn(II) 6.2	- -	- -	Ti 1	In 1	15	Acetyl group	1.9	- -	15	Acetyl group	4	0.5	It is light yellow	2	9	17	75	0.8	Yellow	7	10	17	80
Embodiment B1-33	It is equivalent to ZnO	Embodiment B1-32	It is equivalent to ZnO	Mn(II) 6.5	Bi 2	Mn(II) 5.8	- -	- -	Cu 0.5	- -	15	Acetyl group	1.9	- -	15	Acetyl group	1.7	0.6	It is yellowish	2	12	20	75	0.8	Yellow	7	10	17	80
Embodiment B1-33	It is equivalent to ZnO	Comparative example B1-8	It is equivalent to ZnO	Mn(II) 6.3	- -	Mn(II) 5.8	- -	- -	Cu 0.5	- -	16	Acetyl group	1.5	- -	15	Acetyl group	1.7	0.6	It is yellowish	2	12	20	75	1.2	Yellow	10	20	34	70
Comparative example B1-9	It is equivalent to ZnO	Comparative example B1-8	It is equivalent to ZnO	Mn(II) 6.3	- -	In 1	- -	- -	- -	- -	16	Acetyl group	1.5	- -	15	Acetyl group	3	1.2	It is colourless	20	57	70	87	1.2	Yellow	10	20	34	70

[embodiment B1-34 to B1-40 and comparative example B1-10 to B1-14]:

By dispersion (134) to (140) and (c110) to (c114) that the metal oxide particle reaction solution dispersed therein for being 2wt% containing granule density is made with the identical method of embodiment B1-1, the difference is that as shown in table 14, changing the raw material type of addition.

The dispersion of generation is evaluated with embodiment B1-9 identical method.Its result is included in table 15.

The fine grained in dispersion made from embodiment B1-34 to B1-40 is evaluated with the uniformity of distribution.As a result, not seeing that containing the metallic element (M1, M2, M3 of table 10) being added, as (super) thin monometallic particle of main component or the segregation of metal oxide particle, any situation is all chosen as "○".

For can be worth by the combination that photoelectron spectroscopy measures judgement metalliferous chemical valence material, these chemical valences are tabulated below.

Table 14

	Zinc compound	M1 compound	M2 compound	M3 compound
	Zinc compound	M1 compound	M2 compound	M3 compound	Embodiment B1-34	Anhydrous zinc acetate	Cerium acetate hydrate (III)	Anhydrous acetic acid indium	-
Embodiment B1-35	Anhydrous zinc propionate	Cerium acetate hydrate (III)	Bismuth acetate (III)	-	Embodiment B1-34	Anhydrous zinc acetate	Cerium acetate hydrate (III)	Anhydrous acetic acid indium	-
Embodiment B1-35	Anhydrous zinc propionate	Cerium acetate hydrate (III)	Bismuth acetate (III)	-	Embodiment B1-36	Anhydrous zinc acetate	Tin acetate (II)	Aluminium-sec-butylate (III)	-
Embodiment B1-37	Anhydrous zn formate	Tin acetate (IV)	Four titanium n-butoxides	-	Embodiment B1-36	Anhydrous zinc acetate	Tin acetate (II)	Aluminium-sec-butylate (III)	-
Embodiment B1-37	Anhydrous zn formate	Tin acetate (IV)	Four titanium n-butoxides	-	Embodiment B1-38	Anhydrous zinc acetate	Anhydrous acetic acid silver (I)	Tin acetate (IV)	-
Embodiment B1-39	Anhydrous zinc acetate	Anhydrous acetic acid silver (I)	Bismuth acetate (III) oxide	-	Embodiment B1-38	Anhydrous zinc acetate	Anhydrous acetic acid silver (I)	Tin acetate (IV)	-
Embodiment B1-39	Anhydrous zinc acetate	Anhydrous acetic acid silver (I)	Bismuth acetate (III) oxide	-	Embodiment B1-40	Anhydrous zinc acetate	Anhydrous acetic acid silver (I)	Anhydrous acetic acid indium	Bismuth acetate (III) oxide
Comparative example B1-10	Anhydrous zinc acetate	Aluminium-sec-butylate (III)	-	-	Embodiment B1-40	Anhydrous zinc acetate	Anhydrous acetic acid silver (I)	Anhydrous acetic acid indium	Bismuth acetate (III) oxide
Comparative example B1-10	Anhydrous zinc acetate	Aluminium-sec-butylate (III)	-	-	Comparative example B1-11	Anhydrous zinc acetate	Four titanium n-butoxides	-	-
Comparative example B1-12	Anhydrous zinc acetate	Tin acetate (IV)	-	-	Comparative example B1-11	Anhydrous zinc acetate	Four titanium n-butoxides	-	-
Comparative example B1-12	Anhydrous zinc acetate	Tin acetate (IV)	-	-	Comparative example B1-13	Anhydrous zinc acetate	Cerium acetate hydrate (III)	-	-
Comparative example B1-14	Anhydrous zinc acetate	Anhydrous acetic acid silver (I)	-	-	Comparative example B1-13	Anhydrous zinc acetate	Cerium acetate hydrate (III)	-	-

Table 15

	X-ray diffractogram	Fine grain metal forms (x-ray fluorescence analysis)			Crystal grain diameter Dw (nm)	The binding capacity of acyl group		Transparent turbidity (%)	Tone	Ultraviolet radiation absorption property (%)			Transmission of visible light (%)
		Fine grain metal forms (x-ray fluorescence analysis)				The binding capacity of acyl group				Ultraviolet radiation absorption property (%)			Transmission of visible light (%)	M1 atom %/Zn	M2 atom %/Zn	M3 atom %/Zn	Identification	Binding capacity mol%/Zn	380 nm	400 nm	420 nm	600 nm
		Embodiment B1-34	It is equivalent to ZnO	Ce(III) 1		In 1	- -			13	Acetyl group	3	0.2	M1 atom %/Zn	M2 atom %/Zn	M3 atom %/Zn	Identification	Binding capacity mol%/Zn	380 nm	400 nm	420 nm	600 nm	It is colourless	4	28	41	81
Embodiment B1-35	It is equivalent to ZnO	Embodiment B1-34	It is equivalent to ZnO	Ce(III) 1	Ce(III) 2.5	In 1	- -	Bi 0.5	- -	13	Acetyl group	3	0.2	15	Propiono	1.7	0.9	It is yellowish	4	10	12	83	It is colourless	4	28	41	81
Embodiment B1-35	It is equivalent to ZnO	Embodiment B1-36	It is equivalent to ZnO	Sn(II) 1	Ce(III) 2.5	Al 1	- -	Bi 0.5	- -	14	Acetyl group	2	0.3	15	Propiono	1.7	0.9	It is yellowish	4	10	12	83	It is colourless	6	18	27	83
Embodiment B1-37	It is equivalent to ZnO	Embodiment B1-36	It is equivalent to ZnO	Sn(II) 1	Sn 1	Al 1	- -	Ti 1	- -	14	Acetyl group	2	0.3	13	Formoxyl	2.3	0.5	It is colourless	4	23	35	80	It is colourless	6	18	27	83
Embodiment B1-37	It is equivalent to ZnO	Embodiment B1-38	It is equivalent to ZnO	Ag(I) 0.6	Sn 1	Sn(IV) 1.2	- -	Ti 1	- -	15	Acetyl group	1.8	0.5	13	Formoxyl	2.3	0.5	It is colourless	4	23	35	80	Yellow	3	4	1	77
Embodiment B1-39	It is equivalent to ZnO	Embodiment B1-38	It is equivalent to ZnO	Ag(I) 0.6	Ag 0.5	Sn(IV) 1.2	- -	Bi 1	- -	15	Acetyl group	1.8	0.5	12	Acetyl group	3.1	0.4	Yellow	5	6	3	77	Yellow	3	4	1	77
Embodiment B1-39	It is equivalent to ZnO	Embodiment B1-40	It is equivalent to ZnO	Ag 0.1	Ag 0.5	In 0.9	Bi 0.5	Bi 1	- -	12	Acetyl group	2.9	0.6	12	Acetyl group	3.1	0.4	Yellow	5	6	3	77	Yellow	4	10	12	80
Comparative example B1-10	It is equivalent to ZnO	Embodiment B1-40	It is equivalent to ZnO	Ag 0.1	Al 1.5	In 0.9	Bi 0.5	- -	- -	12	Acetyl group	2.9	0.6	15	Acetyl group	3	0.8	It is colourless	22	58	70	77	Yellow	4	10	12	80
Comparative example B1-10	It is equivalent to ZnO	Comparative example B1-11	It is equivalent to ZnO	Ti 1.5	Al 1.5	- -	- -	- -	- -	15	Acetyl group	3	1	15	Acetyl group	3	0.8	It is colourless	22	58	70	77	It is colourless	21	58	68	76
Comparative example B1-12	It is equivalent to ZnO	Comparative example B1-11	It is equivalent to ZnO	Ti 1.5	Sn 1.5	- -	- -	- -	- -	15	Acetyl group	3	1	15	Acetyl group	3	0.9	It is colourless	26	58	70	77	It is colourless	21	58	68	76
Comparative example B1-12	It is equivalent to ZnO	Comparative example B1-13	It is equivalent to ZnO	Ce(III) 1.5	Sn 1.5	- -	- -	- -	- -	15	Acetyl group	3	0.9	15	Acetyl group	3	0.9	It is colourless	26	58	70	77	It is colourless	23	48	60	77
Comparative example B1-14	It is equivalent to ZnO	Comparative example B1-13	It is equivalent to ZnO	Ce(III) 1.5	Ag 1	- -	- -	- -	- -	15	Acetyl group	3	0.9	14	Acetyl group	0.8	0.8	It is colourless	2	2	1	62	It is colourless	23	48	60	77

The following contents as can be understood from Table 15.Such as in comparative example B1-14, if ZnO argentiferous, the visible light of its absorbable short wavelength, but the transmissivity of its visible light is also lower.It compares, such as in embodiment B1-38 into B1-40, if also containing other miscellaneous metallic element other than silver, while keeping the absorbability of short-wavelength visible light, it is seen that the transmissivity of light is also got higher.

The metal oxide particle made from above-described embodiment B1-9 to B1-40 is not more than 30nm perpendicular to the crystal grain diameter in crystal face (002) direction.Furthermore, the metal oxide particle made from above-described embodiment B1-9 to B1-15, all it is not more than 20nm perpendicular to the crystal grain diameter in crystal face (002) direction under any circumstance, and is all not less than 10nm perpendicular to the crystal grain diameter in crystal face (110) direction under any circumstance.

[embodiment B1-41]:

The dispersion for the reaction solution for being 4wt% containing granule density is made with the identical method of embodiment B1-10, the difference is that reaction dissolvent changes into methanol.About the fine grain crystal grain diameter of generation, the crystal grain diameter perpendicular to crystal face (110) direction is 8nm, and is 16nm perpendicular to the crystal grain diameter in crystal face (002) direction.In addition, the evaluation about film forming, transparency is turbidity 0.3%, and tone is colourless.In the state of particle dispersion, ultraviolet transmittance is 8% at 380nm, and ultraviolet transmittance is 45% at 420nm, and the transmissivity of visible light is 86%.It can be appreciated that from these results, the fine grained of generation has lower UV absorbing properties than embodiment B1-10.

[embodiment B1-42]:

It will be sent into the identical reactor of embodiment B1-1 containing the mixture of 183 parts of anhydrous acetic acid zinc powders, 12 parts of bismuth acetate (III) oxides, 0.4 part of anhydrous cupric acetate (II) powder, 24 parts of anhydrous acetic acid indium powder and 3850 parts of 1- propyl alcohol, and then purge its gas phase portion with nitrogen.Hereafter, the temperature of mixture is increased under stiring, and heating is kept for 10 hours at 180 DEG C ± 1 DEG C, to be reacted, generate metal oxide particle, then it cools down, so that obtained includes the dispersion (142) of the reaction solution of the grey fine grained (metal oxide particle) containing 2wt% concentration.

It has proven to; fine grained in the dispersion (142) of generation is those particles; they contain ZnO crystal; its crystal grain diameter is 14nm; copper, indium and bismuth containing 0.2 atom %, 4.8 atom % and 3 atom % respectively relative to Zn, and combine relative to its surface Zn the acetyl group of 2.5mol%.

The fine metal oxide particles of dispersion (142) are had rated with the method for above-mentioned (5-3) and (5-4).As a result, ultraviolet radiation absorption property is 8% for the transmissivity at 380nm, the transmissivity at 400nm is 35%, it is seen that the transmissivity under the transmission property of light is 600nm is 85%, and transparency is turbidity 1.2%, and tone is colourless.

[embodiment B1-43]:

Dispersion (143) are made with the same procedure of embodiment B1-42, the difference is that 0.5 part of acetic acid dihydrate lithium is used as other raw material.

It has proven to; fine grained in the dispersion (143) of generation is those particles; they contain ZnO crystal; its crystal grain diameter is 12nm; copper, indium, bismuth and lithium containing 0.2 atom %, 7.8 atom %, 3.8 atom % and 0.5 atom % respectively relative to Zn, and combine relative to its surface Zn the acetyl group of 2.4mol%.

The fine metal oxide particles of dispersion (143) are had rated with the identical method of embodiment B1-42.As a result, ultraviolet radiation absorption property is the transmissivity at 380nm for no more than 1%, the transmissivity at 400nm is 20%, it is seen that the transmissivity under the transmission property of light is 600nm is 87%, and transparency is turbidity 0.3%, and tone is colourless.

[embodiment B1-44]:

Dispersion (144) are made with the same procedure of embodiment B1-9, the difference is that 0.07 part of anhydrous sodium acetate is used as other raw material.

The dispersion (144) of generation is had rated with the identical method of embodiment B1-9.As a result, metal oxide particle in dispersion (144) is the fine grained that those crystal grain diameters are 14nm, and contain the ZnO crystal containing Cu, In and Na, Cu, In and Na containing 0.4 atom %, 0.8 atom % and 0.08 atom % respectively relative to Zn.Ultraviolet radiation absorption property is that the transmissivity at 380nm is 3%, and the transmissivity at 420nm is 48%, it is seen that the transmissivity under the transmission property of light is 600nm is 85%.

[embodiment B1-45]:

Dispersion (145) are made with the same procedure of embodiment B1-18, the difference is that 0.3 part of cesium acetate is used as a kind of other raw material.

The dispersion (145) of generation is had rated with the identical method of embodiment B1-18.As a result, the metal oxide particle in dispersion (145) is the fine grained that those crystal grain diameters are 18nm, and contain the ZnO crystal containing Fe, Ce and Cs, Fe, Ce and Cs containing 0.2 atom %, 0.5 atom % and 0.2 atom % respectively relative to Zn.Ultraviolet radiation absorption property is that the transmissivity at 380nm is 2%, and the transmissivity at 420nm is 22%, it is seen that the transmissivity under the transmission property of light is 600nm is 78%.

[embodiment B1-46]:

Dispersion (146) are made with the same procedure of embodiment B1-24, the difference is that 0.1 part of four acetate hydrate magnesium is used as other raw material.

The dispersion (146) of generation is had rated with the identical method of embodiment B1-24.As a result, metal oxide particle in dispersion (146) is the fine grained that those crystal grain diameters are 15nm, they contain the ZnO crystal containing Mn, In and Mg, Mn, In and Mg containing 6.6 atom %, 1 atom % and 0.04 atom % respectively relative to Zn.Ultraviolet radiation absorption property is that the transmissivity at 380nm is not more than 1%, and the transmissivity at 420nm is 15%, it is seen that the transmissivity under the transmission property of light is 600nm is 78%.

[embodiment B2-1]:

Reaction solution (11) (granule density: 4.4wt%) made from 1000 parts of embodiment B1-1 is heated under normal pressure, to distill out 710 parts of solvent composition such as methanol, so that reaction solution (11) be made to be concentrated.When this concentration of reaction solution further heats, ethyl alcohol is continuously added dropwise, to while distilling out remaining solvent composition from reaction solution, solvent displacement is carried out with ethyl alcohol, so that the dispersion (21) of metal oxide particle dispersion in ethanol, which is made, is used as film-forming composition, granule density 25wt%.

The dispersion stabilization and transparency of the dispersion (21) of generation are had rated in aforementioned manners.Its result is included in table 16 together with discrete particles diameter.

[embodiment B2-2 to B2-5]:

The identical method of embodiment B2-1 is used to be made as dispersion (22)-(25) of film-forming composition, the difference is that as shown in table 16, changing the reaction solution used, for the solvent and granule density of solvent displacement.

The dispersion stabilization and transparency of the dispersion (22) to (25) of generation are had rated in aforementioned manners.Its result is included in table 16 together with discrete particles diameter.

[embodiment B2-6]:

Reaction solution (12) (granule density: 4.4wt%) made from 1000 parts of embodiment B1-2 is heated under normal pressure, to distill out 710 parts of solvent compositions such as 1- propyl alcohol, so that reaction solution (12) be made to be concentrated.When this concentration of reaction solution further heats, the tert-butyl alcohol is continuously added dropwise, to carry out solvent displacement with the tert-butyl alcohol while distilling out remaining solvent composition from reaction solution.Furthermore, partial hydrolysis-condensation product (trimer to pentamer) of tetramethoxy-silicane is used as additive to be added in (being replaced by above-mentioned solvent) dispersion, relative to the metal oxide particle in above-mentioned dispersion, its recipe ratio is 6wt%, then the mixture of generation is subjected to ultrasonic wave homogenize process, if desired, then adjusting its granule density.As a result, metal oxide particle, which is made, is dispersed in the dispersion (26) in the tert-butyl alcohol as film-forming composition, granule density 20wt%.

The dispersion stabilization and transparency of the dispersion (26) of generation are had rated in aforementioned manners.Its result is included in table 16 together with discrete particles diameter.

[embodiment B2-7 to B2-9]:

The identical method of embodiment B2-6 is used to be made as dispersion (27)-(29) of film-forming composition, the difference is that as shown in table 16, changing the reaction solution used, for the solvent of solvent displacement, the type of additive and recipe ratio and granule density.

The dispersion stabilization and transparency of the dispersion (27) to (29) of generation are had rated in aforementioned manners.Its result is included in table 16 together with the diameter of discrete particles.

Table 16

	Reaction solution used	Dispersion obtained				Additive		Evaluation result
		Dispersion obtained				Additive		Evaluation result		Number	Solvent	Granule density wt%	Discrete particles diameter μm	Type	Additional amount wt%/particle	Dispersion stabilization	Transparency
		Embodiment B2-1	11	21	Ethyl alcohol	25	0.34	-	0	Number	Solvent	Granule density wt%	Discrete particles diameter μm	Type	Additional amount wt%/particle	Dispersion stabilization	Transparency	C	C
Embodiment B2-2	12	Embodiment B2-1	11	21	Ethyl alcohol	25	0.34	-	0	22	N-butyl alcohol	26	0.31	-	0	C	C	C	C
Embodiment B2-2	12	Embodiment B2-3	13	23	MIBK	25	0.50	-	0	22	N-butyl alcohol	26	0.31	-	0	C	C	C	C
Embodiment B2-4	15	Embodiment B2-3	13	23	MIBK	25	0.50	-	0	24	Butyl acetate	20	0.14	-	0	B	B	C	C
Embodiment B2-4	15	Embodiment B2-5	18	25	PGM	20	0.09	-	0	24	Butyl acetate	20	0.14	-	0	B	B	A	A
Embodiment B2-6	12	Embodiment B2-5	18	25	PGM	20	0.09	-	0	26	The tert-butyl alcohol	20	0.08	*1	6	A	A	A	A
Embodiment B2-6	12	Embodiment B2-7	12	27	N-butyl alcohol	20	0.07	*2	0.8	26	The tert-butyl alcohol	20	0.08	*1	6	A	A	A	A
Embodiment B2-8	12	Embodiment B2-7	12	27	N-butyl alcohol	20	0.07	*2	0.8	28	PGMAC	20	0.05	*3	2	A	A	A	A
Embodiment B2-8	12	Embodiment B2-9	11	29	Ethyl alcohol	20	0.10	*4	4	28	PGMAC	20	0.05	*3	2	A	A	B	B

(note):

* 1: partial hydrolysis-condensation product (trimer to pentamer) of tetramethoxy-silicane

* 2: four titanium n-butoxides (IV) tetramer

* 3: n-butoxy aluminium (III) trimer

* 4: four titanium n-butoxides (IV) (monomer)

PGM: propylene glycol monomethyl ether

PGMAC: propylene glycol monomethyl ether

MIBK: methyl iso-butyl ketone (MIBK)

[embodiment B2-10 to B2-15]:

The identical method of embodiment B2-1 is used to be made as dispersion (210)-(215) of film-forming composition, the difference is that dispersion shown in table 17 is used as the reaction solution used, and it is as shown in table 17, change for the solvent of solvent displacement, the type of additive and recipe ratio and granule density.

The granule density and discrete particles diameter of dispersions obtained (210)-(215) are included in table 17.

Table 17

	Reaction solution used	Dispersion obtained				Additive
		Dispersion obtained				Additive		Number	Solvent	Granule density wt%	Discrete particles diameter μm	Type	Additional amount wt%/particle
		Embodiment B2-10	The dispersion of embodiment B1-10	210	Dipropylene glycol	20	0.04	Number	Solvent	Granule density wt%	Discrete particles diameter μm	Type	Additional amount wt%/particle	-	0
Embodiment B2-11	The dispersion of embodiment B1-16	Embodiment B2-10	The dispersion of embodiment B1-10	210	Dipropylene glycol	20	0.04	211	N-butyl alcohol	20	0.04	-	0	-	0
Embodiment B2-11	The dispersion of embodiment B1-16	Embodiment B2-12	The dispersion of embodiment B1-24	212	MIBK	25	0.04	211	N-butyl alcohol	20	0.04	-	0	*1	5
Embodiment B2-13	The dispersion of embodiment B1-34	Embodiment B2-12	The dispersion of embodiment B1-24	212	MIBK	25	0.04	213	PGMAC	25	0.05	*2	0.5	*1	5
Embodiment B2-13	The dispersion of embodiment B1-34	Embodiment B2-14	The dispersion of embodiment B1-36	214	Toluene	30	0.02	213	PGMAC	25	0.05	*2	0.5	*2	12
Embodiment B2-15	The dispersion of embodiment B1-38	Embodiment B2-14	The dispersion of embodiment B1-36	214	Toluene	30	0.02	215	Dimethylbenzene	20	0.09	-	0	*2	12

(note):

* 2: four titanium n-butoxides (IV) tetramer

PGMAC: propylene glycol monomethyl ether

MIBK: methyl iso-butyl ketone (MIBK)

[embodiment B2-16]:

By 100 parts of dispersions (215) (as made from embodiment B2-15), 50 parts of fluororesin (resin concentrations: 40wt%, solvent: dimethylbenzene) and 50 parts of dimethylbenzene (as retarder thinner) mix, then decentralized processing is carried out with homogenizer, so that a kind of coating be made.

Resin concentration, granule density and the discrete particles diameter for generating coating are included in table 18.

[embodiment B2-17 to B2-20]:

Coating is made with the identical method of embodiment B2-16, the difference is that replacing fluororesin using dispersion shown in table 18 and the resin shown in table 18.

Table 18

	The number of the dispersion used	The resin used	Granule density wt%	Resin concentration wt%	Discrete particles diameter μm
	The number of the dispersion used	The resin used	Granule density wt%	Resin concentration wt%	Discrete particles diameter μm	Embodiment B2-16	215	Fluororesin	10	10	0.03
Embodiment B2-17	212	Polyester resin	10	10	0.07	Embodiment B2-16	215	Fluororesin	10	10	0.03
Embodiment B2-17	212	Polyester resin	10	10	0.07	Embodiment B2-18	213	Butyral resin	1	20	0.05
Embodiment B2-19	211	Acrylic polyol	20	10	0.03	Embodiment B2-18	213	Butyral resin	1	20	0.05
Embodiment B2-19	211	Acrylic polyol	20	10	0.03	Embodiment B2-20	210	Silica sol	10	10	0.03

[embodiment B3-1]:

100 parts of dispersions (27) (as made from embodiment B2-7) and 20 parts of silicate adhesives (are pressed into SiO₂Count solid component content: 51wt%) and 0.2 part of catalyst (n-butylamine) mixing, so that a kind of coating be made.The discrete particles diameter for generating coating is 0.048 μm.

The coating of generation alkali-free glass is coated to stick coating machine (to be produced by CorningInternational Corporation, barium borosilicate glass, glass code 7059, thickness: 0.6mm) on, wet film with a thickness of scheduled thickness (24 μm, 45 μm, 66 μm).Hereafter, they are normally dried at 25 DEG C, so that the glass for forming metal oxide particle dispersion membrane on the surface thereof be made (different based on wet-film thickness, there are three types of different thickness of dry film).The glass of these dispersion films coating is that fabulous ultraviolet light cuts off glass.The transmitted spectrum of the glass of these dispersion films coating is shown in Fig. 8.

The glass that the dispersion film of generation is coated carries out above-mentioned evaluation.As a result, the transparency of visible light is " zero (turbidity: being not more than 1%) ", and coloring degree is "○".By the way, the transmissivity (%) under each wavelength about the only alkali-free glass for being used as substrate, any one transmissivity at 380nm, 400nm and 500nm are all 91% (in embodiment B cited below also so).

[embodiment B3-2]:

Dispersion (27) made from 100 parts of embodiment B2-7 and 50 parts of acrylic resin adhesives (are contained into polyisocyanate curing agent；All solids constituent content: 50wt%) and 50 parts of solvent (butyl acetate-toluene) mixing, so that a kind of coating be made.The discrete particles diameter that coating is made is 0.015 μm.

The coating of generation is coated on PET film with stick coating machine, wet film with a thickness of scheduled thickness (24 μm, 45 μm, 66 μm).Hereafter, they are heated 5 minutes at 100 DEG C, so that the ZnO particle that formation Co-In codope on the surface thereof is made is dispersed in the PET film (three kinds of different film thickness) of the dispersion film in acrylic resin.The fabulous ultraviolet light for the glass that the dispersion film that the PET film of these dispersion films coating is similar embodiment B3-1 coats cuts off film.

The PET film that the dispersion film of generation is coated carries out above-mentioned evaluation.As a result, the transparency of visible light is "○", and coloring degree is "○".By the way, about transmissivity (%) of the only PET film of substrate under each wavelength is used as, any one transmissivity at 380nm, 400nm, 420nm and 500nm is all 85 ± 1%.

[embodiment B3-3]:

Dispersion made from embodiment B2-7 (27) is coated on the identical alkali-free glass of embodiment B3-1 with stick coating machine, then its temperature is increased from room temperature in calcining furnace, and it is kept for 1 hour at 400 DEG C, then it cools down, so that the glass for forming the ZnO particle film of Co-In codope on the surface thereof be made.

The glass of the thin film coated of generation is subjected to above-mentioned evaluation.As a result, the transparency of visible light is "○" (turbidity: being not more than 1%), and coloring degree is "○".About the transmission property of visible light, the transmissivity at 500nm is 88%.About ultraviolet radiation absorption property, the transmissivity at 400nm is 60%.

[embodiment B3-4]:

By dispersion (27) made from 100 parts of embodiment B2-7 and 10 parts of ultraviolet-curable coating agents (" HIC2000 " of KYOEISHA CHEMICAL Co., LTD. production；All solids constituent content: 50wt%；Refractive index: 1.576) mixing (as binder solution) with 15 parts of solvents (methyl ethyl ketone), so that a kind of coating that all solids constituent content is 20wt% be made.

The coating of generation is coated on PET film with stick coating machine, then solidifies 10 minutes and heat drying 1 minute at 100 DEG C, then with ultraviolet light irradiation (the ultraviolet exposure metering: 600mJ/cm of high-pressure sodium lamp²) to the PET film of the obtained film for forming 5 μm of thickness of dry film on the surface thereof.

With the PET film for the film coating that refractive index and visible transparency (turbidity) evaluation generate.As a result, refractive index is not less than 1.7, and turbidity is less than 1%.In addition, the transmissivity of the PET film of resulting film coating is less than 20% at 380nm, and the transmissivity at 500nm is that 80% and film have fabulous ultraviolet light blocking ability.

[embodiment B3-5]:

Use stick coating machine that dispersion made from embodiment B1-9 (19) is coated to as on the alkali glass of substrate, then it dries at normal temperature, it is heated 1 hour under 400 DEG C and nitrogen atmosphere in heating furnace, so that the substrate for forming the film coating of the film of 0.5 μm of film thickness on the surface thereof be made.

The substrate that the film of generation is coated carries out above-mentioned evaluation.As a result, the substrate of film coating is provided with ZnO crystal film, the film Cu, In and Si containing 0.4 atom %, 0.8 atom % and 5 atom % respectively relative to Zn, and block glass for a kind of colourless ultraviolet light, ultraviolet radiation absorption property be 50% in the transmissivity under 380nm and visible transmission property is that transmissivity at 600nm is 88% and transparency is turbidity 0.8%.

[embodiment B3-6]:

Use stick coating machine that dispersion made from embodiment B1-30 (130) is coated to as on the alkali glass of substrate, then it dries at normal temperature, it is heated 1 hour under 400 DEG C and nitrogen atmosphere in heating furnace, so that the substrate for forming the film coating of the film of 1.2 μm of film thickness on the surface thereof be made.

The substrate that the film of generation is coated carries out above-mentioned evaluation.As a result, the substrate of film coating is provided with ZnO crystal film, Mn, Ce and the Ti of the film relative to Zn respectively containing 6.2 atom %, 1.8 atom % and 1 atom %, and block glass for a kind of ultraviolet light, ultraviolet radiation absorption property be 20% in the transmissivity under 380nm and visible transmission property is that transmissivity at 600nm is 88% and transparency is turbidity 0.3%.

[embodiment B4-1]:

It will be packed into reactor identical with embodiment B1-1 containing the mixture of 303 parts of titanium methoxy propyl oxides, the ethanol solution of 3.5 part of 21% ethyoxyl iron (III) compound, the diethylene glycol monoethyl ether solution of 22 part of 15% aluminium (III) ethoxy ethoxy b-oxide, 4 parts of copper (II) 2- (2- Butoxyethoxy) b-oxides, 2400 parts of glycol dimethyl ethers and 270 parts of acetic acid, then with the gas phase portion of nitrogen purge.Then, the temperature of mixture (from 20 DEG C) is increased to 180 DEG C under stiring, then heating keeps being reacted for 5 hours at 180 DEG C ± 1 DEG C, form metal oxide particle, then it cools down, so that the reaction solution (41) that the fine particle concentration containing fine grained (metal oxide particle) is 2wt% be made.In addition, the reaction solution of generation is subjected to heated solvent displacement with embodiment B1-1 identical method, so that the dispersion (41) that above-mentioned metal oxide particle is dispersed in n-butyl alcohol is made, granule density 20wt%.

Metal oxide particle in dispersion (41) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 19.By the way, about ultraviolet radiation absorption property and visible transmission property, they are evaluated by the method for above-mentioned (5-3): diluting dispersion with n-butyl alcohol, to which a kind of sample liquid that granule density is 0.1wt% be made, then this sample liquid is packed into the quartz cell of 1cm thickness, by the automatic record spectrophotometer measurement transmitted spectrum of the quartz cell of this filling, from this transmitted spectrum, ultraviolet radiation absorption property and visible transmission property are evaluated by the transmissivity of 380nm and 600nm respectively.

[comparative example B4-1]:

The metal oxide particle that granule density is 20wt% is made with the identical method of embodiment B4-1 and is dispersed in the dispersion (c41) in n-butyl alcohol, the difference is that not using the diethylene glycol monoethyl ether solution of 22 part of 15% aluminium (III) ethoxy ethoxy b-oxide, 4 parts of copper (II) 2- (2- Butoxyethoxy) b-oxides are not used yet.

Metal oxide particle in dispersion (c41) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 19.By the way, about ultraviolet radiation absorption property and visible transmission property, they are evaluated according to above-mentioned (5-3) in method identical with embodiment B4-1.

Table 19

	X-ray diffractogram	Fine grain metal forms (x-ray fluorescence analysis)		Crystal grain diameter nm Ds (101)	Visible transmission property (%) 600nm	Ultraviolet radiation absorption property (%) 380nm
		Fine grain metal forms (x-ray fluorescence analysis)					M1 atom %/Ti	M2 atom %/Ti
		Embodiment B4-1	It is equivalent to TiO₂				M1 atom %/Ti	M2 atom %/Ti	Fe 0.5	Al 1Cu 1.2	6	95	2
Comparative example B4-1	It is equivalent to TiO₂	Embodiment B4-1	It is equivalent to TiO₂	Fe 0.5	- -	7	95	15	Fe 0.5	Al 1Cu 1.2	6	95	2

[embodiment B4-2]:

In stirring and at room temperature, it will be packed into reactor identical with embodiment B1-1 containing the mixture of 50 part of one cerium acetate hydrate (III), 0.6 part of ferric acetate (III) hydroxide, 0.14 part of copper acetate (II) and 3000 parts of pure water, 50 part of 30% aqueous hydrogen peroxide solution is then added.Then, the temperature of mixture (from room temperature) is increased to 90 DEG C under stiring, then heating is kept for 5 hours at 90 DEG C ± 2 DEG C, and 10 part of 30% aqueous hydrogen peroxide solution is then added.Hereafter, heating keeps being reacted for the temperature other 1 hour, metal oxide particle is formed, is then cooled down, so that the reaction solution (42) of the fine grained (metal oxide particle) containing the yellowish and high transparency sense that fine particle concentration is 0.8wt% be made.Then, it is filtered with reaction solution of the ultrafiltration membrane to generation, to remove foreign ion and remaining hydrogen peroxide, while being also concentrated, so that the dispersion (42) that above-mentioned metal oxide particle is dispersed in water is made, granule density 7wt%.

Metal oxide particle in dispersion (42) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 20.By the way, about crystallographic system and crystal structure, particle is so thin, so that generating wide powder x-ray diffraction peak.Therefore, lattice constant is measured by method of electron diffraction and its result is then judged into crystallographic system and crystal structure compared with the data of standard powder.In addition, being judged about primary particle diameter with transmission electron microscope.Furthermore, about ultraviolet radiation absorption property and visible transmission property, they are evaluated by the method for above-mentioned (5-3): diluting dispersion with pure water, to which a kind of sample liquid that granule density is 0.1wt% be made, then this sample liquid is packed into the quartz cell of 1cm thickness, by the automatic record spectrophotometer measurement transmitted spectrum of the quartz cell of this filling, from this transmitted spectrum, ultraviolet radiation absorption property is evaluated by the transmissivity of 380nm and 400nm, it is seen that light transmission properties are evaluated with the transmissivity of 600nm.

[comparative example B4-2]:

The dispersion (c42) that the metal oxide particle that granule density is 7wt% is dispersed in water is made with the identical method of embodiment B4-2, the difference is that not using 0.6 part of ferric acetate (III) hydroxide, 0.14 part of copper acetate (II) is not used yet.

Metal oxide particle in dispersion (c42) is subjected to above-mentioned measurement and evaluation.Its result is included in table 20.By the way, about crystallographic system and crystal structure, primary particle diameter, ultraviolet radiation absorption property and visible transmission property, they are evaluated with method identical with embodiment B4-2.

[comparative example B4-3]:

The dispersion (c43) that the metal oxide particle that granule density is 7wt% is dispersed in water is made with the identical method of embodiment B4-2, the difference is that not using 0.14 part of copper acetate (II).

Metal oxide particle in dispersion (c43) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 20.By the way, about crystallographic system and crystal structure, primary particle diameter, ultraviolet radiation absorption property and visible transmission property, they are evaluated with method identical with embodiment B4-2.

Table 20

	X-ray diffractogram	Fine grain metal forms (x-ray fluorescence analysis)		Principal crystal grain diameter (nm)	Visible transmission property (%) 600nm	Ultraviolet radiation absorption property (%)
		Fine grain metal forms (x-ray fluorescence analysis)				Ultraviolet radiation absorption property (%)		M1 atom %/Ce	M2 atom %/Ce	380nm	400nm
		Embodiment B4-2	It is equivalent to CeO₂			Fe 2	Cu 0.5	M1 atom %/Ce	M2 atom %/Ce	380nm	400nm	2-4	99	< 1	18
Comparative example B4-2	It is equivalent to CeO₂	Embodiment B4-2	It is equivalent to CeO₂	- -	- -	Fe 2	Cu 0.5	2-4	99	29	75	2-4	99	< 1	18
Comparative example B4-2	It is equivalent to CeO₂	Comparative example B4-3	It is equivalent to CeO₂	- -	- -	Fe 2	- -	2-4	99	29	75	2-4	99	5	24

[embodiment B4-3]:

It will be packed into reactor identical with embodiment B1-1 containing the mixture of 146 parts of anhydrous acetic acid indiums, 1.9 parts of ferric acetate (III) hydroxide, 4.25 part of four titanium n-butoxide and 3322 parts of 1- propyl alcohol, and then use the gas phase portion of nitrogen purge.Then, the temperature of mixture (from 20 DEG C) is increased to 180 DEG C under stiring, then heating keeps being reacted for 5 hours at 180 DEG C ± 1 DEG C, form metal oxide particle, then it cools down, so that the reaction solution (43) containing the yellow fine grained (metal oxide particle) that fine particle concentration is 2wt% be made.In addition, the reaction solution of generation is subjected to heated solvent displacement with embodiment B1-1 identical method, so that the dispersion (43) that above-mentioned metal oxide particle is dispersed in n-butyl alcohol is made, granule density 20wt%.

Metal oxide particle in dispersion (43) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 21.By the way, about ultraviolet radiation absorption property and visible transmission property, they are mentioned below.

[embodiment B4-4]:

The reaction solution (44) for the yellow fine grained (metal oxide particle) for being 2wt% containing fine particle concentration is made with the identical method of embodiment B4-3, the difference is that 1.9 parts of ferric acetate (III) hydroxide and 4.25 part of four titanium n-butoxide, 0.2 part of silver acetate and 3.6 parts of tin acetates (IV) replace.In addition, the reaction solution of generation is subjected to heated solvent displacement with embodiment B1-1 identical method, so that the dispersion (44) that above-mentioned metal oxide particle is dispersed in n-butyl alcohol is made, granule density 20wt%.

Metal oxide particle in dispersion (44) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 21.By the way, about ultraviolet radiation absorption property and visible transmission property, they are mentioned below.

[comparative example B4-4]:

The reaction solution (c44) for the yellow fine grained (metal oxide particle) for being 2wt% containing fine particle concentration is made with the identical method of embodiment B4-3, the difference is that not using 1.9 parts of ferric acetate (III) hydroxide, 4.25 part of four titanium n-butoxide is not used yet.In addition, the reaction solution of generation is subjected to heated solvent displacement with embodiment B1-1 identical method, so that the dispersion (c44) that above-mentioned metal oxide particle is dispersed in n-butyl alcohol is made, granule density 20wt%.

Metal oxide particle in dispersion (c44) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 21.By the way, about ultraviolet radiation absorption property and visible transmission property, they are mentioned below.

About embodiment B4-3, the ultraviolet radiation absorption property and visible transmission property of metal oxide particle in every kind of dispersion made from embodiment B4-4 and comparative example B4-4, they are evaluated by the method for above-mentioned (5-1): diluting dispersion with n-butyl alcohol, to which a kind of sample liquid that granule density is 0.5wt% be made, then this sample liquid is packed into the quartz cell of 1cm thickness, by the automatic record spectrophotometer measurement transmitted spectrum of the quartz cell of this filling, from this transmitted spectrum, ultraviolet radiation absorption property is evaluated with the transmissivity under 380nm and 400nm, visible transmission property is evaluated with the transmissivity under 600nm.As a result, transmissivity, that is, visible light absorbent properties under 600nm are equal under any circumstance.But it is lower than comparative example B4-4 about the transmissivity under 380nm and 400nm, embodiment B4-3 and embodiment B4-4.So embodiment B4-3 and embodiment B4-4 has better ultraviolet radiation absorption property than comparative example B4-4.

Table 21

	X-ray diffractogram	Fine grain metal forms (x-ray fluorescence analysis)		Crystal grain diameter (nm) Ds (222)
		Fine grain metal forms (x-ray fluorescence analysis)			M1 atom %/In	M2 atom %/In
		Embodiment B4-3	It is equivalent to In₂O₃		M1 atom %/In	M2 atom %/In	Fe 2	Ti 2.5	4.2
Embodiment B4-4	It is equivalent to In₂O₃	Embodiment B4-3	It is equivalent to In₂O₃	Ag 0.2	Sn 2	4.5	Fe 2	Ti 2.5	4.2
Embodiment B4-4	It is equivalent to In₂O₃	Comparative example B4-4	It is equivalent to In₂O₃	Ag 0.2	Sn 2	4.5	- -	- -	4.8

[embodiment B4-5]:

Dispersion (45) are made with the identical method of embodiment B4-1, the difference is that 2 part of 0.5 acetate hydrate strontium is used as other raw material.

The dispersion (45) generated with the identical method evaluation of embodiment B4-1.As a result, the metal oxide particle in dispersion (45) is to include Detitanium-ore-type TiO₂The crystal grain diameter of crystal is the fine grained of 5nm, the TiO₂Crystal phase Fe, Al, Cu and Sr containing 0.5 atom %, 1 atom %, 1.2 atom % and 1.2 atom % respectively for Ti.Ultraviolet radiation absorption property is that the transmissivity at 380nm is not more than 1%, and visible transmission property is 96% for the transmissivity at 600nm.

[embodiment B5-1]:

Mixture containing 183 parts of anhydrous zinc acetates, 2 parts of silver acetates, 3.5 parts of indium acetates and 3900 parts of 1- propyl alcohol is packed into the identical reactor of embodiment B1-1, then purges its gas phase portion with nitrogen.Hereafter, the temperature of mixture (from 20 DEG C) is risen to 250 DEG C under stiring, and heating is kept for 5 hours at 250 DEG C ± 1 DEG C, to be reacted, metal oxide particle is generated, is then cooled down, contains fine grain reaction solution (51) to be made.

Fine grained in reaction solution (51) is analyzed, consequently found that containing: the ultra-fine silver particles that the super fine zinc oxide particle and crystal grain diameter that crystal grain diameter is 15nm are 18nm, the Zinc oxide particles contain 0.2 atom %Ag and In relative to Zn.Elemental map measurement is carried out by method identical with XMA analytic approach with the transmission electron microscope in above-mentioned evaluation method (3).Thus as a result, discovery is relative to super fine zinc oxide particle, the content of the ultrafine Ag particles of segregation is about 1% by number ratio.

The n-butyl alcohol dispersion that granule density is 20wt% is made by reaction solution (51) with the same procedure of embodiment B1-1.The dispersion liquid of generation is evaluated with the identical method of embodiment B1-9.There is following discovery from their result.About the evaluation of film forming, transparency is turbidity 0.9%, and tone is yellow.In the state (fine particle concentration: 0.1wt%) of particle dispersion, the ultraviolet transmittance at 380nm is 2%, is 1% at 420nm, and transmission of visible light is 65%.

[embodiment B5-2]:

Being added to 1000 parts of (made from embodiment B2-14) granule densities with the Ag powder of nanometric particles that crystal grain diameter prepared by individual method is 8nm for 6 parts is in the toluene dispersion (214) of 30wt%, mix them, then the mixture of generation is subjected to decentralized processing with homogenizer, so that such a dispersion be made: the dispersion of super fine zinc oxide particle containing Sn and Al and with the ratio of 30wt% with which；And wherein dispersion and the ultrafine Ag particles containing 0.6wt%.

The dispersion of generation is evaluated with the identical method of embodiment B1-9.There is following discovery from their result.About the evaluation of film forming, transparency is turbidity 2%, and tone is yellow.In the state of particle dispersion, the ultraviolet transmittance at 380nm is 5%, is 8% at 420nm, and transmission of visible light is 60%.

Then the dispersion dilution with toluene of generation is evaluated to change the concentration of particle and to be reduced to 0.1-0.01wt% with spectral property.As a result, it was confirmed that being the absorption for having the ultrafine Ag particles for absorbing maximum value at about 430nm due to addition in the absorption under 420nm.

[embodiment B5-3]:

In the identical reactor of embodiment B1-1, the mixture of bismuth acetate (III) oxide powder and 1- propyl alcohol is heated at 200 DEG C, so that the superfine bismuth oxide (Bi that one kind is wherein dispersed with and is 20nm containing 2wt% crystal grain diameter be made₂O₃) particle reaction solution.The n-butyl alcohol dispersion that fine particle concentration is 20wt% is made by this reaction solution with embodiment B1-1 identical method.

By 100 parts generate dispersion and 1000 parts of dipropylene glycol dispersions (as made from embodiment B2-10) mix, then decentralized processing is carried out with homogenizer, so that such a dispersion be made: being wherein dispersed with and the super fine zinc oxide particle containing Cu and Ce containing 18wt%；It is wherein dispersed with and the ultra-fine Bi containing 1.8wt%₂O₃Particle.

The dispersion of generation is evaluated with the identical method of embodiment B1-9.There is following discovery from their result.About the evaluation of film forming, transparency is turbidity 0.9%, and tone is yellow.In the state of particle dispersion, the ultraviolet transmittance at 380nm is 2%, is 20% at 420nm, and transmission of visible light is 80%.

[embodiment B5-4]:

In the identical reactor of embodiment B1-1, the mixture of ferric acetate (III) hydroxide powder and 1- propyl alcohol is heated at 160 DEG C, so that a kind of ultra-fine alpha-ferric oxide (α-Fe for being dispersed with and being 15nm containing 2wt% crystal grain diameter be made₂O₃) particle reaction solution (relative to iron, being combined with 5mol% acetyl group).The n-butyl alcohol dispersion that fine particle concentration is 20wt% is made by this reaction solution with embodiment B1-1 identical method.

By 50 parts generate dispersion liquid and 1000 parts of dipropylene glycol dispersions (as made from embodiment B2-10) mix, then decentralized processing is carried out with homogenizer, so that such a dispersion be made: being wherein dispersed with and the super fine zinc oxide particle containing Cu and Ce containing 19wt%；It is wherein dispersed with and the ultra-fine α-Fe containing 0.95wt%₂O₃Particle.

The dispersion of generation is evaluated with the identical method of embodiment B1-9.There is following discovery from their result.About the evaluation of film forming, transparency is turbidity 0.9%, and tone is yellow.In the state of particle dispersion (fine particle concentration=0.1wt%), the ultraviolet transmittance at 380nm is 2%, is 24% at 420nm, and transmission of visible light is 77%.

[the third metal oxide particle]:

Illustrate the measurement and evaluation method in embodiment and comparative example cited below below.

<evaluation of metal oxide particle>:

(1) the crystal identification of metal oxide particle:

For above-mentioned powder sample, the crystallographic system and crystal structure of metal oxide particle are had rated by powder X-ray diffractometry with powder x-ray diffraction equipment (by Rigaku Denki K.K. production, ProductName: RINT 2400).Measuring condition is illustrated below.

X-ray: 1 ray of CuK α (wavelength: 1.54056)/40kV/200mA

Scanning range: 2 θ=20-80 °

Scanning speed: 5 °/min

By whether observing that the three strong ray peak of ZnO of characterization hexagonal crystal system judges whether metal oxide particle has crystallographic system identical with ZnO and crystal structure.Specifically, judging the metal oxide particle and ZnO crystallographic system having the same and crystal structure if having diffraction maximum in all positions following three angle of diffraction (a)-(c).

(a) 2 θ=31.65-31.95 °

(b) 2 θ=34.30-34.60 °

(c) 2 θ=36.10-36.40 °

(2) particle diameter of metal oxide particle:

(2-1) crystal grain diameter (Ds):

For above-mentioned powder sample, the crystal grain diameter (Ds) of metal oxide particle is evaluated with powder x-ray diffraction (Rigaku Denki K.K. production, ProductName: RINT 2400) by powder X-ray diffractometry.(wherein hkl indicates Miller index: Ds (hkl) is the crystallite dimension perpendicular to the direction of the lattice plane of Miller index (hkl)) is measured with Scherrer equation (analysis) by the width of the diffracted ray in obtained X-ray diffractogram specifically, crystal grain diameter Ds (hkl).

(2-2) primary particle diameter (Dw): crystal grain diameter (Dw)

The particle diameter (Dw) of metal oxide particle is used as primary particle diameter measurement and evaluation.

Crystal grain diameter (Dw) is evaluated using the following method: for above-mentioned powder sample, the crystal grain diameter (Dw) of metal oxide particle is evaluated with powder x-ray diffraction (Rigaku Denki K.K. production, ProductName: RINT 2400) by powder X-ray diffractometry.(wherein hkl indicates Miller index: Ds (hkl) is the crystallite dimension perpendicular to the direction of the lattice plane of Miller index (hkl)) is measured with Scherrer equation (analysis) by the width of the diffracted ray in obtained X-ray diffractogram specifically, crystal grain diameter Ds (hkl).The average value of the respective Ds numerical value of three strong ray is as Dw.That is, unless otherwise noted, crystal grain diameter (Dw) usually calculates using the following method.Measure the x-ray diffractogram of powder of metal oxide particle, for three strong ray (the third-largest peak (3) of the maximum peak (1) of diffracted ray, the second largest peak (2) of diffracted ray and diffracted ray), crystal grain diameter Ds1, Ds2 and the Ds3 being respectively perpendicular in the direction for belonging to diffracted ray (1)-(3) diffraction surfaces by respective maximum intensity half overall with or integral breadth measured according to Scherrer etc., then regard its average value ((Ds1+Ds2+Ds3)/3) as crystal grain diameter (Dw).

(2-3) discrete particles diameter:

The reaction solution of generation, or sample is used as by this reaction solution solvent dispersion as made from solvent displacement, its median diameter is measured with dynamic light scattering type particle diameter distribution analyzer (" LB-500 " that is produced by HoribaSeisakusho), and as discrete particles diameter.

Quantitative analysis is carried out to the metallic element of above-mentioned powder sample with x-ray fluorescence analysis or icp analysis, content to measurement relative to the miscellaneous metallic element (Co, Fe, Ni) of main metal element (M), and for measuring the content of the metallic element (Ms) relative to main metal element (M) above-mentioned metallic compound in the case where metallic compound during particle is formed is used as additive.

Furthermore, when observing each particle in above-mentioned powder sample with the FE-TEM (Flied emission transmission electron microscope) of the XMA equipment (X-ray microanalysis instrument) equipped with resolution ratio 1nm φ, it will be from the superficial layer of particle until any part of its central part carries out local elemental analysis, the deviation of the intensity ratio of the peak intensity of every kind of metallic element peak intensity and main metal element (M) is evaluated, to judge whether every kind of metallic element is uniformly distributed contained in particle (uniformity for namely judging distribution).In addition, also evaluating whether the miscellaneous metallic element of metallic compound (Co, Fe, Ni) or metallic element (Ms) have any segregation when carrying out local elemental analysis to every kind of metallic element.

Zero: uniformly containing the metallic element (Co, Fe, Ni, Ms) different from main metal element (M).

×: unevenly contain the metallic element (Co, Fe, Ni, Ms) different from main metal element (M) and/or observes its metal or compound segregation.

(4) chemical valence of contained miscellaneous metallic element (Co, Fe, Ni) is evaluated in metal oxide particle:

For above-mentioned powder sample, the 2p of contained miscellaneous metallic element (Co, Fe, Ni) in metal oxide particle is measured by x-ray photoelectron spectroscopy (XPS) with photoelectron spectroscopy (Nippon Denshi K.K. production, ProductName: JPS-90 type)_3/2Spectrum, and measured from peak position and combine energy numerical value, to judge the chemical valence of miscellaneous metallic element (Co, Fe, Ni).

In addition, such as shown in " The Handbook of X-rayPhotoelectron Spectroscopy " (1991) that Nippon Denshi K.K. is delivered, the 2p of the compound of various miscellaneous metallic elements (Co, Fe, Ni)_3/2The peak position of spectrum is as known relatively data.

(5) optical property of metal oxide particle:

(5-1) is with the evaluation of dispersion form membrane:

The reaction solution generated to the reaction for generating metal oxide particle carries out heated solvent displacement, so that such a dispersion is made, so that metal oxide particle is dispersed in n-butyl alcohol, and granule density 20wt%.The dispersion that 100 parts are generated (presses SiO with 20 parts of silicate adhesives₂Meter solid component content is 51wt%) and 0.5 part of catalyst (n-butylamine) mixing, the mixture of generation is then subjected to 10 minutes decentralized processings with ultrasonic homogenizer, is stirred for 3 hours, so that a kind of coating be made.By the way, for above-mentioned granule density, the dispersion of generation uses vacuum desiccator to be dried in vacuo 1 hour obtained solid component quantity as particle weight at 120 DEG C.

The coating of generation is coated on alkali-free glass (being produced by CorningInternational Corporation, barium borosilicate glass, glass code 7059, thickness: 0.6mm) with stick coating machine, wet film with a thickness of 24 μm.Hereafter, they are normally dried at 25 DEG C, so that the glass for forming metal oxide particle dispersion membrane on the surface thereof be made.Then, the visible transmission property with (i) based on transmitted spectrum, ultraviolet radiation absorption property and wavelength visible absorbent properties；(ii) visible transparency and (iii) coloring degree evaluate the glass of this dispersion film coating.

- the evaluation-about above-mentioned (i)

(i-a):

This evaluation only is carried out to the membrane part in the glass of dispersion film coating.

The glass of each dispersion film coating and the transmitted spectrum of above-mentioned alkali-free glass (only substrate) are measured using the automatic record spectrophotometer (" UV-3100 " of Shimadzu Corporation production) for having integrating sphere.

Glass and alkali-free glass about the coating of each dispersion film, by obtained transmitted spectrum, with the transmissivity of visible light (transmissivity (the %) (transmissivity under 500nm of 500nm wavelength light, hereafter also refer to identical meaning similar to word)) transmission property of visible light is had rated, and ultraviolet radiation absorption property is had rated with transmissivity under 380nm.Furthermore, have rated the absorbent properties of wavelength visible using the following method: for whether have can absorption band within the scope of the 550-700nm as caused by the ion comprising miscellaneous metallic element (Co, Fe, Ni) and for the degree of such absorption band, measure Δ (%) with following equation:

Δ (%)=[| T⁵⁰⁰-T¹|/T⁵⁰⁰]×100

(wherein T¹For the minimum value of 550-700nm range internal transmission factor (%)；And T⁵⁰⁰For the transmissivity (%) at 500nm), numerical value is evaluated by following standard:

A: Δ (%) < 5%

B:5%≤Δ (%) < 10%

C:10%≤Δ (%)

By the way, only above-mentioned transmissivity of the membrane part under each wavelength is measured with following equation:

Only membrane part is in the transmissivity (%) under each wavelength=[transmissivity (%) of the glass of dispersion film coating in transmissivity (%)/alkali-free glass under each wavelength under each wavelength] × 100

(wherein: being all 91%) in the transmissivity under 500nm, the transmissivity at 380nm and the transmissivity within the scope of 550-700nm about transmissivity (%) of the alkali-free glass measured with above-mentioned evaluation method under each wavelength

(i-b):

Identical evaluation is carried out with the identical method of above-mentioned evaluation method (i-a), the difference is that the coating wet-film thickness of the glass of the coating of the dispersion film made from stick coating machine is 66 μm.By the way, this evaluation only carries out metal oxide particle specified in embodiment.

- the evaluation-about above-mentioned (ii)

Pass through nephelometer (Nippon Denshoku Kogyo Co., Ltd. produce, ProductName: NDH-1001 DP) glass that dispersion film coats is measured with total radiant transmittance, diffusion transmissivity, infinite ray transmissivity and haze values (H (%)).

The transparency of the glass of dispersion film coating is evaluated with following standard.

A:H (%) < 1%

B:1%≤H (%) < 3%

C:3%≤H (%)

- the evaluation-about above-mentioned (iii)

The glass that dispersion film about generation coats, with the naked eye observes its appearance, to evaluate coloring degree with following standard:

×: coloring is obvious.

△: it slightly colours.

Zero: it is colourless, that is, it colours unobvious.

(5-2) is to disperse state evaluation in a solvent:

By using n-butyl alcohol so that the reaction solution generated is diluted to 0.1wt% fine particle concentration the dilution for preparing as retarder thinner, and the dilution is used as sample, and about this sample, the transmitted spectrum in ultraviolet light and visible-range is measured with the automatic record spectrophotometer (" UV-3100 " of Shimadzu Corporation production) for having integrating sphere.

By the way, it is similar above-mentioned, about the transmitted spectrum of film-forming products, its transmitted spectrum in ultraviolet light and visible-range also is measured with the automatic record spectrophotometer (" UV-3100 " of Shimadzu Corporation production) for having integrating sphere.

(6) tone of metal oxide particle:

Observe the appearance of powder sample with the naked eye to evaluate.

<evaluation of film (or substrate of film coating)>:

(1) the visible transmission property based on transmitted spectrum, ultraviolet radiation absorption property and wavelength visible absorbent properties:

This evaluation is carried out to the substrate of film coating.

Substrate about film coating evaluates visible transmission property by the transmissivity (transmissivity (%) at 500nm) of visible light by obtained transmitted spectrum, and ultraviolet radiation absorption property is evaluated with the transmissivity under 380nm.Furthermore, evaluate the absorbent properties of wavelength visible using the following method: for the presence or absence of Δ (%) can be measured with following equation by the degree containing any absorption band and such absorption band caused by miscellaneous metallic element (Co, Fe, Ni) ion within the scope of 550-700nm:

Δ (%)=[| T⁵⁰⁰-T¹|/T⁵⁰⁰]×100

(wherein T¹For the minimum value of 550-700nm range internal transmission factor (%)；And T⁵⁰⁰For the transmissivity (%) at 500nm), value is evaluated by following standard:

A: Δ (%) < 5%

B:5%≤Δ (%) < 10%

C:10%≤Δ (%)

By the way, the substrate about the substrate for being only used for film coating, also measures the transmissivity under each wavelength with above-mentioned identical method.

(2) visible transparency:

With nephelometer (Nippon Denshoku Kogyo Co., Ltd. " NDH-1001DP " produced) substrate and substrate itself of each film coating are measured come (H (%)) by whole radiant transmittances, diffused ray transmissivity, infinite ray transmissivity and turbidity, so as to the transparency with following standard from the haze values evaluated for film of measurement.By the way, the haze values of film are obtained by the haze values that the haze values of the substrate of film coating subtract substrate itself.

A:H (%) < 1%

B:1%≤H (%) < 3%

C:3%≤H (%)

(3) coloring degree:

×: coloring is obvious.

△: it slightly colours.

Zero: it is colourless, it colours unobvious.

[embodiment C1-1]:

Prepare a kind of consersion unit, which includes: can pressure-resistant glass reactor external heating and that mouth is sent into equipped with blender, addition entrance (being directly connected with addition tank), thermometer, retort gas outlet and nitrogen；The addition tank being connected with above-mentioned addition entrance and the condenser (being directly connected with trap) being connected with the outlet of above-mentioned retort gas.

Mixture containing 183 parts of anhydrous acetic acid zinc powders, 3.5 parts of anhydrous cobalt acetate (II) powder, 2 parts of methyltrimethoxysilane and 1700 parts of methanol is packed into above-mentioned reactor, then purges its gas phase portion with nitrogen.Hereafter, the temperature of mixture (from 20 DEG C) is risen to 160 DEG C under stiring, and heating is kept for 5 hours at 160 DEG C ± 1 DEG C, to be reacted, generate metal oxide particle, then it cools down, so that the reaction solution (11) containing blue fine grained (metal oxide particle) be made.

Metal oxide particle in reaction solution (11) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 23.By the way, the chemical valence of the Co contained in the metal oxide particle in reaction solution (11), by the 2p for measuring Co in aforementioned manners_3/2Spectrum is evaluated.As a result, from its peak position for 780.3eV judgement, the Co (Co (II)) containing divalent.

About the metal oxide particle in reaction solution (11), the evaluation (5) (i-b) in above-mentioned evaluation has also been carried out to metal oxide particle.Therefore it obtains, the transmissivity under 380nm is less than 1%, and the transmissivity under 500nm is 80%, and Δ (%) is grade A.

[embodiment C1-2 to C1-4]:

The reaction solution (12) to (14) containing blue fine grained (metal oxide particle) is made with the identical method of embodiment C1-1, the difference is that as shown in Table 22, changing the raw material type and dosage of loading.

Metal oxide particle of the reaction solution (12) to (14) in each is subjected to above-mentioned various measurements and evaluation.Its result is included in table 23.By the way, the chemical valence about the Co contained in metal oxide particle of the reaction solution (12) to (14), by the 2p for measuring Co in aforementioned manners_3/2Spectrum is evaluated.As a result, judging from its peak position, Co (Co (II)) containing divalent similar with embodiment C1-1.

[embodiment C1-5]:

Prepare consersion unit identical with embodiment C1-1, mixture containing 183 parts of anhydrous acetic acid zinc powders, 1.8 parts of anhydrous cobalt acetate (II) powder, 1.9 parts of ferric acetate (III) hydroxide powders, 3 parts of tetramethoxy-silicanes and 1700 parts of 1- propyl alcohol is packed into the pressure-resistant glass reactor that this equipment is matched, then purges its gas phase portion with nitrogen.Hereafter, the temperature of mixture (from 20 DEG C) is risen to 160 DEG C under stiring, and heating is kept for 2 hours at 160 DEG C ± 1 DEG C, to be reacted, generate metal oxide particle, then it cools down, so that the reaction solution (15) containing blue fine grained (metal oxide particle) be made.By the way, made from the embodiment C1-1 to C1-4 compared with metal oxide particle, the color of above-mentioned metal oxide particle more mitigates, and it is advantageous to for needing more colorless and transparent application.

Metal oxide particle in reaction solution (15) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 23.By the way, the chemical valence of the Co contained in the metal oxide particle in reaction solution (15), by the 2p for measuring Co in aforementioned manners_3/2Spectrum is evaluated.As a result, judging from its peak position, Co (Co (II)) containing divalent similar with embodiment C1-1.

[comparative example C1-1]:

The reaction solution (c11) containing white fine grained (metal oxide particle) is made with the identical method of embodiment C1-1, the difference is that anhydrous cobalt acetate (II) is not used as the raw material being added.

Metal oxide particle in reaction solution (c11) is subjected to above-mentioned various measurements and evaluation.Its result is included in table 23.

[embodiment C1-6 to C1-8]:

The reaction solution (16) to (18) containing blue fine grained (metal oxide particle) is made with the identical method of embodiment C1-1, the difference is that as shown in Table 22, changing the raw material type and dosage of addition.

Metal oxide particle of the reaction solution (16) to (18) in each is subjected to above-mentioned various measurements and evaluation.Its result is included in table 23.By the way, the chemical valence about the Co contained in metal oxide particle of the reaction solution (16) to (18), by the 2p for measuring Co in aforementioned manners_3/2Spectrum is evaluated.As a result, judging from its peak position, Co (Co (II)) containing divalent similar with embodiment C1-1.

Table 22

	Zinc compound parts by weight	Cobalt compound parts by weight	Iron compound parts by weight	Additive parts by weight	Weight of solvent part
	Zinc compound parts by weight	Cobalt compound parts by weight	Iron compound parts by weight	Additive parts by weight	Weight of solvent part	Embodiment C1-1	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	- -	Methyltrimethoxysilane 2	Methanol 1700
Embodiment C1-2	Zinc acetate 183	Anhydrous cobalt acetate (II) 7.0	- -	Tetramethoxy-silicane 8	1- propyl alcohol 1700	Embodiment C1-1	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	- -	Methyltrimethoxysilane 2	Methanol 1700
Embodiment C1-2	Zinc acetate 183	Anhydrous cobalt acetate (II) 7.0	- -	Tetramethoxy-silicane 8	1- propyl alcohol 1700	Embodiment C1-3	Zinc acetate 183	Anhydrous cobalt acetate (II) 1.5	- -	Ruthenium trimethoxysilane 10	Ethyl alcohol 1700
Embodiment C1-4	Zinc acetate 183	Anhydrous cobalt acetate (II) 5.0	- -	Four titanium n-butoxide tetramers 16	Methanol 1700	Embodiment C1-3	Zinc acetate 183	Anhydrous cobalt acetate (II) 1.5	- -	Ruthenium trimethoxysilane 10	Ethyl alcohol 1700
Embodiment C1-4	Zinc acetate 183	Anhydrous cobalt acetate (II) 5.0	- -	Four titanium n-butoxide tetramers 16	Methanol 1700	Embodiment C1-5	Zinc acetate 183	Anhydrous cobalt acetate (II) 1.8	Ferric acetate (III) hydroxide 1.9	Tetramethoxy-silicane 3.0	1- propyl alcohol 1700
Comparative example C1-1	Zinc acetate 183	- -	- -	Methyltrimethoxysilane 2	Methanol 1700	Embodiment C1-5	Zinc acetate 183	Anhydrous cobalt acetate (II) 1.8	Ferric acetate (III) hydroxide 1.9	Tetramethoxy-silicane 3.0	1- propyl alcohol 1700
Comparative example C1-1	Zinc acetate 183	- -	- -	Methyltrimethoxysilane 2	Methanol 1700	Embodiment C1-6	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	- -	Methyltrimethoxysilane 15	Methanol 1700
Embodiment C1-7	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	- -	- -	Ethyl alcohol 1700	Embodiment C1-6	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	- -	Methyltrimethoxysilane 15	Methanol 1700
Embodiment C1-7	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	- -	- -	Ethyl alcohol 1700	Embodiment C1-8	Zinc acetate 183	Anhydrous cobalt acetate (II) 3.5	- -	Tetramethoxy-silicane 2	1- propyl alcohol 1700

Table 23

	Metal oxide particle	X-ray diffractogram	Co content atom %/Zn	Fe content atom %/Zn	Distributing homogeneity	Crystal grain diameter (nm)		Dispersion membrane evaluation
						Crystal grain diameter (nm)		Dispersion membrane evaluation				Ds(100)	Ds(002)	Transparency	Visible transmission property (%) 500nm	Ultraviolet radiation absorption property (%) 380nm	Wavelength visible absorbent properties
						Embodiment C1-1	11	It is equivalent to ZnO	2	-	○	Ds(100)	Ds(002)	Transparency	Visible transmission property (%) 500nm	Ultraviolet radiation absorption property (%) 380nm	Wavelength visible absorbent properties	9	15	A	98	36	A
Embodiment C1-2	12	It is equivalent to ZnO	3.8	-	○	Embodiment C1-1	11	It is equivalent to ZnO	2	-	○	8	12	A	97	30	A	9	15	A	98	36	A
Embodiment C1-2	12	It is equivalent to ZnO	3.8	-	○	Embodiment C1-3	13	It is equivalent to ZnO	0.8	-	○	8	12	A	97	30	A	9	21	A	98	49	A
Embodiment C1-4	14	It is equivalent to ZnO	2.8	-	○	Embodiment C1-3	13	It is equivalent to ZnO	0.8	-	○	12	12	A	97	33	A	9	21	A	98	49	A
Embodiment C1-4	14	It is equivalent to ZnO	2.8	-	○	Embodiment C1-5	15	It is equivalent to ZnO	1	1	○	12	12	A	97	33	A	8	17	A	98	29	A
Comparative example C1-1	c11	It is equivalent to ZnO	-	-	-	Embodiment C1-5	15	It is equivalent to ZnO	1	1	○	9	22	A	98	76	A	8	17	A	98	29	A
Comparative example C1-1	c11	It is equivalent to ZnO	-	-	-	Embodiment C1-6	16	It is equivalent to ZnO	2	-	○	9	22	A	98	76	A	6	14	A	98	55	A
Embodiment C1-7	17	It is equivalent to ZnO	2	-	○	Embodiment C1-6	16	It is equivalent to ZnO	2	-	○	16	33	B	94	32	A	6	14	A	98	55	A
Embodiment C1-7	17	It is equivalent to ZnO	2	-	○	Embodiment C1-8	18	It is equivalent to ZnO	2	-	○	16	33	B	94	32	A	15	15	A	97	28	A

[comparative example C1-2]:

Prepare consersion unit identical with embodiment C1-1, the mixture containing 300 part of six acetate hydrate zinc powder, 3 parts of anhydrous cobalt acetate (II) powder and 2000 parts of ion exchange waters is packed into the pressure-resistant glass reactor that this equipment is matched.Hereafter, 20 DEG C are held the mixture under stiring.1000 parts are wherein added dropwise in this mixture dissolved with the ion exchange water of 200 parts of sodium carbonate.Hereafter 2h is stirred, so that a kind of slurry be made.This slurry is centrifuged, the deposit then generated with ion exchange water washing refilters.The filter cake of generation is dry at 100 DEG C, it is then calcined 2 hours at air atmosphere and 500 DEG C in calcining furnace, then cool down.By the powder dusting of generation, it is 20wt% that being then distributed in n-butyl alcohol with sand mill, which becomes concentration, so that dispersion (c12) be made.

The evaluation result of metal oxide particle is as follows in the dispersion (c12) of generation.

As described in above-mentioned evaluation method (3), the Co content in individual particle is non-uniform and immeasurablel.But as the determination of elemental analysis of the powder with metal oxide particle, relative to the atomic ratio of Zn, the average content of Co is 1.3 atom %.Such as with embodiment C1-1 identical method judge as a result, in particle contained Co chemical valence be 3.Crystal grain diameter perpendicular to (002) face direction is 38nm.According to above-mentioned evaluation method (5-1), the evaluation result of the optical property as metal oxide particle, transparency is grade C, and the transmissivity under the transmission property of visible light is 500nm is 78%.

[embodiment C1-9 to C1-16 and comparative example C1-3 to C1-4]:

Reaction solution (19) to (116), (c13) and (c14) containing metal oxide particle is made with the identical method of embodiment C1-1, the difference is that as shown in Table 24, changing the raw material type and dosage of addition.

Metal oxide particle of the reaction solution (19) to (116), (c13) and (c14) in each is subjected to above-mentioned various measurements and evaluation.Its result is included in table 25.By the way, in this table, as a comparison, the identical evaluation result to comparative example C1-1 is also shown.

Table 24

	Zinc compound parts by weight	Iron compound parts by weight	Nickel compound parts by weight	Cobalt compound parts by weight	Weight of additive part	Weight of solvent part	Heating temperature (DEG C)	Heating time (h)
	Zinc compound parts by weight	Iron compound parts by weight	Nickel compound parts by weight	Cobalt compound parts by weight	Weight of additive part	Weight of solvent part	Heating temperature (DEG C)	Heating time (h)	Embodiment C1-9	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	- -	- -	Tetramethoxy-silicane 1	2- propyl alcohol 1700	120	12
Embodiment C1-10	Zinc acetate 183	Ferric acetate (II) 3.5	- -	- -	Tetramethoxy-silicane 2	Ethyl alcohol 1700	120	12	Embodiment C1-9	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	- -	- -	Tetramethoxy-silicane 1	2- propyl alcohol 1700	120	12
Embodiment C1-10	Zinc acetate 183	Ferric acetate (II) 3.5	- -	- -	Tetramethoxy-silicane 2	Ethyl alcohol 1700	120	12	Embodiment C1-11	Zinc acetate 183	Ferric acetate (II) 5.2	- -	- -	Tetramethoxy-silicane 9	Methanol 1700	160	2
Embodiment C1-12	Zinc acetate 183	Ferric acetate (II) 3.5	- -	- -	- -	Ethyl alcohol 1700	120	12	Embodiment C1-11	Zinc acetate 183	Ferric acetate (II) 5.2	- -	- -	Tetramethoxy-silicane 9	Methanol 1700	160	2
Embodiment C1-12	Zinc acetate 183	Ferric acetate (II) 3.5	- -	- -	- -	Ethyl alcohol 1700	120	12	Embodiment C1-13	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	- -	- -	Tetramethoxy-silicane 2	1- propyl alcohol 1700	120	12
Ferric acetate (II) 1.8											Ferric acetate (III) hydroxide 2.0
Ferric acetate (II) 1.8	Embodiment C1-14	Zinc acetate 183	- -	Nickel acetate tetrahydrate (II) 5	- -	- -	Ethyl alcohol 1700	200			12
Embodiment C1-15	Embodiment C1-14	Zinc acetate 183	- -	Nickel acetate tetrahydrate (II) 5	- -	- -	Ethyl alcohol 1700	200	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	12	- -	Four acetate hydrate cobalts (II) 0.13	Tetramethoxy-silicane 1	2- propyl alcohol 1700	120	12
Embodiment C1-15	Embodiment C1-16	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	Nickel acetate tetrahydrate (II) 0.3	- -	Tetramethoxy-silicane 1	2- propyl alcohol 1700	120	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	12	- -	Four acetate hydrate cobalts (II) 0.13	Tetramethoxy-silicane 1	2- propyl alcohol 1700	120	12
Comparative example C1-3	Embodiment C1-16	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	Nickel acetate tetrahydrate (II) 0.3	- -	Tetramethoxy-silicane 1	2- propyl alcohol 1700	120	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	12	- -	- -	Tetramethoxy-silicane 9	Methanol 1700	120	12
Comparative example C1-3	Comparative example C1-4	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	- -	- -	- -	1- propyl alcohol 1700	120	Zinc acetate 183	Ferric acetate (III) hydroxide 2.0	12	- -	- -	Tetramethoxy-silicane 9	Methanol 1700	120	12

Table 25

	Metal oxide particle	X-ray diffractogram	Fe content atom %/Zn	Ni content atom %/Zn	Co content atom %/Zn	The chemical valence of metallic element (M ')	Distributing homogeneity	Crystal grain diameter (nm)		The tone of particle powder	Dispersion membrane evaluation
								Crystal grain diameter (nm)			Dispersion membrane evaluation				Ds(100)	Ds(002)	Transparency	Coloring degree	Visible transmission property (%) 500nm	Ultraviolet radiation absorption property (%) 380nm
								Embodiment C1-9	19		It is equivalent to ZnO	1	-	-	Ds(100)	Ds(002)	Transparency	Coloring degree	Visible transmission property (%) 500nm	Ultraviolet radiation absorption property (%) 380nm	Fe(III)	A	14	15	Yellow	A	△	93	47
Embodiment C1-10	110	It is equivalent to ZnO	2	-	-	Fe(II)	A	Embodiment C1-9	19	12	It is equivalent to ZnO	1	-	-	15	Green	A	○	92	36	Fe(III)	A	14	15	Yellow	A	△	93	47
Embodiment C1-10	110	It is equivalent to ZnO	2	-	-	Fe(II)	A	Embodiment C1-11	111	12	It is equivalent to ZnO	3	-	-	15	Green	A	○	92	36	Fe(II)	A	7	12	Green	A	○	95	45
Embodiment C1-12	112	It is equivalent to ZnO	2	-	-	Fe(II)	A	Embodiment C1-11	111	16	It is equivalent to ZnO	3	-	-	33	Green	B	○	86	38	Fe(II)	A	7	12	Green	A	○	95	45
Embodiment C1-12	112	It is equivalent to ZnO	2	-	-	Fe(II)	A	Embodiment C1-13	113	16	It is equivalent to ZnO	2	-	-	33	Green	B	○	86	38	Fe(II) Fe(III)	A	15	15	Yellow green	A	○	90	40
Embodiment C1-14	114	It is equivalent to ZnO	-	2	-	Ni(II)	A	Embodiment C1-13	113	20	It is equivalent to ZnO	2	-	-	18	Light green color	A	○	89	38	Fe(II) Fe(III)	A	15	15	Yellow green	A	○	90	40
Embodiment C1-14	114	It is equivalent to ZnO	-	2	-	Ni(II)	A	Embodiment C1-15	115	20	It is equivalent to ZnO	1	-	0.05	18	Light green color	A	○	89	38	Fe(III) Co(II)	A	14	14	Yellow green	A	○	93	40
Embodiment C1-16	116	It is equivalent to ZnO	1	0.12		Fe(III) Ni(II)	A	Embodiment C1-15	115	12	It is equivalent to ZnO	1	-	0.05	14	Yellow green	A	△	92	41	Fe(III) Co(II)	A	14	14	Yellow green	A	○	93	40
Embodiment C1-16	116	It is equivalent to ZnO	1	0.12		Fe(III) Ni(II)	A	Comparative example C1-3	c13	12	It is equivalent to ZnO	1	-	-	14	Yellow green	A	△	92	41	Fe(III)	A	6	15	Yellow	A	△	94	58
Comparative example C1-4	c14	It is equivalent to ZnO	1	-	-	Fe(III)	A	Comparative example C1-3	c13	16	It is equivalent to ZnO	1	-	-	33	Yellow	C	×	75	48	Fe(III)	A	6	15	Yellow	A	△	94	58
Comparative example C1-4	c14	It is equivalent to ZnO	1	-	-	Fe(III)	A	Comparative example C1-1	c11	16	It is equivalent to ZnO	-	-	-	33	Yellow	C	×	75	48	-	-	9	22	White	A	○	98	76

[embodiment C1-17]:

The reaction solution (117) containing metal oxide particle is made with the identical method of embodiment C1-10, the difference is that 0.18 part of acetic acid dihydrate lithium powder is used as other raw material.

Reaction solution (117) are subjected to the identical evaluation of embodiment C1-10.As a result, ultraviolet radiation absorption property (transmissivity under 380nm) is 32%, enhanced compared with the reaction solution (110) made from the embodiment C1-10.In addition, containing 0.18 atom % lithium ion relative to Zn.Other evaluation results are identical as reaction solution (110).

[embodiment C1-18]:

The reaction solution (118) containing metal oxide particle is made with the identical method of embodiment C1-10, the difference is that 0.14 part of one acetate hydrate calcium powder is used as other raw material.

Reaction solution (118) are subjected to the identical evaluation of embodiment C1-10.As a result, ultraviolet radiation absorption property (transmissivity under 380nm) is 33%, enhanced compared with the reaction solution (110) made from the embodiment C1-10.In addition, containing 0.08 atom % calcium ion relative to Zn.Other evaluation results are identical as reaction solution (110).

[embodiment C1-19]:

The reaction solution (119) containing metal oxide particle is made with the identical method of embodiment C1-9, the difference is that 0.05 part of four acetate hydrate magnesium dust is used as other raw material.

Reaction solution (119) are subjected to the identical evaluation of embodiment C1-9.As a result, ultraviolet radiation absorption property (transmissivity under 380nm) is 43%, enhanced compared with the reaction solution (19) made from the embodiment C1-9.In addition, containing 0.02 atom % magnesium ion relative to Zn.Other evaluation results are identical as reaction solution (19).

[embodiment C1-20]:

The reaction solution (120) containing metal oxide particle is made with the identical method of embodiment C1-9, the difference is that 0.78 part of anhydrous acetic acid caesium powder is used as other raw material.

Reaction solution (120) are subjected to the identical evaluation of embodiment C1-9.As a result, ultraviolet radiation absorption property (transmissivity under 380nm) is 44%, enhanced compared with the reaction solution (19) made from the embodiment C1-9.In addition, containing 0.4 atom % cesium ion relative to Zn.Other evaluation results are identical as reaction solution (19).

[embodiment C1-21]:

The reaction solution (121) containing metal oxide particle is made with the identical method of embodiment C1-14, the difference is that 0.4 part of anhydrous sodium acetate powder is used as other raw material.

Reaction solution (121) are subjected to the identical evaluation of embodiment C1-14.As a result, ultraviolet radiation absorption property (transmissivity under 380nm) is 35%, enhanced compared with the reaction solution (114) made from the embodiment C1-14.In addition, containing 0.4 atom % sodium ion relative to Zn.Other evaluation results are identical as reaction solution (114).

[embodiment C1-22]:

The reaction solution (122) containing metal oxide particle is made with the identical method of embodiment C1-1, the difference is that 0.51 part of anhydrous acetic acid barium dust is used as other raw material.

Reaction solution (122) are subjected to the identical evaluation of embodiment C1-1.As a result, ultraviolet radiation absorption property (transmissivity under 380nm) is 34%, enhanced compared with the reaction solution (11) made from the embodiment C1-1.In addition, containing 0.2 atom % barium ions relative to Zn.Other evaluation results are identical as reaction solution (11).

[embodiment C1-23]:

It will be packed into the identical reactor of embodiment C1-1 containing the mixture of 2400 parts of glycol dimethyl ethers (as reaction dissolvent), 303 parts of titanium methoxy propyl oxides, 2.8 parts of ferric acetate (II) powder and 270 parts of acetic acid (as additive), and purge its gas phase portion with nitrogen.Hereafter, mixture is risen to 160 DEG C from 20 DEG C under stiring, and is heated 5 hours at 160 DEG C ± 1 DEG C, then cooled down, so that the reaction solution (123) that fine particle concentration is 2wt% be made.

Judge that fine grain crystallographic system and crystal structure in reaction solution (123) are equal to anatase-type titanium oxide from the result of powder x-ray diffraction.

Fine grained in reaction solution (123) carries out above-mentioned various evaluations.Its result is included in table 26.By the way, evaluation about optical property, reaction solution is used to have rated visible transmission property and ultraviolet radiation absorption property (still by above-mentioned evaluation method (5-2) as sample, ultraviolet radiation absorption property is evaluated with the transmissivity under 400nm), and coloring degree is evaluated by above-mentioned evaluation method (5-1), wherein n-butyl alcohol dispersion is used as sample to carry out the evaluation of dispersion form membrane.

[embodiment C1-24]:

The reaction solution (124) containing metal oxide particle is made with the identical method of embodiment C1-23, the difference is that replacing 2.8 parts of ferric acetate (II) powder with 8 parts of anhydrous cobalt acetate (II) powder.

Judge from the result of powder x-ray diffraction, the fine grain crystallographic system and crystal structure in reaction solution (124) are equal to anatase-type titanium oxide.

Fine grained in reaction solution (124) is carried out to the identical evaluation of embodiment C1-23.Its result is included in table 26.

[embodiment C1-25]:

The reaction solution (125) containing metal oxide particle is made with the identical method of embodiment C1-23, the difference is that replacing 2.8 parts of ferric acetate (II) powder with 1 part of nickel acetate tetrahydrate (II) powder.

Judge from the result of powder x-ray diffraction, the fine grain crystallographic system and crystal structure in reaction solution (125) are equal to anatase-type titanium oxide.

Fine grained in reaction solution (125) is carried out to the identical evaluation of embodiment C1-23.Its result is included in table 26.

[embodiment C1-26]:

The reaction solution (126) containing metal oxide particle is made with the identical method of embodiment C1-23, the difference is that replacing 2.8 parts of ferric acetate (II) powder with 0.65 part of ferric acetate (II) powder and 3 parts of ferric acetate (III) hydroxide.

Judge from the result of powder x-ray diffraction, the fine grain crystallographic system and crystal structure in reaction solution (126) are equal to anatase-type titanium oxide.

Fine grained in reaction solution (126) is carried out to the identical evaluation of embodiment C1-23.Its result is included in table 26.

[embodiment C1-27]:

The reaction solution (127) containing metal oxide particle is made with the identical method of embodiment C1-23, the difference is that replacing 2.8 parts of ferric acetate (II) powder with 0.1 part of anhydrous cobalt acetate (II) powder and 1.5 parts of ferric acetate (III) hydroxide powders.

Judge from the result of powder x-ray diffraction, the fine grain crystallographic system and crystal structure in reaction solution (127) are equal to anatase-type titanium oxide.

Fine grained in reaction solution (127) is carried out to the identical evaluation of embodiment C1-23.Its result is included in table 26.

[comparative example C1-5]:

The reaction solution (c15) containing metal oxide particle is made with the identical method of embodiment C1-23, the difference is that not using 2.8 parts of ferric acetate (II) powder.

Judge from the result of powder x-ray diffraction, the fine grain crystallographic system and crystal structure in reaction solution (c15) are equal to anatase-type titanium oxide.

Fine grained in reaction solution (c15) is carried out to the identical evaluation of embodiment C1-23.Its result is included in table 26.

[comparative example C1-6]:

The reaction solution (c16) containing metal oxide particle is made with the identical method of embodiment C1-23, the difference is that replacing 2.8 parts of ferric acetate (II) powder with 3 parts of ferric acetate (III) hydroxide powders.

Judge from the result of powder x-ray diffraction, the fine grain crystallographic system and crystal structure in reaction solution (c16) are equal to anatase-type titanium oxide.

Fine grained in reaction solution (c16) is carried out to the identical evaluation of embodiment C1-23.Its result is included in table 26.

Table 26

	X-ray diffractogram	Metal composition				Crystal grain diameter Dw (nm)	Visible transmission property (%) 600nm	Ultraviolet radiation absorption property (%) 400nm	The tone of particle powder	Disperse the coloring degree in form membrane
		Metal composition									M’(1)	Atom %/Ti	M’(2)	Atom %/Ti
		Embodiment C1-23	It is equivalent to Detitanium-ore-type TiO₂	Fe(II)	2						M’(1)	Atom %/Ti	M’(2)	Atom %/Ti	-	-	7	72	15	Green	○
Embodiment C1-24	It is equivalent to Detitanium-ore-type TiO₂	Embodiment C1-23	It is equivalent to Detitanium-ore-type TiO₂	Fe(II)	2	Co(II)	6	-	-	6	77	15	Blue	○	-	-	7	72	15	Green	○
Embodiment C1-24	It is equivalent to Detitanium-ore-type TiO₂	Embodiment C1-25	It is equivalent to Detitanium-ore-type TiO₂	Ni(II)	0.5	Co(II)	6	-	-	6	77	15	Blue	○	-	-	8	73	15	Green	○
Embodiment C1-26	It is equivalent to Detitanium-ore-type TiO₂	Embodiment C1-25	It is equivalent to Detitanium-ore-type TiO₂	Ni(II)	0.5	Fe(II)	0.5	Fe(III)	2	5	74	11	Yellow green	○	-	-	8	73	15	Green	○
Embodiment C1-26	It is equivalent to Detitanium-ore-type TiO₂	Embodiment C1-27	It is equivalent to Detitanium-ore-type TiO₂	Co(II)	0.07	Fe(II)	0.5	Fe(III)	2	5	74	11	Yellow green	○	Fe(III)	1	7	72	9	Blue	○
Comparative example C1-5	It is equivalent to Detitanium-ore-type TiO₂	Embodiment C1-27	It is equivalent to Detitanium-ore-type TiO₂	Co(II)	0.07	-	-	-	-	8	78	60	It is yellowish	○	Fe(III)	1	7	72	9	Blue	○
Comparative example C1-5	It is equivalent to Detitanium-ore-type TiO₂	Comparative example C1-6	It is equivalent to Detitanium-ore-type TiO₂	Fe(III)	2	-	-	-	-	8	78	60	It is yellowish	○	-	-	8	72	20	Yellow	×

[embodiment C1-28]:

It will be packed into the identical reactor of embodiment C1-1 containing the mixture of 3000 parts of pure water, 50 part of one cerium acetate hydrate (III) powder, 1.5 parts of ferric acetate (III) hydroxide powders and 0.19 part of nickel acetate tetrahydrate (II) powder, hereafter 50 part of 30% aqueous hydrogen peroxide solution will be added in stirring and at room temperature.The temperature of mixture is then risen to 90 DEG C from room temperature under stiring, and it is heated 5 hours at 90 DEG C ± 2 DEG C, then 10 part of 30% aqueous hydrogen peroxide solution is added, hereafter, temperature is reheated and is kept for 1 hour, then it cools down, to be made yellowish, the fine particle concentration that has the reaction solution of high transparency sense and have is 0.8wt%.Then, the reaction solution of generation is filtered with ultrafiltration membrane, to remove foreign ion and remaining hydrogen peroxide, and is concentrated through, so that the aqueous dispersion (128) that fine particle concentration is 7wt% be made.

Fine grained in aqueous dispersion (128) carries out above-mentioned various evaluations.Its result is included in table 27.By the way, evaluation about optical property, water-dispersible body has rated visible transmission property and ultraviolet radiation absorption property (still by above-mentioned evaluation method (5-2) as sample, ultraviolet radiation absorption property is evaluated with the transmissivity under 380nm and 400nm), and coloring degree is evaluated by above-mentioned evaluation method (5-1), to carry out the evaluation of dispersion form membrane.About crystallographic system and crystal structure, the particle is so thin, so that generating wide X-ray diffraction.Therefore, by the way that its result is then judged crystallographic system and crystal structure compared with the data of standard powder with electronics diffraction measurement lattice constant.About primary particle diameter, judged with transmission electron microscope.

[comparative example C1-7]:

The aqueous dispersion (c17) for being 7wt% with granule density is made with the identical method of embodiment C1-28, the difference is that not using 0.19 part of nickel acetate tetrahydrate (II) powder.

Fine grained in aqueous dispersion (c17) is carried out to the identical evaluation of embodiment C1-28.Its result is included in table 27.

[comparative example C1-8]:

The aqueous dispersion (c18) for being 7wt% with granule density is made with the identical method of embodiment C1-28, the difference is that not using 1.5 parts of ferric acetate (III) hydroxide powders, 0.19 part of nickel acetate tetrahydrate (II) powder is not used yet.

Fine grained in aqueous dispersion (c18) is carried out to the identical evaluation of embodiment C1-28.Its result is included in table 27.

Table 27

	X-ray diffractogram	Metal composition				Crystal grain diameter Dw (nm)	Visible transmission property (%) 600nm	Ultraviolet radiation absorption property (%)		The tone of particle powder	Disperse the coloring degree of form membrane
		Metal composition						Ultraviolet radiation absorption property (%)				M’(1)	Atom %/Ce	M’(2)	Atom %/Ce	380nm	400nm
		Embodiment C1-28	It is equivalent to CeO₂	Ni(II)	0.5			Fe(III)	5			M’(1)	Atom %/Ce	M’(2)	Atom %/Ce	380nm	400nm	2-4	98	10	40	Yellow green	○
Comparative example C1-7	It is equivalent to CeO₂	Embodiment C1-28	It is equivalent to CeO₂	Ni(II)	0.5	Fe(III)	5	Fe(III)	5	-	-	2-4	98	30	60	Yellow	×	2-4	98	10	40	Yellow green	○
Comparative example C1-7	It is equivalent to CeO₂	Comparative example C1-8	It is equivalent to CeO₂	-	-	Fe(III)	5	-	-	-	-	2-4	98	30	60	Yellow	×	2-4	99	29	75	Yellow	△

[embodiment C1-29]:

It will be packed into the identical reactor of embodiment C1-1 containing the mixture of 146 parts of anhydrous acetic acid indium powder, 1.72 parts of ferric acetate (III) hydroxide powders, 0.18 part of ferric acetate (II) powder and 3322 parts of methanol, and then purge its gas phase portion with nitrogen.Hereafter, the temperature of mixture is risen to 180 DEG C from room temperature under stiring, and is heated 5 hours at 180 DEG C ± 1 DEG C, to be reacted, metal oxide particle is generated, is then cooled down, so that the fine grain reaction solution (129) for being 2wt% containing fine particle concentration be made.

Fine grained in reaction solution (129) is subjected to above-mentioned various evaluations.Its result is included in table 28.By the way, dispersion is used to carry out the evaluation of discrete particles diameter as sample, so that metal oxide particle is dispersed in n-butyl alcohol, dispersion is made wherein carrying out heated solvent by the reaction solution that will be generated and replacing in granule density 20wt%.Coloring degree is evaluated according to above-mentioned evaluation method (5-1), wherein n-butyl alcohol dispersion is used as sample, is evaluated to disperse form membrane.

[embodiment C1-30 to C1-32]:

Reaction solution (130) to (132) are made with the identical method of embodiment C1-29, the difference is that changing the ratio between ferric acetate (III) hydroxide powder and ferric acetate (II) powder being packed into, so that the ratio between divalent Fe and trivalent Fe is the composition of metal shown in table 28.

Fine grained of the reaction solution (130) into (132) is carried out to the identical evaluation of embodiment C1-29.Its result is included in table 28.

[comparative example C1-9]:

Reaction solution (c19) is made with the identical method of embodiment C1-29, the difference is that not using 0.18 part of ferric acetate (II) powder, but usage amount is 1.9 parts of ferric acetate (III) hydroxide powders.

Fine grained in reaction solution (c19) is subjected to the identical evaluation such as embodiment C1-29.Its result is included in table 28.

Table 28

	X-ray diffractogram	Metal composition		Crystal grain diameter Dw (nm)	The tone of particle powder	Disperse the coloring degree of form membrane	Discrete particles diameter (nm)
		Metal composition						Fe (II) atom %/In	Fe (III) atom %/In
		Embodiment C1-29	It is equivalent to In₂O₃					Fe (II) atom %/In	Fe (III) atom %/In	0.2	1.8	5	Yellow green	△	< 50
Embodiment C1-30	It is equivalent to In₂O₃	Embodiment C1-29	It is equivalent to In₂O₃	1	1	5	Green	○	< 50	0.2	1.8	5	Yellow green	△	< 50
Embodiment C1-30	It is equivalent to In₂O₃	Embodiment C1-31	It is equivalent to In₂O₃	1	1	5	Green	○	< 50	1.8	0.2	5	Green	○	< 50
Embodiment C1-32	It is equivalent to In₂O₃	Embodiment C1-31	It is equivalent to In₂O₃	2	0	5	Green	○	< 50	1.8	0.2	5	Green	○	< 50
Embodiment C1-32	It is equivalent to In₂O₃	Comparative example C1-9	It is equivalent to In₂ O ₃	2	0	5	Green	○	< 50	0	2	5	Yellow	×	< 50

[embodiment C2-1]:

Reaction solution (11) (granule density: 4.4wt%) made from 1000 parts of embodiment C1-1 is heated under normal pressure, distills out 710 parts of solvent composition such as methanol, so that reaction solution (11) be made to be concentrated.When this concentration of reaction solution further heats, n-butyl alcohol is continuously added dropwise, to carry out solvent displacement with n-butyl alcohol while distilling out remaining solvent composition from reaction solution, so that the dispersion (21) of metal oxide particle dispersion in ethanol, which is made, is used as film-forming composition, granule density 20wt%.

With the discrete particles diameter for the dispersion (21) that dynamic optical scanning-type particle diameter distribution measuring device (Horiba Seisakusho, ProductName: LB-500) measurement generates.Therefore it obtains, average discrete particles diameter is not more than 100nm.

[embodiment C2-2 to C2-5]:

The dispersion (22) to (25) as film-forming composition is made with the identical method of embodiment C2-1, the difference is that as shown in table 29, changing the reaction solution used, for the solvent and granule density of solvent displacement.

Each discrete particles diameter of the dispersion (22) to (25) generated with the identical device measuring of embodiment C2-1.Therefore it obtains, under any circumstance, average discrete particles diameter is not more than 100nm.

[comparative example C2-1]:

The dispersion (c21) as film-forming composition is made with the identical method of embodiment C2-1, the difference is that as shown in table 29, changing the reaction solution used, for the solvent and granule density of solvent displacement.

With the discrete particles diameter for the dispersion (c21) that the identical device measuring of embodiment C2-1 generates.As a result, average discrete particles diameter is not more than 100nm.

Table 29

	The reaction solution used	Dispersion obtained			Discrete particles diameter
		Dispersion obtained				Number	Solvent	Granule density wt%
		Embodiment C2-1	11	21		Number	Solvent	Granule density wt%	N-butyl alcohol	20	< 100nm
Embodiment C2-2	12	Embodiment C2-1	11	21	22	N-butyl alcohol	20	< 100nm	N-butyl alcohol	20	< 100nm
Embodiment C2-2	12	Embodiment C2-3	13	23	22	N-butyl alcohol	20	< 100nm	Toluene	20	< 100nm
Embodiment C2-4	14	Embodiment C2-3	13	23	24	Butyl acetate	30	< 100nm	Toluene	20	< 100nm
Embodiment C2-4	14	Embodiment C2-5	15	25	24	Butyl acetate	30	< 100nm	N-butyl alcohol	20	< 100nm
Comparative example C2-1	c11	Embodiment C2-5	15	25	c21	N-butyl alcohol	20	< 100nm	N-butyl alcohol	20	< 100nm

[embodiment C3-1]:

Dispersion (21) made from 100 parts of embodiment C2-1 and 20 parts of silicate adhesives (are pressed into SiO₂Count solid component content: 51wt%) and 0.2 part of catalyst (n-butylamine) mixing, to prepare a kind of coating.

The coating of generation is coated on alkali-free glass (being produced by CorningInternational Corporation, barium borosilicate glass, glass code 7059, thickness: 0.6mm) with stick coating machine, wet film with a thickness of 45 μm.Hereafter, they are normally dried at 25 DEG C, is then heated at 250 DEG C, so that the glass for forming metal oxide particle dispersion membrane on the surface thereof be made.

The glass that the dispersion film of generation is coated carries out above-mentioned evaluation.Therefore it obtains, it is seen that the transparency of light is " A ", and coloring degree is "○".About visible transmission property, the transmissivity at 500nm is 76%.About ultraviolet radiation absorption property, the transmissivity at 380nm is less than 2%, and ultraviolet radiation absorption property is that can almost absorb the property no more than 380nm light.Wavelength visible absorbent properties are " A ".By the way, about transmissivity (%) of the only alkali-free glass of substrate under each wavelength is used as, any one transmissivity at 500nm, 380nm and 500-700nm is all 91% (also identical in embodiment (C) cited below).

[embodiment C3-2]:

Dispersion made from embodiment C2-1 (21) is coated on the identical alkali-free glass of embodiment C3-1 with stick coating machine, then its temperature is increased from normal temperature in calcining furnace, it is kept for 1 hour at 500 DEG C, then it cools down, so that glass of the formation containing the Co ZnO particle film adulterated on its surface be made.

The glass of the thin film coated of generation is that one kind has absorbability in nearly 450nm to ultraviolet ray range (shorter wavelength side) and can almost absorb and block the material of the light no more than 370nm.In addition, the glass to this thin film coated carries out above-mentioned evaluation.Therefore it obtains, it is seen that the transparency of light is " A ", and coloring degree is "○".About visible transmission property, the transmissivity at 500nm is 88%.Wavelength visible absorbent properties are " A ".

[embodiment C3-3]:

A kind of coating is made with the identical method of embodiment C3-1, the difference is that the dispersion (25) made from 100 parts of embodiment C2-5 replaces 100 parts of dispersions (21).

The coating of generation is coated on the identical alkali-free glass of embodiment C3-1 with stick coating machine, wet-film thickness is 42 μm.Hereafter, they are normally dried at 25 DEG C, is then heated at 250 DEG C, so that the glass for forming metal oxide particle dispersion membrane on its surface be made.

The glass of the dispersion film coating of generation carries out above-mentioned evaluation.As a result, the transparency of visible light is " A ", and coloring degree is "○".About visible transmission property, the transmissivity at 500nm is 78%.About ultraviolet radiation absorption property, the transmissivity at 380nm is less than 1%, and ultraviolet radiation absorption property is that can almost absorb the property no more than 380nm light.Wavelength visible absorbent properties are " A ".By the way, the glass phase ratio coated with the film of the glass of the dispersion film of embodiment C3-1 coating and embodiment C3-2, coloring degree more mitigate, and it is advantageous to for needing more colorless and transparent application.

[embodiment C3-4]:

Use stick coating machine that reaction solution made from embodiment C1-10 (110) is coated on the identical alkali-free glass as substrate of embodiment C3-1, then it dries at normal temperature, then it is heated 1 hour in nitrogen atmosphere at 400 DEG C in heating furnace, so that the substrate of the film of 0.6 μm of film thickness of formation on its surface be made.

The substrate for the film coating that evaluation generates.As a result, the substrate of this film coating is provided with ZnO crystal film, the film contains 2 atom %Fe (II) relative to Zn, and be a kind of micro- green and good colourless ultraviolet light block glass: the transmissivity under ultraviolet radiation absorption property is 380nm is 30%, and visible transmission property is 90% for the transmissivity at 500nm, and transparency is turbidity 0.3%.

[comparative example C3-1]:

The substrate of the coating of the film of 0.6 μm of film thickness of formation on its surface is made with the identical method of embodiment C3-4, the difference is that reaction solution (c13) the surrogate response liquid (110) made from comparative example C1-3.

Have rated the substrate of the film coating of generation.As a result, the substrate of this film coating is provided with ZnO crystal film, the film contains 2 atom %Fe (III) relative to Zn, and be a kind of ultraviolet light blocking glass obviously to turn yellow: the transmissivity under ultraviolet radiation absorption property is 380nm is 50%, and visible transmission property is 88% for the transmissivity at 500nm, and transparency is turbidity 0.6%.

[the 4th kind of metal oxide particle]:

Illustrate the measurement and evaluation in embodiment and comparative example cited below below.

<evaluation of metal oxide particle>:

(1) the crystal identification of metal oxide particle:

X-ray: 1 ray of CuK α (wavelength: 1.54056)/40kV/200mA

Scanning range: 2 θ=20-80 °

Scanning speed: 5 °/min

(a) 2 θ=31.65-31.95 °

(b) 2 θ=34.30-34.60 °

(c) 2 θ=36.10-36.40 °

Equally in the case where metal oxide particle contains the metallic element different from Zn as main metal component, by whether observing that the three strong ray peak of oxide crystal of above-mentioned metallic element judges whether the metal oxide particle has crystallographic system identical with above-mentioned metallic element and crystal structure.

(2) particle diameter of metal oxide particle:

(2-1) primary particle diameter:

It measures the crystal grain diameter (Dw) of metal oxide particle and is evaluated as primary particle diameter.

Crystal grain diameter (Dw) is evaluated using the following method: about above-mentioned powder sample, the crystal grain diameter (Dw) of metal oxide particle is evaluated with powder x-ray diffraction (Rigaku Denki K.K. production, ProductName: RINT 2400) by powder X-ray diffractometry.Specifically, crystal grain diameter Ds (hkl) (wherein hkl indicates Miller index: Ds (hkl) is the crystallite dimension perpendicular to the direction of the lattice plane of Miller index (hkl)) is measured with Scherrer equation (analysis) by the width of the diffracted ray in obtained X-ray diffractogram, and the average value of the respective Ds numerical value of three strong ray is as Dw.That is, unless otherwise noted, crystal grain diameter (Dw) usually calculates using the following method.Measure the x-ray diffractogram of powder of metal oxide particle, about three strong ray (the third-largest peak (3) of the maximum peak (1) of diffracted ray, the second largest peak (2) of diffracted ray and diffracted ray), vertically crystal grain diameter Ds1, Ds2 and Ds3 for being belonging respectively in the direction of diffracted ray (1)-(3) diffraction surfaces by respective maximum intensity half overall with or integral breadth measured according to Scherrer equation, then regard its average value ((Ds1+Ds2+Ds3)/3) as crystal grain diameter (Dw).

(2-2) discrete particles diameter:

The reaction solution of generation, or sample is used as by this reaction solution solvent dispersion as made from solvent displacement, its median diameter is measured with dynamic light scattering type particle size distribution analyzer (" LB-500 " that is produced by HoribaSeisakusho), and as discrete particles diameter.In the case where being diluted in the preparation for measurement, solvent used in reaction is used as retarder thinner.Evaluation criterion is as follows:

A: 0.1 μm of discrete particles diameter <

0.5 μm of B:0.1 μm≤discrete particles diameter <

C:0.5 μm≤discrete particles diameter

(3) composition of metal oxide particle:

The content of (3-1) N, S and the 17th race's element:

Them are measured by carrying out elemental analysis to above-mentioned powder sample.

The content for the metallic element (M ') that (3-2) is added:

It is measured by the way that above-mentioned powder sample is dissolved in strong acid aqueous solution and then carries out icp analysis to the solution of generation.

The binding capacity of (3-3) acyl group:

The above-mentioned powder sample of 1g is added in 0.1N sodium hydrate aqueous solution, is then stirred 24 hours.Hereafter, acyl group is identified with ion chromatography and binding capacity is quantified.

The chemical valence evaluation for the metallic element (M ') that (3-4) is added:

If desired, evaluating the chemical valence of the metallic element (M ') of the addition in metal oxide particle using the following method.That is, about above-mentioned powder sample, the 2p of the metallic element (M ') of contained addition in metal oxide particle is measured by x-ray photoelectron spectroscopy (XPS) with photoelectron spectroscopy (NipponDenshi K.K. production, ProductName: JPS-90 type)_3/2Spectrum, and measured from its peak position and combine energy numerical value, to judge the chemical valence for the metallic element (M ') being added.

In addition, as shown in " The Handbook of X-rayPhotoelectron Spectroscopy " (1991) that Nippon Denshi K.K. is delivered, the 2p of the compound of various metallic elements_3/2The peak position of spectrum is as known relatively data.

(4) optical property of metal oxide particle:

(4-1) absorbent properties:

A kind of dilution prepared by the dispersion for using n-butyl alcohol to generate as retarder thinner dilution to fine grain concentration is 0.1wt%, and it is used as sample, and about this sample, the transmitted spectrum in ultraviolet light and visible-range is measured with the automatic record spectrophotometer (" UV-3100 " of Shimadzu Corporation production) for having integrating sphere.Ultraviolet radiation absorption property is evaluated with the transmissivity (T1) under 400nm, and evaluates visible transmission property with the transmissivity (T2) under 600nm, and judged with following standard:

Ultraviolet radiation absorption property: A:T1 < 30%

B:30%≤T1 < 60%

C:60%≤T1

Visible transmission property: A:T2 >=80%

B:80% > T2 >=60%

C:60% > T2

The evaluation of (4-2) coloring degree and transparency:

It is made and evaluates fine grained dispersion membrane.Specifically, the dispersion that 100 parts are generated (presses SiO with 20 parts of silicate adhesives₂Count solid component content: 51wt%) and 0.5 part of catalyst (n-butylamine) mixing, so that a kind of coating be made.

The coating of generation is coated on alkali-free glass (being produced by CorningInternational Corporation, barium borosilicate glass, glass code 7059, thickness: 0.6mm) with stick coating machine, wet film with a thickness of 24 μm.Hereafter, they are normally dried at 25 DEG C, so that the glass for forming metal oxide particle dispersion membrane on the surface thereof be made.

About coloring degree, the appearance for the glass that with the naked eye dispersion liquid film coats in observation, to evaluate coloring degree with following standard:

Zero: not seeing coloring.

△: it slightly colours.

×: coloring is obvious.

About transparency, the appearance for the glass that with the naked eye dispersion liquid film coats in observation, to evaluate transparency with following standard:

Zero: transparency is high.

△: it is transparent, but see slightly muddy.

×: it is muddy.

(5) tone of powder sample:

Observe the appearance of powder sample with the naked eye to evaluate.

(6) fine grain concentration:

The fine grain concentration of reaction solution or dispersion is calculated by the weight of measurement residual dry powder after weighing up 0.5g reaction solution or dispersion in fusing crucible and be dried in vacuo 1 hour at 120 DEG C.

[embodiment D1-1]:

Prepare a kind of consersion unit, it includes can pressure-resistant glass reactor external heating and that mouth is sent into equipped with blender, addition entrance (being directly connected with addition tank), thermometer, retort gas outlet and nitrogen；The addition tank being connected with above-mentioned addition entrance and the condenser (being directly connected with trap) being connected with the outlet of above-mentioned retort gas.

Mixture containing 156 parts of anhydrous formic acid zinc powders, 3912 parts of n-butyl alcohols and 0.1 part of urea is sent into above-mentioned reactor, then purges its gas phase portion with nitrogen.Hereafter, the temperature of mixture is risen to 150 DEG C from 20 DEG C under stiring, and heating keeps 10h at 150 DEG C ± 1 DEG C, to be reacted, metal oxide particle is generated, is then cooled down, so that the fine grain reaction solution (11) for being 2wt% containing concentration be made.The reaction solution (11) of generation is heated under reduced pressure, thus from reaction solution part distilling off solvent component, so that a kind of dispersion (11) is made, wherein the particle for being 20wt% containing concentration.

The metal oxide particle in the dispersion and this dispersion of generation is evaluated according to above-mentioned various evaluation methods.Its result is included in table 31.

[embodiment D1-2 to D1-5]:

Reaction solution (12) to (15) are made with the identical method of embodiment D1-1, the difference is that as shown in Table 30, changing the raw material type and dosage of addition.Also with identical method, the fine grain dispersion liquid (12) to (15) for being wherein 20wt% containing concentration is made.

[embodiment D1-6]:

After reaction solution (12) are made with the identical method of embodiment D1-2, the reaction solution (12) of generation is centrifuged, is then dried in vacuo the deposit of generation at 80 DEG C, then dusting, so that a kind of particulate powders be made.This powder is heated in the nitrogen of hydrogeneous-sulfide at 300 DEG C, then the powder of generation is dispersed in n-butyl alcohol with bead mill, makes fine grain concentration 20wt%, so that a kind of dispersion (16) be made.

[comparative example D1-1]:

Dispersion (c11) is made with the identical method of embodiment D1-6, the difference is that replacing the nitrogen of hydrogeneous-sulfide with nitrogen and heat treatment temperature being changed to 400 DEG C from 300 DEG C.

[comparative example D1-2]:

After reaction solution (13) are made with the identical method of embodiment D1-3, the reaction solution (13) of generation is centrifuged, is then dried in vacuo the deposit of generation at 80 DEG C, then dusting, so that a kind of particulate powders be made.This powder is exposed in the nitrogen containing ammonia, is then heated in nitrogen at 350 DEG C, then the powder of generation is dispersed in n-butyl alcohol with bead mill, makes fine grain concentration 20wt%, so that a kind of dispersion (c12) be made.

[embodiment D1-7]:

After reaction solution (12) are made with the identical method of embodiment D1-2, the reaction solution (12) of generation is centrifuged, is then dried in vacuo the deposit of generation at 80 DEG C, then dusting, so that a kind of particulate powders be made.It is dispersed the powder into n-butyl alcohol with bead mill, makes fine grain concentration 20wt%, so that a kind of dispersion (17) be made.

Fine grained in the dispersion liquid made from embodiment D1-1 to D1-5 and D1-7, compared with the fine grained in the dispersion made from the comparative example D1-2, the transparency and coloring degree dispersed in membrane stage mitigates in terms of flavescence.By the way, the dispersion membrane that the dispersion as made from comparative example D1-1 obtains is muddy in terms of white, so being evaluated as " △ " about coloring degree.

Table 30

	Zinc compound parts by weight	Additive parts by weight	Ms compound by weight part
	Zinc compound parts by weight	Additive parts by weight	Ms compound by weight part	Embodiment D1-1	Zinc formate 156	Urea 0.1	- 0
Embodiment D1-2	Zinc acetate 183	Urea 0.5	- 0	Embodiment D1-1	Zinc formate 156	Urea 0.1	- 0
Embodiment D1-2	Zinc acetate 183	Urea 0.5	- 0	Embodiment D1-3	Zinc propionate 212	Urea 1.5	- 0
Embodiment D1-4	Zinc acetate 183	Urea 0.3	Four titanium butoxide tetramers 0.5	Embodiment D1-3	Zinc propionate 212	Urea 1.5	- 0
Embodiment D1-4	Zinc acetate 183	Urea 0.3	Four titanium butoxide tetramers 0.5	Embodiment D1-5	Zinc acetate 183	Urea 1.0	Tetramethoxy-silicane 6.0

Table 31

	X-ray diffractogram	Miscellaneous nonmetalloid atom %/Zn	In conjunction with acyl group atom %/Zn	Ms atom %/Zn	Crystal grain diameter (nm)			The tone of powder	Discrete particles diameter	Coloring degree	Transparency	Visible transmission property (%) 600nm	Ultraviolet radiation absorption property (%) 400nm
					Crystal grain diameter (nm)									Dw	Ds(100)	Ds(002)
					Embodiment D1-1	It is equivalent to ZnO	Nitrogen 0.2							Dw	Ds(100)	Ds(002)	Formoxyl 6	- 0	17	16	17	Yellow	B	△	△	A	B
Embodiment D1-2	It is equivalent to ZnO	Nitrogen 1	Acetyl group 3	- 0	Embodiment D1-1	It is equivalent to ZnO	Nitrogen 0.2	15	14	16	Yellow	B	△	△	A	B	Formoxyl 6	- 0	17	16	17	Yellow	B	△	△	A	B
Embodiment D1-2	It is equivalent to ZnO	Nitrogen 1	Acetyl group 3	- 0	Embodiment D1-3	It is equivalent to ZnO	Nitrogen 3	15	14	16	Yellow	B	△	△	A	B	Propiono 1	- 0	17	10	30	Yellow	B	△	△	A	B
Embodiment D1-4	It is equivalent to ZnO	Nitrogen 0.5	Acetyl group 3	Ti*1 0.2	Embodiment D1-3	It is equivalent to ZnO	Nitrogen 3	17	15	20	Yellow	A	△	○	A	B	Propiono 1	- 0	17	10	30	Yellow	B	△	△	A	B
Embodiment D1-4	It is equivalent to ZnO	Nitrogen 0.5	Acetyl group 3	Ti*1 0.2	Embodiment D1-5	It is equivalent to ZnO	Nitrogen 2	17	15	20	Yellow	A	△	○	A	B	Acetyl group 0.2	Si*2 4	14	12	18	Yellow	A	△	○	A	B
Embodiment D1-6	It is equivalent to ZnO	0.7 sulphur 3 of nitrogen	- 0	- 0	Embodiment D1-5	It is equivalent to ZnO	Nitrogen 2	15	14	16	Buff	C	×	×	A	A	Acetyl group 0.2	Si*2 4	14	12	18	Yellow	A	△	○	A	B
Embodiment D1-6	It is equivalent to ZnO	0.7 sulphur 3 of nitrogen	- 0	- 0	Embodiment D1-7	It is equivalent to ZnO	Nitrogen 1	15	14	16	Buff	C	×	×	A	A	Acetyl group 3	- 0	15	14	16	Yellow	B	△	△	A	B
Comparative example D1-1	It is equivalent to ZnO	- 0	- 0	- 0	Embodiment D1-7	It is equivalent to ZnO	Nitrogen 1	16	15	17	White	C	△	×	A	C	Acetyl group 3	- 0	15	14	16	Yellow	B	△	△	A	B
Comparative example D1-1	It is equivalent to ZnO	- 0	- 0	- 0	Comparative example D1-2	It is equivalent to ZnO	Nitrogen 2	16	15	17	White	C	△	×	A	C	- 0	- 0	18	11	31	Yellow	C	×	×	A	C

* 1: (part) hydrolysate as four titanium butoxide tetramers combines

2*: (part) hydrolysate as tetramethoxy-silicane combines

[embodiment D2-1]:

Reaction solution (21) are made with the identical method of embodiment D1-1, the difference is that raw mixture also contains 1.8 parts of anhydrous acetic acid iron (II) powder.Also with identical method, the fine grain dispersion (21) for being wherein 20wt% containing concentration is made.

The metal oxide particle in the dispersion and this dispersion of generation is evaluated according to above-mentioned various evaluation methods.Its result is included in table 32.

[comparative example D2-1]:

Reaction solution (c21) is made with the identical method of embodiment D1-1, the difference is that not using urea, but raw mixture also contains 1.8 parts of anhydrous acetic acid iron (II) powder.Also with same method, a kind of fine grain dispersion (c21) for being wherein 20wt% containing concentration is made.

As shown in table 32, fine grained in dispersion made from embodiment D2-1 (21) is yellow green, it is more less obvious than the fine grained in dispersion made from embodiment D1-1 (11) in dispersion liquid film coloring, and have better ultraviolet radiation absorption property than fine grained made from embodiment D1-1 and comparative example D2-1.

[embodiment D2-2]:

Reaction solution (22) are made with the identical method of embodiment D1-3, the difference is that raw mixture also contains 0.25 part of anhydrous cupric acetate (I) powder.Also with identical method, the fine grain dispersion (22) for being wherein 20wt% containing concentration is made.

[comparative example D2-2]:

Reaction solution (c22) is made with the identical method of embodiment D1-3, the difference is that not using urea, but raw mixture also contains 0.25 part of anhydrous cupric acetate (I) powder.Also with same method, a kind of fine grain dispersion (c22) for being wherein 20wt% containing concentration is made.

As shown in table 32, fine grained in dispersion made from embodiment D2-2 (22) is light gray, it is more less obvious than the fine grained in dispersion made from embodiment D1-3 (13) in dispersion membrane coloring, and have better ultraviolet radiation absorption property than fine grained made from embodiment D1-3 and comparative example D2-2.

[embodiment D2-3]:

Reaction solution (23) are made with the identical method of embodiment D1-2, the difference is that raw mixture also contains 1.3 parts of nickel acetate tetrahydrate (II) powder.Also with identical method, the fine grain dispersion (23) for being wherein 20wt% containing concentration is made.

[embodiment D2-4]:

Reaction solution (24) are made with the identical method of embodiment D1-2, the difference is that raw mixture also contains 1.8 parts of anhydrous cobalt acetate (II) powder.Also with identical method, the fine grain dispersion (24) for being wherein 20wt% containing concentration is made.

As shown in table 32, particle in dispersion (23) and (24) made from embodiment D2-3 and D2-4 is more less obvious than the fine grained in dispersion made from embodiment D1-2 (12) in dispersion membrane coloring, and has better ultraviolet radiation absorption property than fine grained made from embodiment D1-2.

Table 32

	X-ray diffractogram	Miscellaneous nonmetalloid atom %/Zn		M ' atom %/Zn	In conjunction with acyl group atom %/Zn		Crystal grain diameter (nm)			The tone of powder	Coloring degree	Visible transmission property (%) 600nm	Ultraviolet radiation absorption property (%) 400nm
							Crystal grain diameter (nm)							Dw	Ds(100)	Ds(002)
							Embodiment D1-1	It is equivalent to ZnO	Nitrogen					Dw	Ds(100)	Ds(002)	0.2	- -	Formoxyl	6	17	16	17	Yellow	△	A	B
Embodiment D2-1	It is equivalent to ZnO	Nitrogen	0.2	Fe(II) 1	Formoxyl	5	Embodiment D1-1	It is equivalent to ZnO	Nitrogen	15	15	15	Pistac	○	A	A	0.2	- -	Formoxyl	6	17	16	17	Yellow	△	A	B
Embodiment D2-1	It is equivalent to ZnO	Nitrogen	0.2	Fe(II) 1	Formoxyl	5	Comparative example D2-1	It is equivalent to ZnO	-	15	15	15	Pistac	○	A	A	-	Fe(II) 1	Formoxyl	5	16	15	17	Green	○	A	B
Embodiment D1-3	It is equivalent to ZnO	Nitrogen	3	- -	Propiono	1	Comparative example D2-1	It is equivalent to ZnO	-	17	10	30	Yellow	△	A	B	-	Fe(II) 1	Formoxyl	5	16	15	17	Green	○	A	B
Embodiment D1-3	It is equivalent to ZnO	Nitrogen	3	- -	Propiono	1	Embodiment D2-2	It is equivalent to ZnO	Nitrogen	17	10	30	Yellow	△	A	B	2.8	Cu(I) 0.2	Propiono	0.8	12	10	16	Grey	○	A	A
Comparative example D2-2	It is equivalent to ZnO	-	-	Cu(I) 0.2	Propiono	1.5	Embodiment D2-2	It is equivalent to ZnO	Nitrogen	13	10	18	Grey	○	A	C	2.8	Cu(I) 0.2	Propiono	0.8	12	10	16	Grey	○	A	A
Comparative example D2-2	It is equivalent to ZnO	-	-	Cu(I) 0.2	Propiono	1.5	Embodiment D1-2	It is equivalent to ZnO	Nitrogen	13	10	18	Grey	○	A	C	1	- -	Acetyl group	3	15	14	16	Yellow	△	A	B
Embodiment D2-3	It is equivalent to ZnO	Nitrogen	0.9	Ni(II) 0.5	Acetyl group	2.5	Embodiment D1-2	It is equivalent to ZnO	Nitrogen	15	14	16	Green	○	A	A	1	- -	Acetyl group	3	15	14	16	Yellow	△	A	B
Embodiment D2-3	It is equivalent to ZnO	Nitrogen	0.9	Ni(II) 0.5	Acetyl group	2.5	Embodiment D2-4	It is equivalent to ZnO	Nitrogen	15	14	16	Green	○	A	A	1.1	Co(II) 1	Acetyl group	2	14	13	15	Blue	○	A	A

[embodiment D2-5]:

It will be packed into the identical reactor of embodiment D1-1 containing the mixture of 183 parts of anhydrous acetic acid zinc powders, 0.05 part of anhydrous zinc fluoride, 12 parts of bismuth acetate (III) oxide powders, 0.07 part of anhydrous cupric acetate (I) and 3880 parts of methanol, and then purge its gas phase portion with nitrogen.Hereafter, the temperature of mixture is risen to 180 DEG C from 20 DEG C under stiring, and heating is kept for 10 hours at 180 DEG C ± 1 DEG C, to be reacted, metal oxide particle is generated, is then cooled down, so that the fine grain reaction solution (25) for being 2wt% containing concentration be made.The reaction solution (25) of generation is heated under reduced pressure, thus from reaction solution part distilling off solvent component, so that a kind of dispersion (25) is made, wherein the fine grain particle for being 20wt% containing concentration.

The metal oxide particle in the dispersion and this dispersion of generation is evaluated according to above-mentioned various evaluation methods.Its result is included in table 34.

[embodiment D2-6 to D2-12]:

Reaction solution (26) to (212) are made with the identical method of embodiment D2-5, the difference is that changing the type and dosage of the raw material of addition as shown in table 33.Also with identical method, the fine grain dispersion (26) to (212) for being wherein 20wt% containing concentration is made.

Table 33

	Zinc compound parts by weight	Compound by weight part of addition	M ' compound by weight part
	Zinc compound parts by weight	Compound by weight part of addition	M ' compound by weight part	Embodiment D2-5	Zinc acetate 183	Anhydrous zinc fluoride 0.05	12 anhydrous cupric acetate (I) 0.07 of bismuth acetate (III) oxide
Embodiment D2-6	Zinc acetate 183	Anhydrous zinc fluoride 0.18	12 anhydrous cupric acetate (II) 1 of anhydrous manganese acetate (II)	Embodiment D2-5	Zinc acetate 183	Anhydrous zinc fluoride 0.05
Embodiment D2-6	Zinc acetate 183	Anhydrous zinc fluoride 0.18		Embodiment D2-7	Zinc acetate 183	Anhydrous sodium sulfide 0.18	Anhydrous acetic acid indium (III) 19
Embodiment D2-8	Zinc propionate 212	Anhydrous zinc fluoride 0.35	5 four acetate hydrate magnesium (II) 0.05 of tri sec-butoxy aluminum	Embodiment D2-7	Zinc acetate 183	Anhydrous sodium sulfide 0.18	Anhydrous acetic acid indium (III) 19
Embodiment D2-8	Zinc propionate 212	Anhydrous zinc fluoride 0.35		Embodiment D2-9	Zinc propionate 212	Urea 0.6	Anhydrous acetic acid tin (IV) 8
Embodiment D2-10	Zinc propionate 212	Urea 3	8 anhydrous cupric acetate (I) 0.15 of cerous acetate (III)	Embodiment D2-9	Zinc propionate 212	Urea 0.6	Anhydrous acetic acid tin (IV) 8
Embodiment D2-10	Zinc propionate 212	Urea 3	8 anhydrous cupric acetate (I) 0.15 of cerous acetate (III)	Embodiment D2-11	Zinc formate 156	Anhydrous zinc chloride 0.14	Silver acetate 1.8
Embodiment D2-12	Zinc formate 156	Anhydrous lithium iodide 1.4	- -	Embodiment D2-11	Zinc formate 156	Anhydrous zinc chloride 0.14	Silver acetate 1.8

Table 34

	X-ray diffractogram	Miscellaneous nonmetalloid atom %/Zn	M ' atom %/Zn	In conjunction with acyl group atom %/Zn	Crystal grain diameter (nm)			The tone of powder	Coloring degree	Transparency	Visible transmission property (%) 600nm	Ultraviolet radiation absorption property (%) 400nm
					Crystal grain diameter (nm)								Dw	Ds(100)	Ds(002)
					Embodiment D2-5	It is equivalent to ZnO	Fluorine 0.05						Dw	Ds(100)	Ds(002)	Bi(III) 4Cu(I) 0.05	Acetyl group 0.5	17	17	18	Grey	○	A	A
Embodiment D2-6	It is equivalent to ZnO	Fluorine 0.3	Mn (II) 6.3Cu (I, II) 0.5	Acetyl group 0.8	Embodiment D2-5	It is equivalent to ZnO	Fluorine 0.05	15	16	13	Yellow green	△		A	A	Bi(III) 4Cu(I) 0.05	Acetyl group 0.5	17	17	18	Grey	○	A	A
Embodiment D2-6	It is equivalent to ZnO	Fluorine 0.3	Mn (II) 6.3Cu (I, II) 0.5	Acetyl group 0.8	Embodiment D2-7	It is equivalent to ZnO	Sulphur 0.2	15	16	13	Yellow green	△		A	A	In(III) 6Na(I) 0.4	Acetyl group 1.5	18	18	17	Blue-green	○	A	A
Embodiment D2-8	It is equivalent to ZnO	Fluorine 0.2	Al(III) 2Mg(II) 0.02	Propiono 1	Embodiment D2-7	It is equivalent to ZnO	Sulphur 0.2	15	11	23	Grey	○		A	B	In(III) 6Na(I) 0.4	Acetyl group 1.5	18	18	17	Blue-green	○	A	A
Embodiment D2-8	It is equivalent to ZnO	Fluorine 0.2	Al(III) 2Mg(II) 0.02	Propiono 1	Embodiment D2-9	It is equivalent to ZnO	Nitrogen 1	15	11	23	Grey	○		A	B	Sn (II, IV) 2	Propiono 4	14	11	20	Grey	○	A	B
Embodiment D2-10	It is equivalent to ZnO	Nitrogen 4	Ce(III) 2Cu(I) 0.1	Propiono 8	Embodiment D2-9	It is equivalent to ZnO	Nitrogen 1	12	11	14	Grey	○		A	A	Sn (II, IV) 2	Propiono 4	14	11	20	Grey	○	A	B
Embodiment D2-10	It is equivalent to ZnO	Nitrogen 4	Ce(III) 2Cu(I) 0.1	Propiono 8	Embodiment D2-11	It is equivalent to ZnO	Chlorine 0.1	12	11	14	Grey	○		A	A	Ag (0, I) 1	Formoxyl 0.5	24	22	28	Yellow	×	A	A
Embodiment D2-12	It is equivalent to ZnO	Iodine 1	Li(I) 1	Formoxyl 4	Embodiment D2-11	It is equivalent to ZnO	Chlorine 0.1	13	15	10	White	○		A	B	Ag (0, I) 1	Formoxyl 0.5	24	22	28	Yellow	×	A	A

[embodiment D3-1]:

Mixture containing 340 part of four titanium n-butoxide, 300 parts of acetic acid, 1 part of urea and 3360 parts of 2- propyl alcohol is packed into the identical reactor of embodiment D1-1, then purges its gas phase portion with nitrogen.Hereafter, the temperature of mixture is risen to 160 DEG C from 20 DEG C under stiring, and heating is kept for 5 hours at 160 DEG C ± 1 DEG C, to be reacted, metal oxide particle is generated, is then cooled down, so that the yellow reaction liquid (31) that fine particle concentration is 2wt% be made.In addition, a kind of n-butyl alcohol dispersion (31) that fine particle concentration is 20wt% is made from the reaction solution of generation.

Fine grained in the dispersion of generation is the fine grained that 0.2mol% acetyl group is combined with relative to Ti.

The metal oxide particle in the dispersion and this dispersion of generation is evaluated according to above-mentioned various evaluation methods.Its result is included in table 36.

[embodiment D3-2 to D3-6]:

Reaction solution (32) to (36) are made with the identical method of embodiment D3-1, the difference is that changing the type and dosage of the raw material of addition as shown in table 35.Also with identical method, the fine grain dispersion (32) to (36) for being wherein 20wt% containing concentration is made.

Table 35

	Compound by weight part of addition	M ' compound by weight part
	Compound by weight part of addition	M ' compound by weight part	Embodiment D3-1	Urea 1	- -
Comparative example D3-1	- -	- -	Embodiment D3-1	Urea 1	- -
Comparative example D3-1	- -	- -	Embodiment D3-2	Urea 1	Anhydrous acetic acid iron (II) 4
Embodiment D3-3	Urea 0.2	Anhydrous cobalt acetate (II) 0.2	Embodiment D3-2	Urea 1	Anhydrous acetic acid iron (II) 4
Embodiment D3-3	Urea 0.2	Anhydrous cobalt acetate (II) 0.2	Embodiment D3-4	Urea 4	Nickel acetate tetrahydrate (II) 1
Embodiment D3-5	Anhydrous cupric iodide (I) 2	- -	Embodiment D3-4	Urea 4	Nickel acetate tetrahydrate (II) 1
Embodiment D3-5	Anhydrous cupric iodide (I) 2	- -	Embodiment D3-6	Lithium fluoride 0.13	Bismuth acetate (III) oxide 12

Table 36

	X-ray diffractogram	Miscellaneous nonmetalloid atom %/Ti	M ' atom %/Ti	Crystal grain diameter (nm) Dw	The tone of powder	Coloring degree	Visible transmission property (%) 600nm	Ultraviolet radiation absorption property (%) 400nm
	X-ray diffractogram	Miscellaneous nonmetalloid atom %/Ti	M ' atom %/Ti	Crystal grain diameter (nm) Dw	The tone of powder	Coloring degree	Visible transmission property (%) 600nm	Ultraviolet radiation absorption property (%) 400nm	Embodiment D3-1	It is equivalent to TiO₂	Nitrogen 1	- -	14	Yellow	△	B	B
Comparative example D3-1	It is equivalent to TiO₂	- -	- -	16	It is light yellow	○	B	C	Embodiment D3-1	It is equivalent to TiO₂	Nitrogen 1	- -	14	Yellow	△	B	B
Comparative example D3-1	It is equivalent to TiO₂	- -	- -	16	It is light yellow	○	B	C	Embodiment D3-2	It is equivalent to TiO₂	Nitrogen 1	Fe(II) 2	10	Yellow green	○	B	A
Embodiment D3-3	It is equivalent to TiO₂	Nitrogen 0.2	Co(II) 0.1	14	Blue	○	B	B	Embodiment D3-2	It is equivalent to TiO₂	Nitrogen 1	Fe(II) 2	10	Yellow green	○	B	A
Embodiment D3-3	It is equivalent to TiO₂	Nitrogen 0.2	Co(II) 0.1	14	Blue	○	B	B	Embodiment D3-4	It is equivalent to TiO₂	Nitrogen 3	Ni(II) 0.4	13	Yellow green	○	B	A
Embodiment D3-5	It is equivalent to TiO₂	Iodine 0.9	Cu(I) 0.8	16	Grey	○	B	B	Embodiment D3-4	It is equivalent to TiO₂	Nitrogen 3	Ni(II) 0.4	13	Yellow green	○	B	A
Embodiment D3-5	It is equivalent to TiO₂	Iodine 0.9	Cu(I) 0.8	16	Grey	○	B	B	Embodiment D3-6	It is equivalent to TiO₂	Fluorine 0.4	Bi(III) 4Li(I) 0.5	14	Yellowish-brown	△	B	A

[embodiment D4-1]:

Dispersion (21) made from 100 parts of embodiment D2-1 and 20 parts of silicate adhesives (are pressed into SiO₂Count solid component content: 51wt%) and 0.2 part of catalyst (n-butylamine) mixing, to prepare a kind of coating.

The coating of generation is coated on alkali glass with stick coating machine, is then dried at normal temperature, after heat 1 hour under 200 DEG C and nitrogen atmosphere, form the glass that metal oxide particle dispersion membrane coats on the surface thereof to be made.

With the glass for the dispersion membrane coating that optics properties evaluations generate.As a result, this glass is that a kind of ultraviolet light blocks glass, it has fabulous colourless property, and the transmissivity under 600nm is 92%, and the transmissivity at 400nm is 25%, and turbidity is 0.3%.

By the way, the identical equipment used in above-mentioned evaluation method (4) measures the transmissivity under each wavelength by measurement transmitted spectrum, and evaluates turbidity with nephelometer.In addition, with the naked eye observation is to evaluate coloring degree.

[embodiment D4-2]:

Dispersion (25) made from 100 parts of embodiment D2-5 is mixed with 50 parts of acrylic resin adhesives (solid component content: 50wt%), to prepare a kind of coating.

The coating of generation is coated on polyester film with stick coating machine, is then dried at normal temperature, after heated 10 minutes at 100 DEG C, thus be made on the surface thereof formed metal oxide particle dispersion membrane dispersion membrane coating glass.

With the identical method of embodiment D4-1, the glass coated with the dispersion membrane that optics properties evaluations generate.As a result, this film is a kind of ultraviolet blocking film, it has fabulous colourless property, and the transmissivity under 600nm is 88%, and the transmissivity at 400nm is 25%, and turbidity is 0.5%.

[embodiment D4-3]:

Dispersion made from embodiment D2-10 (210) is coated on alkali glass with stick coating machine, then it dries at normal temperature, it is heated 30 minutes under 300 DEG C and nitrogen atmosphere afterwards, so that the glass for forming the film coating of metal oxide film on the surface thereof be made.

The glass of film coating obtained has ZnO crystal film, its N, Ce and Cu containing 3.4 atom %, 2 atom % and 0.1 atom % respectively relative to Zn, and glass is blocked for a kind of ultraviolet light, the result for using the identical method of embodiment D4-1 to evaluate as optical property, there is fabulous colourless property, transmissivity under 600nm is 90%, and the transmissivity at 400nm is 20%, and turbidity is 0.2%.

[embodiment D4-4]:

Dispersion made from embodiment D3-5 (35) is coated on alkali glass with stick coating machine, is then dried at normal temperature, after heated under 400 DEG C and nitrogen atmosphere, so that the glass for forming the film coating of metal oxide film on the surface thereof be made.

The glass of film coating obtained has TiO crystal film, its I and Cu containing 0.8 atom % and 0.8 atom % respectively relative to Ti, and glass is blocked for a kind of ultraviolet light, the result evaluated with the identical method of embodiment D4-1 by optical property, there is fabulous colourless property, transmissivity under 600nm is 90%, and the transmissivity at 400nm is 30%, and turbidity is 0.3%.

Industrial application

Film of the invention is for example preferred for: the glazing of building；The glazing of automobile (such as automobile, electric trains)；The glazing of aircraft (such as aircraft, helicopter)；Plastic film for agricultural use and various packaging films.But purposes is not limited to these.Various preferred purposes are all possible, not only to being provided with the various functional membranes of ultraviolet light block function, and have the various functional membranes of such as infrared ray block function and conducting function also for offer.

Composition of the present invention for forming a film for example cuts off coating preferably as the coating liquid for being used to form ultraviolet blocking film or as ultraviolet light, in addition to this, also as the material for being used to form above-mentioned film of the invention.

Metal oxide particle of the invention for example provides the component of ultraviolet light blocking ability preferably as in various application such as film (membranes or films), coating and cosmetic materials, in addition to this, the component further preferably as the present invention above-mentioned film and above-mentioned composition of the present invention.

Claims

1. a kind of metal oxide particle of fine particulate form, it is such a metal oxide particle, so that the metal oxide particle is characterized in that containing the component for being originated from the metallic element (M ') different from metallic element (M) in the particle of the oxide containing metallic element (M): metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And metallic element (M ') is selected from least one of Cu, Ag, Mn and Bi.

2. a kind of metal oxide particle, it is such a metal oxide particle, so that the metal oxide particle is characterized in that containing the component for being originated from the metallic element (M ') different from metallic element (M) in the particle of the oxide containing metallic element (M): metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And metallic element (M ') includes different from metallic element (M) and at least two in Co, Cu, Fe, Bi, In, Al, Ga, Ti, Sn, Ce, Ni, Mn and Ag.

3. metal oxide particle according to claim 2, wherein metallic element (M ') includes following basic component: selected from least one of Co, Cu and Fe and selected from least one of Bi, In, Al, Ga, Ti, Sn and Ce.

4. wherein metallic element (M ') includes a kind of as basic component in Co, Cu, Fe, Ag, Mn, Ni and Bi according to the metal oxide particle of Claims 2 or 3.

5. metal oxide particle as claimed in one of claims 2-4, wherein at least part is divalent in the case where metallic element (M ') is any element in Fe, Co and Ni.

6. a kind of metal oxide particle, it is such a metal oxide particle, so that the metal oxide particle is characterized in that containing the component for being originated from the metallic element (M ') different from metallic element (M) in the particle of the oxide containing metallic element (M): metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And metallic element (M ') is selected from least one of Co, Fe and Ni, wherein at least a part these Co, Fe and Ni are divalent.

7. a kind of metal oxide particle, it is such a metal oxide particle, so that the metal oxide particle is characterized in that containing the component for being originated from the metallic element (M ') different from metallic element (M) in the particle of the oxide containing metallic element (M): metallic element (M) is Zn；And metallic element (M ') is selected from least one of Co, Fe and Ni；And metal oxide particle is not more than 30nm perpendicular to the crystal grain diameter in (002) face direction, and it is not less than 8nm perpendicular to the crystal grain diameter in (100) face direction.

8. a kind of metal oxide particle, it is a kind of metal oxide particle for containing metallic element (M) oxide, and the metal oxide particle is characterized in that: metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And containing selected from least one of N, S and the 17th race (7B race) element in the oxide of metallic element (M).

9. a kind of metal oxide particle, it is a kind of metal oxide particle for containing metallic element (M) oxide, and the metal oxide particle is characterized in that: metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And containing at least two in N, S and the 17th race (7B race) element in the oxide of metallic element (M).

10. a kind of metal oxide particle, it is a kind of metal oxide particle for containing metallic element (M) oxide, and the metal oxide particle is characterized in that: metallic element (M) is selected from least one of Zn, Ti, Ce, In, Sn, Al and Si；And containing selected from least one of N, S and the 17th race (7B race) element in the oxide of metallic element (M)；And in the grain containing the component for being originated from the metallic element (M ') different from metallic element (M).

11. metal oxide particle according to claim 10, wherein metallic element (M ') is different from metallic element (M) and selected from Co, Cu, Fe, Bi, In, Al, Ga, Ti, Sn, Ce, Ni, B, Mn, Ag, Au, platinum group, alkali metal element and alkali earth metal at least one metallic element.

12. any one of -11 metal oxide particle according to claim 1, wherein primary particle diameter is 3-50nm.

13. any one of -12 metal oxide particle according to claim 1, in which: the oxide of metallic element (M) is crystal；And the crystal grain diameter of metal oxide particle is not more than 30nm (according to the average value of Scherrer equation line computation three strong for the peak XRD).

14. any one of -13 metal oxide particle according to claim 1, wherein the oxide of metallic element (M) is zincite crystal；And the crystal grain diameter in metal oxide particle perpendicular lattice face (002) direction is not more than 30nm, and it is not less than 10nm perpendicular to lattice plane (100) and/or the crystal grain diameter in lattice plane (110) direction.

15. any one of -14 metal oxide particle according to claim 1, wherein the particle containing metallic element (M) oxide contains 0.1-14mol% acyl group relative to metallic element (M) in molar ratio.

16. any one of -15 metal oxide particle according to claim 1, wherein the oxide of metallic element (M) is the oxide that its surface is combined with alkoxide or part thereof hydrolysate, and wherein alkoxide includes at least one metallic element for being different from contained metallic element (M ') in oxide.

17. any one of -16 metal oxide particle according to claim 1, wherein other than metallic element (M '), relative to metallic element (M), the also component for being originated from alkali metal element and/or alkali earth metal containing 0.001-5 atom %.

18. a kind of composition, containing metal oxide particle and medium, wherein metal oxide particle dispersion is in the medium and the composition includes the metal oxide particle of any one of claim 1-17 as basic component.

19. 8 composition according to claim 1 is used to form a film, contain following basic component: the metal oxide particle and dispersion solvent and/or adhesive of any one of claim 1-17.

20. 8 or 19 composition according to claim 1, wherein form of the metal oxide particle with discrete particles diameter no more than 1 μm is dispersed.

21. the composition of any one of 8-20 according to claim 1, also includes: containing selected from least one of Cu, Fe, Ag and Bi as the metal oxide particle of metallic element and/or containing selected from the ultra-fine metallic particles of at least one of Ag, Cu, Au and platinum group as metallic element.

22. a kind of film contains metal oxide as basic component, wherein the metal oxide includes following basic component: the metal oxide particle of any one of claim 1-17 and/or the metal oxide crystal from this particle.

23. film according to claim 22, it also includes: containing selected from least one of Cu, Fe, Ag and Bi as the metal oxide particle of metallic element and/or the metal oxide crystal from this particle；And/or contain the crystal selected from least one of Ag, Cu, Au and platinum group as the crystal and/or the metal oxide comprising being originated from this particle of the ultra-fine metallic particles of metallic element and/or the metal comprising being originated from this particle.

24. a kind of product of containing metal oxide, the product is the product of metal oxide crystal containing metal oxide particle and/or from this particle, wherein the product include any one of claim 1-17 metal oxide particle with: contain the metal oxide particle selected from least one of Cu, Fe, Ag and Bi as metallic element；And/or containing selected from least one of Cu, Ag, Au and platinum group as the ultra-fine metallic particles of metallic element combination as basic component.

25. a kind of ultraviolet absorption material, the metal oxide particle containing any one of claim 1-17.