JP2011116620A - Composite and method for manufacturing the same, photocatalytic functional member, and hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a composite having a photocatalyst layer excellent in photocatalytic activity and also durability which is prepared on the base material, and a photocatalytic functional member and a hydrophilic member which contain the composite produced by the method. <P>SOLUTION: The composite is a composite which is equipped with a base material and a glass ceramic layer located on the base material.The glass ceramic layer has a crystal phase and a glass phase, and contains, by mol% based on oxides, 5.0-95.0% in total of one or more kinds selected from Nb<SB>2</SB>O<SB>5</SB>component and Ta<SB>2</SB>O<SB>5</SB>component and 10.0-85.0% in total of one or more kinds selected from the group consisting of SiO<SB>2</SB>component, B<SB>2</SB>O<SB>3</SB>component, P<SB>2</SB>O<SB>5</SB>component and GeO<SB>2</SB>component. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a composite comprising a base material and a glass ceramic layer, a method for producing the same, and a photocatalytic functional member and a hydrophilic member containing the composite produced by the production method.

  Titanium oxide, niobium oxide, and tantalum oxide are known to have high photocatalytic activity. These compounds having photocatalytic activity (hereinafter sometimes simply referred to as “photocatalyst”) generate electrons and holes when irradiated with light having energy higher than the band gap energy. Near the surface, the redox reaction is strongly promoted. Further, it is known that the surface of a molded body containing a photocatalyst has a so-called self-cleaning action in which it is washed with water droplets such as rain because it exhibits hydrophilicity that easily wets water.

  As a photocatalyst, titanium oxide has been mainly studied. However, since titanium oxide has a band gap of 3 to 3.2 eV, it is necessary to irradiate ultraviolet rays with a wavelength of 400 nm or less, and visible light has sufficient photocatalytic activity. There is a disadvantage that it cannot be obtained. In addition, pure titanium oxide is a white powder and has almost no substance adsorbing ability, and the photocatalytic activity is not sufficient. Therefore, in order to impart high photoresponsiveness and catalytic activity to titanium oxide, for example, methods for performing plasma treatment, nitrogen doping, sulfur doping, and the like have been studied. On the other hand, research for finding new photocatalysts has been actively conducted, and niobium oxide and tantalum oxide have attracted attention among them. For example, potassium niobate is attracting attention as a photodecomposition catalyst for water that converts light energy into chemical energy because it causes charge separation by light irradiation. Patent Document 1 discloses a particle size as a photocatalyst used for water decomposition. Discloses a method for producing a potassium niobate photocatalyst having a small and large specific surface area, preferably a nickel niobate photocatalyst supported with nickel oxide as a cocatalyst, by a hydrothermal synthesis method.

  According to Non-Patent Document 1, tantalum oxynitrite (TaON) doped with nitrogen in tantalum oxide has been studied as a water-decomposing material in the presence of visible light irradiation and sacrificial agent, and is expected as a material exhibiting visible light responsiveness. Has been.

  Furthermore, regarding the tantalum oxide photocatalyst, in Patent Document 2, a precursor obtained by polymerizing a chemically modified tantalum alkoxide by partial hydrolysis is converted into powder, fiber, thin film or nanosheet, and then in the atmosphere or air, oxygen, ammonia, A method for producing a tantalum oxide photocatalyst having a light absorption edge in the near ultraviolet region by firing in one or more atmospheres selected from hydrogen is disclosed.

On the other hand, tantalum and niobium oxides and composite oxides are known as high dielectric constant materials, and have long been used as capacitor electrodes, piezoelectric elements, or light modulation elements. For example, Patent Document 3 discloses a two-layer capacitor mainly composed of niobium oxide obtained by thermally decomposing a complex containing niobium, and Patent Document 4 discloses a single crystal thin film substrate of LiNbO _3. A piezoelectric element having electrodes formed thereon is disclosed. Patent Document 5 discloses a high-dielectric material for an optical element, in which a glass containing a niobium component is heat-treated to precipitate a niobium composite salt crystal. Patent Document 6 discloses a solid electrolytic capacitor having a dielectric layer made of tantalum pentoxide.

JP 2003-126695 A JP 2006-263504 A JP 2000-188243 A Japanese Patent Laid-Open No. 03-190292 US Patent 3,140,066 JP 2002-2222736 A

G. Hitoki, et al. Chem. Commum. , 2002, Vol. 16, p. 1698-1699 Kenichi Katsumata and 4 others, Development of photocatalytic glass using nanosheets, Photofunctional Materials Study Group 15th Symposium “Recent Development of Photocatalytic Reaction” Vol. 27, pp. 126-127, 2008

  While various substances have been found as novel photocatalysts, many conventional techniques related to photocatalysts adopt the concept of supporting a photocatalyst by forming a film containing the photocatalyst on the surface of a substrate. However, a problem common to techniques based on such a concept is that it is difficult to ensure the adhesion between the substrate and the film containing the photocatalyst and the durability of the film itself. In other words, the photocatalytic functional products manufactured by these methods, for example, use a binder to adhere the thin film to the substrate, but over time, the film may peel off or deteriorate and the photocatalytic function may be impaired. There is a risk. For example, as described in Non-Patent Document 2, when a titania nanosheet is applied to the most commonly used soda lime glass, a base film that becomes an alkali barrier layer is required, and thus the manufacturing process is complicated. There is a problem in that it becomes expensive.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a composite having a photocatalytic layer having excellent photocatalytic activity and excellent durability on a substrate, and a method for producing the same. And

  As a result of intensive studies in order to solve the above problems, the present inventors have determined that the composition of the glass ceramic layer of the composite is in a specific range, so that the niobium and / or tantalum component-containing niobium is removed from the glass body. A glass ceramic layer in which a crystal phase containing one or more of the group consisting of the above compound and tantalum compound is deposited is obtained. By applying this glass ceramic layer to a substrate, excellent photocatalytic properties, more specifically Has found that a complex having decomposition characteristics of organic substances and / or high hydrophilicity caused by light irradiation can be obtained. Further, when obtaining the composite, the present inventors arrange a powder body containing a glass body containing a niobium component and / or a tantalum component on a base material, and firing the composite to obtain a target composite. It has been found that the body can be easily manufactured. The glass ceramic layer formed on the base material by this method can be easily adjusted in thickness, and the adhesion between the glass ceramic layer and the base material is enhanced by the binder effect of the glass itself. It has been found that it has strength and a photocatalytic function, and has completed the present invention. Specifically, the present invention provides the following.

(1) A composite comprising a base material and a glass ceramic layer positioned on the base material, wherein the glass ceramic layer has a crystal phase and a glass phase, and the glass ceramic layer is oxidized 1% or more selected from Nb ₂ O ₅ component and Ta ₂ O ₅ component in a total mol% of 5.0% to 95.0% in total, and SiO ₂ component and B ₂ O ₃ component A composite containing one or more selected from the group consisting of a P ₂ O ₅ component and a GeO ₂ component in a total of 10.0% to 85.0%.

  (2) The composite according to (1), wherein the glass ceramic layer exhibits catalytic activity by light having a wavelength from an ultraviolet region to a visible region.

  (3) The composite according to (1) or (2), wherein a contact angle between a surface of the glass ceramic layer irradiated with light having a wavelength from an ultraviolet region to a visible region and a water droplet is 30 ° or less.

(4) A method for producing a composite comprising a substrate and a glass ceramic layer having photocatalytic activity located on the substrate,
The manufacturing method which has a baking process which heats and bakes after arrange | positioning the granular material which consists of a glass body containing a niobium component and / or a tantalum component on a base material.

(5) The glass body contains 5.0 to 95.0% in total of at least one selected from the group consisting of Nb ₂ O ₅ component and Ta ₂ O ₅ component in mol% based on oxide. (4) The manufacturing method as described.

(6) The glass body is mol% based on oxide, and at least one selected from the group consisting of SiO ₂ component, P ₂ O ₅ component, B ₂ O ₃ component and GeO ₂ component is 10. The production method according to (4) or (5), containing 0 to 85.0%.

  (7) The manufacturing method according to any one of (4) to (6), wherein the powder body is made of crushed glass obtained by pulverizing the glass body.

  (8) The manufacturing method according to any one of (4) to (7), further including a crystallization step in which heat treatment is performed on the glass body or the granular material to precipitate crystals therein.

  (9) The manufacturing method according to any one of (4) to (8), wherein the baking is performed at a temperature of 1200 ° C. or lower.

  (10) The manufacturing method according to any one of (4) to (9), wherein the baking is performed at an atmospheric temperature that is equal to or higher than a glass transition temperature (Tg) of the glass body and is 600 ° C. higher than Tg.

(11) One or more selected from the group consisting of crystalline TiO ₂ , niobium compound, tantalum compound and WO ₃ is mixed in a mass ratio of 95.0% or less with respect to the total amount of the powder and granular material. The manufacturing method in any one of (4) to (10) which has the process of producing a mixture.

  (12) An additive containing one or more selected from the group consisting of an N component, an S component, an F component, a Cl component, a Br component, and a C component is added in a mass ratio of 20.0 with respect to the granular material or the mixture. % Or less, the manufacturing method in any one of (4) to (11).

  (13) A step of mixing 10.0% or less of a metal element component composed of one or more selected from the group consisting of Cu, Ag, Au, Pd, and Pt in a mass ratio with respect to the powder or the mixture. (4) The manufacturing method in any one of (12).

  (14) The manufacturing method according to any one of (4) to (13), including a step of dispersing the powder or the mixture in a solvent to make a slurry state.

  (15) The method according to any one of (4) to (14), wherein the firing is performed for 3 minutes to 24 hours.

  (16) The method according to any one of (4) to (15), further including a step of immersing or etching the composite in an acidic or alkaline solution.

(17) The glass body is an oxide based mol%,
TiO ₂ component 0-60.0% and / or
Alkali metal oxide component and / or alkaline earth metal oxide component 0-50.0%, and / or
M _a O _b (wherein M is one or more selected from the group consisting of W and Mo. a and b are the smallest natural numbers satisfying a: b = 2: (valence of M)) .) Component 0-50.0% and / or
M ¹ _c O _d (wherein, M ¹ is at least one selected from the group consisting of Zr and Sn. C and d are the minimum satisfying c: d = 2: (valence of M ¹ )) A natural number) component 0-30% and / or
M ² ₂ O ₃ (wherein M ² is one or more selected from the group consisting of B, Al, Ga, and In) component 0 to 50.0%, and / or
Ln ₂ O ₃ (wherein Ln is selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. One or more) component 0-30.0% and / or
M ³ _e O _f (wherein M ³ is at least one selected from the group consisting of V, Cr, Mn, Fe, Co, and Ni. E and f are e: f = 2: (M ³ ), the smallest natural number satisfying 0) to 10.0%, and / or
Bi ₂ O ₃ component + TeO ₂ component 0 to 20.0%, and / or
As ₂ O ₃ component + Sb ₂ O ₃ component 0-5.0%
Each component of,
In mass% with respect to the total mass of the oxide equivalent composition of the glass body,
15.0% or less of at least one nonmetallic element component selected from the group consisting of F component, Cl component, Br component, S component, N component, and C component, and / or
The manufacturing method according to any one of (4) to (16), which contains 10.0% or less of at least one metal element component selected from the group consisting of Cu, Ag, Au, Pd, and Pt.

  (18) A photocatalytic functional member comprising a composite produced by the production method according to any one of (4) to (17).

  (19) A hydrophilic member comprising a composite produced by the production method according to any one of (4) to (17).

  According to the present invention, a composite in which a glass ceramic layer is formed on a substrate, containing a crystal phase containing at least one of the group consisting of a niobium compound and a tantalum compound and having sufficient durability. Can provide the body. Since the crystal phase containing one or more of the group consisting of niobium compound and tantalum compound is homogeneously present inside and on the surface of the glass ceramic layer of the composite, it has excellent photocatalytic properties, Specifically, it has decomposition characteristics such as organic substances caused by light irradiation and / or high hydrophilicity. In particular, the composite produced by the production method of the present invention can utilize the binder effect of the glass itself, and thus can provide high adhesion to the substrate. And since the thickness and shape of a glass-ceramics layer can be designed with a high freedom degree according to the use and the shape of a base material, a composite_body | complex is useful in various uses. Furthermore, in the method of the present invention, a crystal phase containing a photocatalytic crystal exhibiting photocatalytic activity is generated from the glass phase by controlling the blend composition of the raw materials and the heat treatment temperature. It is not always necessary to use materials, and it is not necessary to use special equipment. Therefore, according to the method of the present invention, a composite having excellent photocatalytic properties and useful for various applications such as a photocatalytic functional member and a hydrophilic member can be easily produced on an industrial scale.

It is an XRD pattern about the glass ceramic layer in the composite_body | complex of Example 1 of this invention. It is an XRD pattern about the glass ceramic layer in the composite_body | complex of Example 31 of this invention.

  Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited thereto, and can be implemented with appropriate modifications within the scope of the object of the present invention. In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the meaning of invention is not limited.

  In the present invention, a glass ceramic composite (hereinafter sometimes referred to as “composite”) includes a glass ceramic layer and a base material. A layer composed of an amorphous solid and a crystal. The glass ceramic layer contains a photocatalytic crystal containing at least one of the group consisting of at least a niobium compound and a tantalum compound, and the photocatalytic crystal is uniformly dispersed inside and on the surface of the glass ceramic. .

  In general, the glass ceramics that make up the glass ceramic layer are solidified powdered materials containing glass powder, which are produced by heat-treating bulk glass materials (also called crystallized glass). It can mean sintered or both. The glass ceramic layer of the composite of the present invention can be either the former or the latter depending on the production method, and is used in the present specification to include both of them.

<Method for producing glass-ceramic composite>
It is preferable that the manufacturing method which manufactures the composite_body | complex which concerns on this invention has the baking process of the granular material obtained from a glass body as a main process. Details of each step will be described below. In a preferred embodiment of the method of the present invention, a vitrification step for producing a glass body by melting and vitrifying the raw material composition, a pulverization step for producing a granule from the glass body, and firing the granule on a substrate By doing, the baking process which forms a glass-ceramics layer can be included.

  Here, in the present invention, the “powder body” is obtained, for example, by pulverizing a glass body obtained from a raw material composition, and has an amorphous glass pulverized product and a crystalline phase. It is used to include a pulverized product of crystallized glass and a product obtained by precipitating a crystal phase in a pulverized product of glass. That is, the “powder” may or may not have a crystal phase. In particular, by using a granular material having a crystalline phase, the amount of photocatalytic crystals having photocatalytic properties is increased when firing on a substrate, so that a glass ceramic layer with enhanced photocatalytic function can be reliably produced. . In addition, since a photocatalytic crystal having photocatalytic activity already exists in the stage before firing, a glass ceramic layer having a desired photocatalytic function can be formed without using a temperature condition necessary for precipitating the crystal. On the other hand, since the photocatalyst function is imparted in the heat treatment and firing steps by using a granular material having no crystal phase, a glass ceramic layer having a desired photocatalytic function can be produced. At the same time, in the state of the granular material before precipitating the photocatalytic crystal, for example, it is difficult to decompose the organic matter that is in contact with or mixed with the granular material, so that the convenience of storage and handling can be enhanced. Here, when the powdery body has a crystal phase, it may be produced by heat treating the glass body to precipitate photocatalyst crystals and then pulverizing it, or after heat treating the glass body and performing powder treatment. You may manufacture by depositing a photocatalyst crystal | crystallization in a body. At this time, the crystal phase exists or is uniformly dispersed in the inside and the surface of the amorphous glass constituting the granular material. When the “powder” does not contain a crystal phase, the photocatalytic crystal can be precipitated in the glass by arranging the powder on the substrate and controlling the firing temperature. As described above, the heat treatment for precipitating photocatalytic crystals in glass is called “crystallization treatment”.

The crystallization treatment is performed at, for example, (a) after the vitrification step and before the pulverization step, (b) after the pulverization step and before the firing step, and (c) at the same time as the firing step. Can be implemented. Among these, from the viewpoints of easy sintering of the glass ceramic layer and no need for a binder, improvement of throughput due to simplification of the process, energy saving, etc. It is preferable to perform the conversion treatment. However, when using a substrate having low heat resistance as the base material constituting the composite, (a) after the vitrification step and before the pulverization step, or (b) after the pulverization step and before the firing step, It is preferable to perform crystallization at the timing.
Hereinafter, details of each process will be described.

[Vitrification process]
In the vitrification process, a predetermined raw material composition is melted and vitrified to produce a glass body. Specifically, the raw material composition is prepared and mixed uniformly so that the above-described components are within a predetermined content range. The resulting mixture is melted by putting the raw material composition into a container made of platinum or refractory and heating the raw material composition to a high temperature. The molten glass obtained in this way flows out and is cooled appropriately to form a vitrified glass body. Thereby, the raw material composition is uniformly mixed, and a base for generating nano-sized photocatalytic crystals is formed while imparting desired characteristics to the glass body. Therefore, the photocatalytic properties of the glass ceramic layer can be enhanced without necessarily using nano-sized photocatalytic crystals. The conditions for melting and vitrification of the raw material composition are not particularly limited, and can be appropriately set according to the composition and amount of the raw material composition. Moreover, the shape of the glass body formed is not specifically limited, For example, plate shape, a granule, etc. may be sufficient. The melting temperature and time vary depending on the glass composition, but are preferably in the range of, for example, 1200 to 1650 ° C. and 1 to 24 hours, respectively. In addition, even if the raw material composition used in the vitrification step is a non-glass raw material (usually a powder, referred to as a batch) containing a glass-forming oxide or the like, the non-glass body has been vitrified. It may be a glass raw material (usually a crushed material and called cullet). In addition, the glass body obtained by the vitrification step is not limited to a glass phase only, and a crystallized glass body containing at least a crystal phase (for example, a crystallized glass body crystallized at least partly). And a crystallized glass body crystallized at least partially). That is, the “glass body” in the subsequent step of the vitrification step includes a glass body that has been crystallized after the vitrification step.

In the production method of the present invention, the glass body that is the basis of the powder is a niobium compound (for example, Nb ₂ O ₅ , RnNbO ₃ , RNb ₂ O ₆ , where Rn is one selected from Li, Na, and K). And R represents one or more selected from Mg, Ca, Sr, Ba and Zn)), tantalum compounds (for example, Ta ₂ O ₅ , RnTaO ₃ , RTa ₂ O ₆ (Rn is Li, 1 or more selected from Na and K, and R means one or more selected from Mg, Ca, Sr, Ba and Zn). Therefore, the granular material obtained from the glass body has the same composition as the glass body.

  Hereinafter, the composition range of each component which comprises a glass body is described below. In the present specification, unless otherwise specified, the content of each component is expressed in mol% with respect to the total amount of the glass body having an oxide conversion composition. Here, the “oxide equivalent composition” means that the oxide, composite salt, metal fluoride, etc. used as the raw material of the glass component of the present invention are all decomposed and changed into oxides when melted. It is the composition which described each component contained in a glass body by making the total substance amount of the said production | generation oxide into 100 mol%.

(About essential and optional ingredients)
A crystal containing a niobium component and / or a tantalum component, for example, a niobium oxide crystal, a tantalum oxide crystal, a niobate crystal, a tantalate crystal and / or a solid solution thereof is a glass ceramic layer formed into a composite It is an essential component that provides photocatalytic properties. Niobium oxide and tantalum oxide are converted into divalent to pentavalent oxides depending on raw materials and preparation methods. The crystals are NbO crystal, Nb ₂ O ₃ crystal, NbO ₂ crystal, Nb ₂ O ₅ crystal, TaO crystal, Ta _2. O ₃ crystal, TaO ₂ crystal, Ta ₂ O ₅ crystal and the like are known, but Nb ₂ O ₅ crystal and Ta ₂ O ₅ crystal having a pentavalent oxidation number are most stable and preferable. Niobate is considered to be a composite oxide of Nb ₂ O ₅ and oxides of other elements, and the crystals thereof include, for example, lithium niobate (LiNbO ₃ ) crystals, sodium niobate (NaNbO ₃ ) crystals, niobium Potassium oxide (KNbO ₃ ) crystal, calcium niobate (CaNb ₂ O ₆ ) crystal, strontium niobate (SrNb ₂ O ₆ ) crystal, barium niobate (BaNb ₂ O ₆ ) crystal, magnesium niobate (MgNb ₂ O ₆ ) Crystal, strontium diniobate (Sr ₂ Nb ₂ O ₇ ) crystal, potassium strontium diniobate (K ₂ SrNb ₂ O ₇ ) crystal and the like, but not limited thereto. Further, the tantalate is considered to be a composite oxide of Ta ₂ O ₅ and an oxide of another element, and the crystal thereof is, for example, a lithium tantalate (LiTaO ₃ ) crystal or a sodium tantalate (NaTaO ₃ ) crystal. Potassium tantalate (KTaO ₃ ) crystal, calcium tantalate (CaTa ₂ O ₆ ) crystal, strontium tantalate (SrTa ₂ O ₆ ) crystal, barium tantalate (BaTa ₂ O ₆ ) crystal, magnesium tantalate (MgTa ₂ O) ₆ ) crystal, strontium tantalate (Sr ₂ Ta ₂ O ₇ ) crystal, potassium strontium tantalate (K ₂ SrTa ₂ O ₇ ) crystal and the like, but not limited thereto. The glass body used in the present invention is not particularly limited in the type of niobium oxide crystal, tantalum oxide crystal, niobate crystal and / or tantalate crystal as long as it has photocatalytic activity, but has particularly strong photocatalytic activity. RnNbO ₃ (Rn is at least one selected from the group consisting of Li, Na, and K) crystals and / or RnTaO ₃ are preferably included. It is known that the crystal structure of potassium niobate (KNbO ₃ ) crystal, which is a typical example of niobate and tantalate, is a perovskite structure, and is rhombohedral, orthorhombic, tetragonal, or cubic depending on the temperature. However, any crystal lattice may be used as long as it has photocatalytic activity.

The crystals of niobate may exist in the form of a solid solution with other elements. Here, as the solid solution, for example, _{Rn (Ta q Nb 1-q} ) O 3, Rn α R β (Ta q Nb 1-q) γ O δ ( wherein, Rn is Li, Na, K, Rb, One or more selected from Cs, R is one or more selected from Mg, Ca, Sr, and Ba, q means a stoichiometric number, α + 2β + 5γ = 2δ, and γ is It means an integer greater than 1). The solid solution may be a substitutional solid solution or an interstitial solid solution.

In the present invention, the total amount of one or more selected from the group consisting of the Nb ₂ O ₅ component and the Ta ₂ O ₅ component in mol% is 5.0 to 95 in total with respect to the total amount of the glass body having an oxide conversion composition. It is preferable to make it contain within the range of 0.0%. When the content of the Nb ₂ O ₅ component and / or Ta ₂ O ₅ component is less than 5.0%, a photocatalytic crystal containing a niobium component and / or a tantalum component is not sufficiently generated, and thus sufficient photocatalytic properties cannot be obtained. . On the other hand, if the content of the Nb ₂ O ₅ component and / or the Ta ₂ O ₅ component exceeds 95.0%, the stability of the glass is impaired. Accordingly, the content of one or more selected from the group consisting of the Nb ₂ O ₅ component and the Ta ₂ O ₅ component with respect to the total amount of the glass body having an oxide equivalent composition is preferably 5.0%, more preferably 10 0.0%, most preferably 15.0% is the lower limit, preferably 95.0%, more preferably 80.0%, and most preferably 75.0%. Further, the content of each of the Nb ₂ O ₅ component and / or the Ta ₂ O ₅ component is preferably 50.0%, more preferably 40.0%, and most preferably 35.0%. The Nb ₂ O ₅ component and the Ta ₂ O ₅ component can be introduced into the glass body using, for example, Nb ₂ O ₅ , Ta ₂ O ₅ or the like as a raw material.

The SiO ₂ component constitutes a glass network structure and is a component that enhances the stability and chemical durability of the glass, and is present in the vicinity of a photocatalytic crystal containing a niobium component and / or a tantalum component in which Si ⁴⁺ ions are deposited. In addition, it is a component that contributes to the improvement of the photocatalytic properties and can be optionally added. However, when the content of the SiO ₂ component exceeds 75.0%, the meltability of the glass is deteriorated, and the photocatalytic crystal containing the niobium component and / or the tantalum component is hardly precipitated. Therefore, when the SiO ₂ component is added, the content of the SiO ₂ component is preferably 0.5%, more preferably 1.0%, and most preferably 2.0% with respect to the total amount of substances in the oxide equivalent composition. The lower limit is preferably set to 75.0%, more preferably 70.0%, and most preferably 65.0%. SiO ₂ component can be introduced into the glass body is used as a raw material such as _{SiO 2, K 2 SiF 6,} Na 2 SiF 6 or the like.

The GeO ₂ component is a component having a function similar to that of the above-mentioned SiO ₂ and can be arbitrarily added. In particular, by making the content of the GeO ₂ component 20.0% or less, use of an expensive GeO ₂ component can be suppressed, so that the material cost of the glass ceramic layer can be reduced. Accordingly, the content of the GeO ₂ component with respect to the total amount of the oxide-converted composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%. The GeO ₂ component can be introduced into the glass body using, for example, GeO ₂ as a raw material.

The B ₂ O ₃ component is a component that constitutes a glass network structure and improves the stability of the glass, and can be optionally added. However, if the content exceeds 75.0%, the chemical durability of the glass is lowered, and the tendency of the photocatalytic crystals containing the niobium component and / or the tantalum component to be difficult to precipitate increases. Therefore, when the B ₂ O ₃ component is added, the content of the B ₂ O ₃ component is preferably 0.5%, more preferably 1.0%, most preferably 2 with respect to the total amount of the oxide-converted composition. 0.0% is the lower limit, preferably 75.0%, more preferably 70.0%, and most preferably 65.0%. The B ₂ O ₃ component can be introduced into the glass body using, for example, H ₃ BO ₃ , Na ₂ B ₄ O ₇ , Na ₂ B ₄ O ₇ .10H ₂ O, BPO ₄ or the like as a raw material.

P ₂ O ₅ component is a component which constitutes the network structure of the glass is a component that can be added optionally. Here, by including the P ₂ O ₅ component, it is possible to precipitate crystals containing a niobium component and / or a tantalum component at a lower firing temperature. Furthermore, by using the P ₂ O ₅ component as the main component of the network structure, more niobium component and / or tantalum component can be incorporated into the glass. However, when the content of P ₂ O ₅ exceeds 60.0%, a photocatalytic crystal containing a niobium component and / or a tantalum component becomes difficult to precipitate. Therefore, when the P ₂ O ₅ component is added, the content of the P ₂ O ₅ component with respect to the total amount of the oxide-converted composition is preferably 0.5%, more preferably 1.0%, and preferably Is 60.0%, more preferably 50.0%, and most preferably 45.0%. The P ₂ O ₅ component is introduced into the glass body using, for example, Al (PO ₃ ) ₃ , Ca (PO ₃ ) ₂ , Ba (PO ₃ ) ₂ , NaPO ₃ , BPO ₄ , H ₃ PO _4, etc. as raw materials. be able to.

The glass body contains at least one component selected from SiO ₂ component, GeO ₂ component, B ₂ O ₃ component, and P ₂ O ₅ component in the range of 10.0% or more and 85.0% or less. It is preferable. In particular, when the total amount is 85.0% or less, the melting property, stability, and chemical durability of the glass are improved, and the target photocatalytic crystal is more easily precipitated. Therefore, the total amount of one or more selected from the SiO ₂ component, the GeO ₂ component, the B ₂ O ₃ component, and the P ₂ O ₅ component is preferably 85.0% with respect to the total amount of the oxide-converted composition. The upper limit is more preferably 75.0%, and most preferably 70.0%. In addition, since it becomes difficult to obtain glass when this total amount is less than 10.0%, addition of 10.0% or more is preferable, 30.0% or more is more preferable, and 40.0% or more is most preferable. . In addition, among the SiO ₂ component, GeO ₂ component, B ₂ O ₃ component, and P ₂ O ₅ component, it is easy to improve the stability and durability of the glass, and to easily precipitate the desired photocatalytic crystal. A SiO ₂ component is most preferable, and by containing at least 10.0% of the SiO ₂ component, a glass body that is a precursor of the glass ceramic layer can be stably produced, and a glass ceramic layer having high durability and photocatalytic properties is provided. can get.

In addition to the niobium component and / or tantalum component, which are the essential components, and the P ₂ O ₅ component, the B ₂ O ₃ component, the SiO ₂ component, and the GeO ₂ component, the raw material composition is added to at least one of the components. Furthermore, the obtained glass body is mol% of the oxide conversion composition,
Alkali metal oxide component and / or alkaline earth metal oxide component 0-50.0%, and / or
M _a O _b (wherein M is one or more selected from the group consisting of W and Mo. a and b are the smallest natural numbers satisfying a: b = 2: (valence of M)) .) Component 0 to 30.0% and / or
TiO ₂ component 0-60.0%
M ¹ _c O _d (wherein M ¹ is at least one selected from the group consisting of Zr and Sn. C and d are the smallest natural numbers satisfying the valence of c: d = 2: M ¹ ) Component 0-20.0% and / or
M ² ₂ O ₃ (wherein M ² is one or more selected from the group consisting of Al, Ga, and In) Component 0 to 50.0%, and / or
Ln ₂ O ₃ (wherein Ln is selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) 1) or more components) 0-30.0% and / or
M ³ _e O _f (wherein M ³ is at least one selected from the group consisting of V, Cr, Mn, Fe, Co and Ni. E and f are e: f = 2: (M ³ The minimum natural number satisfying the valence of 0) to 10.0% and / or
Bi ₂ O ₃ component + TeO ₂ component 0 to 20.0%, and / or
As ₂ O ₃ component + Sb ₂ O ₃ component 0-5.0%
Each component of,
In the externally divided mass% with respect to the total mass of the oxide equivalent composition of the glass body,
15.0% or less of at least one nonmetallic element component selected from the group consisting of F component, Cl component, Br component, S component, N component, and C component, and / or
It is preferable to use a material prepared so as to contain 10.0% or less of at least one metal element component selected from the group consisting of Cu, Ag, Au, Pd, and Pt.

Li ₂ O component, Na ₂ O component and K ₂ O component are photocatalytic crystals (for example, lithium niobate crystal, lithium tantalate crystal, sodium niobate crystal, etc.) between Nb ₂ O ₅ component and Ta ₂ O ₅ component. It is a component that generates one or more of a sodium tantalate crystal, a potassium niobate crystal, and a potassium tantalate crystal, and improves the meltability and stability of the glass, and can be optionally added. Moreover, it is a component which lowers | hangs the glass transition temperature and makes it easy to produce | generate the crystal | crystallization containing a niobium component and a tantalum component, and suppresses the calcination temperature in a baking process lower. However, if the content of each of these components exceeds 40.0%, the stability of the glass deteriorates, and it becomes difficult to deposit photocatalytic crystals containing a niobium component or a tantalum component. Therefore, the content of each of the Li ₂ O component, the Na ₂ O component, and the K ₂ O component with respect to the total amount of the oxide-converted composition is preferably 40.0%, more preferably 35.0%, and most preferably The upper limit is 30.0%. Li ₂ O component, Na ₂ O component and K ₂ O component are raw materials such as Li ₂ CO ₃ , LiNO ₃ , LiF, Na ₂ O, Na ₂ CO ₃ , NaNO ₃ , NaF, Na ₂ S, Na ₂ SiF. ₆ , K ₂ CO ₃ , KNO ₃ , KF, KHF ₂ , K ₂ SiF ₆ or the like can be used for introduction into the glass body.

The Rb ₂ O component and the Cs ₂ O component are components that improve the meltability and stability of the glass, and can be optionally added. Moreover, it is a component which lowers | hangs the glass transition temperature and makes it easy to produce | generate the crystal | crystallization containing a niobium component and a tantalum component, and suppresses the calcination temperature in a baking process lower. However, if the content of each of these components exceeds 10.0%, the stability of the glass becomes worse, and it becomes difficult to produce photocatalytic crystals containing a niobium component or a tantalum component. Therefore, the content of each of the Rb ₂ O component and the Cs ₂ O component is preferably 10.0%, more preferably 8.0%, and most preferably 5. The upper limit is 0%. The Rb ₂ O component and the Cs ₂ O component can be contained in the glass body using, for example, Rb ₂ CO ₃ , RbNO ₃ , Cs ₂ CO ₃ , CsNO _{3 and the} like as raw materials.

The glass body comprises 40.0% in total of at least one component selected from Rn ₂ O (wherein Rn is one or more selected from the group consisting of Li, Na, K, Rb and Cs). It is preferable to contain below. In particular, when the total amount of the Rn ₂ O component is 40.0% or less, the stability of the glass is improved, and photocatalytic crystals containing a niobium component and a tantalum component are easily precipitated. Can be secured. Therefore, the total amount of the Rn ₂ O component is preferably 40.0%, more preferably 35.0%, and most preferably 30.0% with respect to the total amount of the oxide-converted composition.

MgO component, CaO component, SrO component, BaO component and ZnO component are photocatalytic crystals (for example, magnesium niobate crystal, magnesium tantalate crystal, calcium niobate crystal) between Nb ₂ O ₅ component and Ta ₂ O ₅ component. Calcium tantalate crystal, strontium niobate crystal, strontium tantalate crystal, barium niobate crystal, barium tantalate crystal, zinc niobate crystal and zinc tantalate crystal) It is a component that improves stability, and can be optionally added. In addition, it is a component that lowers the glass transition temperature to facilitate generation of crystals containing a niobium component or a tantalum component, and suppresses the firing temperature to a lower level. However, if the content of each of these components exceeds 40.0%, the stability of the glass deteriorates, and it becomes difficult to deposit photocatalytic crystals containing a niobium component or a tantalum component. Therefore, the upper limit of the content of the MgO component with respect to the total amount of the oxide-converted composition is preferably 40.0%, more preferably 30.0%, and most preferably 20.0%. Further, the content of each of the CaO component, the SrO component, the BaO component and the ZnO component with respect to the total amount of the oxide-converted composition is preferably 40.0%, more preferably 30.0%, and most preferably 25.0. % Is the upper limit. MgO component, CaO component, SrO component, BaO component and ZnO component are raw materials such as MgCO ₃ , MgF ₂ , CaCO ₃ , CaF ₂ , Sr (NO ₃ ) ₂ , SrF ₂ , BaCO ₃ , Ba (NO ₃ ) _2. , BaF ₂ , ZnO, ZnF ₂ or the like can be introduced into the glass body.

  The glass body preferably contains 40.0% or less in total of RO (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba and Zn). In particular, by making the total amount of RO components 40% or less, the stability of the glass is improved, and photocatalytic crystals containing a niobium component and a tantalum component are likely to precipitate, so that the catalytic activity of the glass ceramic layer is ensured. Can do. Accordingly, the total amount of the RO component with respect to the total amount of the oxide-converted composition is preferably 45.0%, more preferably 40.0%, and most preferably 35.0%.

Further, the glass body is composed of RO (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba and Zn) and Rn ₂ O (wherein Rn is Li, Na, K, It is preferable to contain 50.0% or less of at least one component selected from one or more components selected from the group consisting of Rb and Cs. In particular, when the total amount of the RO component and the Rn ₂ O component is 50.0% or less, the stability of the glass is improved, the glass transition temperature (Tg) is lowered, and the glass ceramic layer having the target photocatalytic crystal is obtained. More easily obtained. On the other hand, when the total amount of the RO component and the Rn ₂ O component is more than 50.0%, the stability of the glass is deteriorated, and it is difficult to deposit a photocatalytic crystal containing a niobium component or a tantalum component. Accordingly, the total amount (RO + Rn ₂ O) with respect to the total amount of oxide-converted composition is preferably 50.0%, more preferably 40.0%, and most preferably 35.0%. Further, among the RO component and the Rn ₂ O component, it is most preferable to use a Na ₂ O component particularly in order to obtain high photocatalytic properties. Therefore, higher photocatalytic properties can be obtained by containing at least 0.5% Na ₂ O component in the glass body.

Here, the glass body is composed of RO (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba and Zn) and Rn ₂ O (wherein Rn is Li, Na, K). , One or more selected from the group consisting of Rb and Cs), by containing two or more components selected from the components, the stability and chemical durability of the glass are greatly improved, and the glass ceramic after firing The mechanical strength of the layer becomes higher, and photocatalytic crystals containing a niobium component or a tantalum component are more likely to precipitate from the glass. Accordingly, the glass body preferably contains two or more types of components selected from the RO component and the Rn ₂ O component, and more preferably contains three or more types.

The WO ₃ component and the MoO ₃ component are components that enhance the melting property and stability of the glass, and are dissolved in a photocatalytic crystal containing a niobium component or a tantalum component, or are present in the vicinity thereof, thereby providing photocatalytic properties. It is a component to be improved and can be optionally added. However, if the content of each of the WO ₃ component and the MoO ₃ component exceeds 20.0%, the stability of the glass is remarkably deteriorated. Accordingly, the content of each of the WO ₃ component and the MoO ₃ component with respect to the total amount of the oxide-converted composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%. To do. The WO ₃ component and the MoO ₃ component can be introduced into the glass body using, for example, WO ₃ , MoO ₃ or the like as raw materials.

The glass body is a M _a O _b component (wherein M is one or more selected from the group consisting of W and Mo. a and b are the minimum satisfying a: b = 2: M valence) That is, it is preferable to contain 30.0% or less of at least one component selected from WO ₃ component and MoO ₃ component. In particular, when the total amount of these components is 30.0% or less, the stability of the glass is ensured, so that a good glass ceramic layer can be formed. Accordingly, the total amount of the M _a O _b component with respect to the total amount of the glass body having an oxide conversion composition is preferably 30.0%, more preferably 20.0%, and most preferably 15.0%. Although it is possible to obtain a glass ceramic layer having high photocatalytic properties even if it does not contain any M _a O _b component, the glass ceramic layer can be obtained by making the total amount of these components 0.1% or more. The photocatalytic properties of can be further improved. Therefore, the total amount of the M _a O _b component with respect to the total amount of the glass body having the oxide conversion composition is preferably 0.1%, more preferably 0.5%, and most preferably 1.0%.

TiO ₂ component is glass meltability, a component for improving the stability and chemical durability, which is a component that can be added optionally. The TiO ₂ component also has the effect of acting as a nucleating agent for a photocatalytic crystal containing a niobium component or a tantalum component, thus contributing to the precipitation of the photocatalytic crystal containing a niobium component or a tantalum component. However, when the content of the TiO ₂ component exceeds 30.0%, vitrification becomes difficult, and precipitation of photocatalytic crystals other than the intended purpose becomes significant. Therefore, when the TiO ₂ component is added, the content of the TiO ₂ component is preferably 30.0%, more preferably 20.0%, and most preferably 10.0% with respect to the total amount of substances in the oxide equivalent composition. The upper limit. The TiO ₂ component can be introduced into the glass body using, for example, TiO ₂ as a raw material.

The ZrO ₂ component is a component that increases the chemical durability of the glass ceramic layer, and can be optionally added. Further, it is a component that promotes the precipitation of crystals containing a niobium component or a tantalum component and contributes to the improvement of the photocatalytic properties by the solid solution of Zr ⁴⁺ ions in the photocatalytic crystal containing the niobium component or the tantalum component. However, when the content of the ZrO ₂ component exceeds 20.0%, vitrification becomes difficult. Therefore, the content of the ZrO ₂ component is preferably 20.0%, more preferably 15.0%, and most preferably 10.0% with respect to the total amount of substances in oxide equivalent composition. The ZrO ₂ component can be introduced into the glass body using, for example, ZrO ₂ or ZrF ₄ as a raw material.

The glass body preferably contains 20.0% or less of a TiO ₂ component and / or a ZrO ₂ component. In particular, when the total amount of these components is 20.0% or less, the stability of the glass ceramic layer is ensured, so that a good glass ceramic layer can be formed. Therefore, the total amount (TiO ₂ + ZrO ₂ ) with respect to the total amount of the oxide-converted composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%. In addition, although it is possible to obtain a glass ceramic layer having high photocatalytic characteristics even if neither of the TiO ₂ component and the ZrO ₂ component is contained, the total amount of these components is set to 0.1% or more. The photocatalytic properties of the glass ceramic layer can be further improved. Therefore, the total amount (TiO ₂ + ZrO ₂ ) with respect to the total amount of the oxide-converted composition is preferably 0.1%, more preferably 0.5%, still more preferably 1.0%, and most preferably 2.0. % Is the lower limit.

The Al ₂ O ₃ component enhances the stability of the glass and the chemical durability of the glass ceramic layer, promotes the precipitation of the photocatalytic crystal containing the niobium component and the tantalum component from the glass, and Al ³⁺ ions contain the niobium component and the tantalum. It is a component that contributes to the improvement of photocatalytic properties by dissolving in a photocatalytic crystal containing the component, and can be optionally added. However, when the content exceeds 30.0%, the melting temperature is remarkably increased and vitrification becomes difficult. Therefore, when the Al ₂ O ₃ component is added, the content of the Al ₂ O ₃ component is preferably 0.1%, more preferably 0.5%, most preferably 1 with respect to the total amount of the oxide-converted composition. 0.0% is the lower limit, preferably 30.0%, more preferably 20.0%, and most preferably 10.0%. The Al ₂ O ₃ component can be introduced into the glass body using, for example, Al ₂ O ₃ , Al (OH) ₃ , AlF ₃ or the like as a raw material.

The SnO component is a component that promotes the precipitation of crystals containing a niobium component or a tantalum component and is effective in improving the photocatalytic properties by dissolving in a photocatalytic crystal containing a niobium component or a tantalum component. When added together with Ag, Au or Pt ions, which will be described later, which has an enhancing action, it serves as a reducing agent and indirectly contributes to the improvement of the photocatalytic properties, and can be optionally added. However, when the content of these components exceeds 10.0%, the stability of the glass is deteriorated, and the photocatalytic properties are liable to deteriorate. Accordingly, the total content of the SnO component with respect to the total amount of the oxide-converted composition is preferably 10.0%, more preferably 8.0%, and most preferably 5.0%. When these components are added, the lower limit is preferably 0.01%, more preferably 0.02%, and most preferably 0.03%. The SnO component can be introduced into the glass body using, for example, SnO, SnO ₂ , SnO ₃ or the like as a raw material.

Glass ^body, in _M 1 c _{O d} component (wherein, ^{M 1} is one or more than that .c and d selected from the group consisting of Zr and Sn is c: d = 2: valence of ^{M 1,} In other words, it is preferable to contain 20.0% or less in total of at least one component selected from the ZrO ₂ component and the SnO component. In particular, when the total amount of these components is 20.0% or less, the stability of the glass is secured, so that a good glass ceramic layer can be formed. Therefore, the total amount of the M ¹ _c O _d component with respect to the total amount of the glass body having an oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%. To do. Although it is possible to obtain a glass ceramic layer having high photocatalytic properties even if it does not contain any M ¹ _c O _d component, glass ceramics can be obtained by making the total amount of these components 0.1% or more. The photocatalytic properties of the layer can be further improved. Accordingly, the total amount of the M ¹ _c O _d component with respect to the total amount of the glass body having an oxide conversion composition is preferably 0.01%, more preferably 0.02%, and most preferably 0.03%. .

The Ga ₂ O ₃ component and the In ₂ O ₃ component are components that increase the stability of the glass and promote precipitation of the photocatalytic crystal containing the niobium component and the tantalum component from the glass, and can be optionally added. Further, Ga ³⁺ ions and In ³⁺ ions are components that contribute to the improvement of the photocatalytic properties by dissolving in a photocatalytic crystal containing a niobium component or a tantalum component. However, when the content of the Ga ₂ O ₃ component exceeds 20.0%, the melting temperature is remarkably increased and vitrification becomes difficult. Therefore, the upper limit of the content of the Ga ₂ O ₃ component with respect to the total amount of substances in oxide equivalent composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%. In addition, since the In ₂ O ₃ component is expensive, its content is preferably 10.0% or less, more preferably 8.0% or less, and most preferably 5.0% or less. . The Ga ₂ O ₃ component and the In ₂ O ₃ component can be introduced into the glass body using, for example, Ga ₂ O ₃ , GaF ₃ , In ₂ O ₃ , InF ₃ or the like as a raw material.

The glass body is an M ² ₂ O ₃ component (wherein M ² is one or more selected from the group consisting of Al, Ga, and In), that is, an Al ₂ O ₃ component, Ga ₂ O _3. It is preferable to contain 50.0% or less of one or more components among the components and In ₂ O ₃ components. In particular, by making the total amount of these components 50.0% or less, photocatalytic crystals containing a niobium component and a tantalum component are more likely to precipitate, which contributes to further improvement of the photocatalytic properties of the glass ceramic layer. it can. Accordingly, the total amount of the M ² ₂ O ₃ component with respect to the total amount of the glass body having an oxide conversion composition is preferably 40.0%, more preferably 30.0%, and most preferably 25.0%. . Although it is possible to obtain a glass ceramic layer having high photocatalytic properties without containing any M ² ₂ O ₃ component, the niobium component can be obtained by setting the total amount of these components to 0.1% or more. Since the precipitation of the photocatalytic crystal containing tantalum and a tantalum component is further promoted, it can contribute to further improvement of the photocatalytic properties of the glass ceramic layer. Therefore, the total amount of the M ² ₂ O ₃ component with respect to the total amount of the glass body having an oxide conversion composition is preferably 0.1%, more preferably 0.5%, and most preferably 1.0%. .

The Bi ₂ O ₃ component and the TeO ₂ component are components that increase the meltability and stability of the glass and contribute to the improvement of the photocatalytic properties, and can be optionally added. Further, it is a component that lowers the glass transition temperature to facilitate the formation of crystals containing a niobium component or a tantalum component, and suppresses the heat treatment temperature to a lower level. However, if the total content of one or more of the group consisting of the Bi ₂ O ₃ component and the TeO ₂ component exceeds 20.0%, the stability of the glass deteriorates, and on the contrary, crystals containing a niobium component or a tantalum component. Precipitation becomes difficult. Therefore, the total content of one or more of the group consisting of the Bi ₂ O ₃ component and the TeO ₂ component with respect to the total substance amount of the oxide conversion composition is preferably 20.0%, more preferably 15.0%, Most preferably, the upper limit is 10.0%. Bi ₂ O ₃ component and TeO ₂ component can be introduced into the glass body using, for example, Bi ₂ O ₃ , TeO ₂ or the like as raw materials.

Ln ₂ O ₃ component (wherein Ln is selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) Is a component that enhances the chemical durability of the glass ceramic layer, and can be optionally added. Further, it is a component that improves the photocatalytic properties by being dissolved in the photocatalytic crystal containing a niobium component or a tantalum component or existing in the vicinity thereof. However, if the total content of the Ln ₂ O ₃ components exceeds 10.0%, the stability of the glass is significantly deteriorated. Accordingly, the total amount of the Ln ₂ O ₃ component with respect to the total amount of substances in oxide equivalent composition is preferably 10.0%, more preferably 8.0%, and most preferably 5.0%. The Ln ₂ O ₃ component includes, for example, La ₂ O ₃ , La (NO ₃ ) ₃ .XH ₂ O (X is an arbitrary integer), Gd ₂ O ₃ , GdF ₃ , Y ₂ O ₃ , YF ₃ , CeO as raw materials. ₂ , CeF ₃ , Nd ₂ O ₃ , Dy ₂ O ₃ , Yb ₂ O ₃ , Lu ₂ O ₃ or the like can be used for introduction into the glass ceramic layer.

In the case of containing Na 2 _O ingredient as a Rn 2 _O components described above, they tend to color the glass ceramic layer. Therefore, particularly when forming a colorless glass ceramic layer, Sc ₂ O ₃ component, Ce ₂ O ₃ component, Pr ₂ O ₃ component, Nd ₂ O ₃ component, Pm ₂ O ₃ component, Sm ₂ O ₃ component, Does not contain Eu ₂ O ₃ component, Tb ₂ O ₃ component, Dy ₂ O ₃ component, Ho ₂ O ₃ component, Er ₂ O ₃ component, Tm ₂ O ₃ component, Yb ₂ O ₃ component and Lu ₂ O ₃ component It is preferable.

M _x O _y component (wherein M is at least one selected from the group consisting of V, Cr, Mn, Fe, Co, and Ni, and x and y are valences of x: y = 2: M, respectively) Is the component that contributes to the improvement of the photocatalytic properties by being dissolved in the photocatalytic crystal containing the niobium component or the tantalum component or in the vicinity thereof. It is an optional component. In particular, when the total amount of the M _x O _y components is 10.0% or less, the stability of the glass ceramic can be improved and the color of the appearance of the glass ceramic layer can be easily adjusted. Therefore, the total amount of the M _x O _y components with respect to the total amount of substances in oxide equivalent composition is preferably 10.0%, more preferably 8.0%, and most preferably 5.0%. When these components are added, the lower limit is preferably 0.0001%, more preferably 0.002%, and most preferably 0.005%.

As ₂ O ₃ component and Sb ₂ O ₃ component are components for clarifying and defoaming glass, and when added together with Ag, Au, and Pt ions, which will be described later, and have the effect of enhancing photocatalytic activity, Since it plays the role of a reducing agent, it is a component that indirectly contributes to the improvement of the photocatalytic properties and can be optionally added. However, when the content of these components exceeds 5.0% in total, the stability of the glass is deteriorated, and the photocatalytic properties are liable to deteriorate. Therefore, the total content of the As ₂ O ₃ component and / or Sb ₂ O ₃ component with respect to the total amount of the oxide-converted composition is preferably 5.0%, more preferably 3.0%, and most preferably 1. 0.0% is the upper limit. When these components are added, the lower limit is preferably 0.001%, more preferably 0.002%, and most preferably 0.005%. As ₂ O ₃ component and Sb ₂ O ₃ component are, for example, As ₂ O ₃ , As ₂ O ₅ , Sb ₂ O ₃ , Sb ₂ O ₅ , Na ₂ H ₂ Sb ₂ O ₇ .5H ₂ O and the like as raw materials. And can be introduced into the glass body.

The components for clarifying and defoaming the glass are not limited to the above As ₂ O ₃ component and Sb ₂ O ₃ component. For example, such as CeO ₂ component, TeO ₂ component, etc. Well-known fining agents and defoaming agents in the field, or a combination thereof can be used.

The glass body may contain at least one nonmetallic element component selected from the group consisting of an F component, a Cl component, and a Br component. These components are components that improve the photocatalytic properties by being dissolved in the photocatalytic crystal containing a niobium component or a tantalum component, or existing in the vicinity thereof, and can be optionally added. However, when the content of these components exceeds 15.0% in total, the stability of the glass is remarkably deteriorated, and the photocatalytic properties are easily lowered. Therefore, in order to ensure good characteristics, the total of the externally divided mass ratio of the content of the nonmetallic element component to the total mass of the glass body having an oxide conversion composition is preferably 15.0%, more preferably 10. The upper limit is 0%, most preferably 5.0%. These non-metallic element components are preferably introduced into the glass body in the form of fluorides, chlorides, bromides, sulfides, nitrides, carbides or the like of alkali metals or alkaline earth metals. In addition, the content of the nonmetallic element component in this specification is assumed to be made of an oxide in which all of the cation components constituting the glass body are combined with oxygen that has a balanced charge, and the glass made of these oxides. The total mass is 100%, and the mass of the nonmetallic element component is expressed in mass% (extra divided mass% with respect to the oxide-based mass). The raw material of the nonmetallic element component is not particularly limited. For example, ZrF ₄ , AlF ₃ , NaF, CaF ₂ , etc. are used as the F component raw material, NaCl, AgCl, etc. are used as the Cl component raw material, and NaBr is used as the Br component raw material. Thus, it can be introduced into the glass body. These raw materials may be added in combination of two or more, or may be added alone.

Further, this glass body may contain at least one metal element component selected from a Cu component, an Ag component, an Au component, a Pd component, and a Pt component. These metal element components are components that improve photocatalytic properties by being present in the vicinity of the photocatalytic crystal containing a niobium component or a tantalum component, and can be optionally added. However, if the total content of these metal element components exceeds 5.0%, the stability of the glass is remarkably deteriorated, and the photocatalytic properties tend to be lowered. Accordingly, the total outer mass ratio of the content of the metal element component to the total mass of the glass body having an oxide conversion composition is preferably 5.0%, more preferably 3.0%, and most preferably 1.0%. Is the upper limit. These metal element components can be introduced into the glass body using, for example, CuO, Cu ₂ O, Ag ₂ O, AuCl ₃ , PtCl ₂ , PtCl ₄ , H ₂ PtCl ₆ , PdCl ₂ or the like as a raw material. Note that the content of the metal element component in the present specification is based on the assumption that all the cation components constituting the glass body are made of an oxide combined with oxygen that balances the charge, and the entire glass made of these oxides. The mass of the metal element component is expressed in terms of mass% (externally divided mass% with respect to the oxide-based mass). When these components are added, the lower limit is preferably 0.0001%, more preferably 0.002%, and most preferably 0.005%.

(About ingredients that should not be included)
Next, components that should not be contained in the glass body and components that are not preferably contained will be described.

  If necessary, other components can be added to the glass body as long as the properties of the glass ceramic layer are not impaired. However, lead compounds such as PbO, each component of Th, Cd, Tl, Os, Be, Se, and Hg tend to refrain from being used as harmful chemical substances in recent years, not only in the manufacturing process of glass ceramic composites, Environmental measures are required until processing and disposal after commercialization. Therefore, when importance is placed on the environmental impact, it is preferable not to substantially contain them except for inevitable mixing. As a result, the glass body is substantially free from substances that pollute the environment. Therefore, the glass-ceramic composite can be manufactured, processed, and discarded without taking special environmental measures.

The composition of the glass body is expressed by mol% with respect to the total amount of the glass body of the oxide conversion composition, so it cannot be expressed directly in the description of mass%, but it satisfies the characteristics required in the present invention. The composition represented by mass% of each component present in the product generally takes the following values in terms of oxide conversion.
Ta ₂ O ₅ component and / or Nb ₂ O ₅ component 8-80 mass% in total
And SiO ₂ component 0 to 50% by mass and / or GeO ₂ component 0 to 10% by mass and / or B ₂ O ₃ component 0 to 50% by mass and / or P ₂ O ₅ component 0 to 50% by mass and / or Li ₂ O component 0-20% by weight and / or Na ₂ O component 0-25% by weight and / or K ₂ O ingredient 0-25% by weight and / or Rb ₂ O component 0 to 15 wt% and / or Cs ₂ O Component 0-20% by mass and / or MgO component 0-25% by mass and / or CaO component 0-30% by mass and / or SrO component 0-30% by mass and / or BaO component 0-30% by mass and / or ZnO Component 0-30 mass% and / or WO ₃ component 0-30 mass% and / or MoO ₃ component 0-10 mass% and / or TiO ₂ component 0-20 mass% and / or ZrO ₂ component 0-15 mass % And / or Al ₂ O ₃ component 0-20 mass% and / or SnO component 0-10 mass% and / or Ga ₂ O ₃ component 0-15 mass% and / or In ₂ O ₃ component 0-10 mass% and / or Bi ₂ O ₃ component 0-30% by weight and / or TeO ₂ component 0-30% by weight and / or Ln ₂ O ₃ 0 to 15% by weight sum of component and / or M ³ _e O _f component total 0 to 10% by weight and / or As ₂ O ₃ component and _Sb 2 _{O 3} component in total 0-5% by weight
further,
In the externally divided mass ratio with respect to 100% of the total mass of the glass body of the oxide conversion composition,
At least one nonmetallic element component selected from the group consisting of N component, S component, F component, Cl component, Br component, and C component 0 to 15.0% by mass and / or Cu component, Ag component, Au 0 to 10.0% by mass of at least one metal element component selected from the group consisting of a component, a Pd component, and a Pt component

  As long as this condition is satisfied, the raw material composition is a glass in which a non-glass body is vitrified even if it is a non-glass raw material (usually a powder, referred to as a batch) containing a glass-forming oxide or the like. It may be a raw material (usually a crushed material and called cullet).

[Crushing process]
In the pulverization step, the glass body is pulverized to form a pulverized glass, and a granular material is produced. By producing the powder body, the glass body has a relatively small particle size, so that the placement on the substrate is facilitated. Moreover, it becomes easy to mix other components by setting it as a granular material. The particle diameter and shape of the granular material can be appropriately set according to the type of base material and the surface characteristics required for the composite. Specifically, if the average particle size of the powder is too large, it becomes difficult to form a glass ceramic layer having a desired shape on the substrate. Therefore, the average particle size is preferably as small as possible. Therefore, the upper limit of the average particle size of the powder is preferably 100 μm, more preferably 50 μm, and most preferably 10 μm. In addition, the value of D50 (cumulative 50% diameter) when measured by the laser diffraction scattering method can be used for the average particle diameter of the granular material, for example. Specifically, a value measured by a particle size distribution measuring apparatus MICROTRAC (MT3300EXII) manufactured by Nikkiso Co., Ltd. can be used.

  In addition, although the grinding | pulverization of a glass body is not specifically limited, For example, it can carry out using a ball mill, a jet mill, etc.

[Crystalling process]
In the method of the present invention, when the crystallization treatment is performed at the timing after the vitrification step / before the pulverization step or after the pulverization step / before the firing step, they can be carried out as independent steps (crystallization steps). . As described above, the purpose of the crystallization treatment is to heat-treat the glass body or powder and precipitate crystals inside. Since the photocatalytic crystal containing the niobium compound and / or the tantalum compound is precipitated inside and on the surface of the glass body or the granular material by the crystallization treatment, the glass ceramic layer contains the niobium compound and / or the tantalum compound. A crystal phase can be reliably contained. The heat treatment conditions (temperature, time) can be appropriately set according to the composition of the glass body, the required degree of crystallization, and the like.

  Specifically, the lower limit of the heat treatment temperature in the crystallization step is the glass transition temperature (Tg) of the glass body, preferably Tg + 10 ° C., more preferably Tg + 50 ° C., more preferably Tg + 100 ° C., most preferably Tg + 150 ° C. is there. On the other hand, if the temperature is too high, photocatalytic crystals such as niobium compounds and tantalum compounds decrease, and the tendency to deposit other crystals that are not intended becomes strong, so that the photocatalytic properties are easily lost. Therefore, the upper limit of the temperature in the heat treatment is preferably Tg + 600 ° C. of the glass body, more preferably Tg + 500 ° C., and most preferably Tg + 450 ° C. The heat treatment time for crystallization is the same as in the above baking step.

  In the case where the crystallization treatment is performed simultaneously with the firing step, as described above, a powder or granular material in which no crystals are precipitated is used, and the firing temperature in the firing step is set to a temperature at which crystallization is possible. By controlling, it becomes possible to precipitate a desired crystal from the glass phase.

[Mixing process]
In this manufacturing method, the mixing process which mixes arbitrary components with the granular material obtained at a grinding | pulverization process can be included. The mixing of the components into the powder can be arbitrarily performed before the molding of the powder. Thereby, since content of each component contained in a glass ceramic layer is fluctuate | varied, the glass ceramic layer which has a desired characteristic can be formed. Here, the component to be added to the granule is not particularly limited, but the component that can enhance the function of the component by increasing the amount at the stage of the granule or the vitrification of the molten glass becomes difficult. Although only a small amount can be blended in the raw material composition, it is preferable to mix components that promote photocatalytic action.

In addition, in this specification, the state after mixing another component with a granular material may be named generically as a "mixture." When the mixing step is performed, in each step performed after the mixing step, the “powder body” in the case where the mixing step is not performed is replaced with “mixture” in the same manner.
Hereinafter, components that can be added to the granular material will be described in detail.

(Addition of photocatalytic crystals)
In this production method, photocatalytic crystals, that is, TiO _{2 in} a crystalline state, niobium compounds (for example, Nb ₂ O ₅ , RnNbO ₃ , RNb ₂ O ₆ , (Rn is one or more selected from Li, Na, and K, and R represents one or more selected from Mg, Ca, Sr, Ba and Zn)), tantalum compounds (for example, Ta ₂ O ₅ , RnTaO ₃ , RTa ₂ O ₆ (Rn is Li, Na, and 1 or more types selected from K, and R means one or more types selected from Mg, Ca, Sr, Ba and Zn)) and one or more types selected from the group consisting of WO ₃ It may have the process of mixing in and producing a mixture. In the method of the present invention, a crystal phase having photocatalytic properties can be produced from a glass body without mixing photocatalytic crystals. However, the addition of one or more selected from the group consisting of TiO ₂ , niobium compound, tantalum compound and WO ₃ that are already in a crystalline state increases the amount of crystals having photocatalytic properties, so that the photocatalytic function It is possible to reliably manufacture a glass-ceramic layer with enhanced resistance.

  Here, the mixing amount of the photocatalytic crystal can be appropriately set so that a desired amount of the photocatalytic crystal is generated in the glass ceramic layer according to the composition of the glass body, the temperature in the production process, and the like. Mixing of photocatalytic crystals is optional, but if the amount of photocatalytic crystals is too small, it is difficult to enrich the amount of crystals having photocatalytic crystals in the glass ceramic layer. On the other hand, when the amount of the photocatalytic crystal is excessive, problems such as difficulty in sintering are likely to occur. Therefore, the lower limit of the amount of the photocatalytic crystal to be mixed is preferably 0.5% by mass ratio with respect to the mixture, more preferably 3.0%, and most preferably 10.0%. On the other hand, the upper limit of the amount of the photocatalytic crystal to be mixed is preferably 95.0%, more preferably 80.0%, and most preferably 60.0% by mass ratio to the mixture.

The niobium compound, tantalum compound and WO ₃ added in this step are known to have orthorhombic, tetragonal and cubic crystal structures, but as long as they have photocatalytic activity, It may be a thing. In general, there are three types of crystal forms of TiO ₂ : anatase, rutile, and brookite. Of these, the crystalline TiO ₂ used in this step may be one or more of these three types, but is preferably a combination of anatase and brookite in terms of excellent photocatalytic function, More preferably, it is anatase.

  The raw material particle size of the photocatalytic crystal added to the powder is preferably as small as possible from the viewpoint of enhancing the photocatalytic activity, but if the raw material particle size is too small, the glass contained in the powder during firing and the like There is a risk of reacting and disappearing without maintaining the crystalline state. Moreover, when the raw material particles are too fine, there is a problem that handling in the manufacturing process becomes difficult. On the other hand, if the raw material particle size is too large, it tends to remain in the final product in the form of raw material particles, and the tendency to hardly obtain desired photocatalytic properties becomes strong. Accordingly, the size of the raw material particles is preferably in the range of 11 to 10 μm, more preferably in the range of 15 to 5 μm, and most preferably in the range of 20 to 1 μm. In particular, from the viewpoint of facilitating handling in the production process, the range of 11 to 500 nm is preferable, the range of 15 to 100 nm is more preferable, and the range of 20 to 50 nm is most preferable.

(Addition of non-metallic element components)
In this production method, a step of mixing an additive containing one or more selected from the group consisting of N component, S component, F component, Cl component, Br component, and C component into the above-mentioned powder or mixture. You may have. These non-metallic element components can be blended as part of the components of the raw material composition at the stage of making a batch or cullet before producing the glass body as described above. However, it is easier to introduce and mix these non-metallic element components into the glass powder after making the glass body. It becomes possible to easily obtain a glass ceramic layer having

  When a nonmetallic element component is added, the mixing amount of the additive can be appropriately set according to the composition of the glass body. From the viewpoint of sufficiently improving the photocatalytic function of the glass ceramic layer, the amount of this mixture is preferably 0.01% or more, more preferably 0, in terms of the mass ratio with respect to the granular material or mixture thereof as the sum of the nonmetallic components. 0.05% or more, and most preferably 0.1% or more. On the other hand, when added excessively, the photocatalytic properties are liable to be reduced, so the amount of addition is preferably 20.0% or less in terms of the mass ratio of the powder or its mixture as the sum of the nonmetallic components, More preferably, it is 10.0% or less, Most preferably, it is 5.0% or less.

The raw material in the case of adding a nonmetallic element component is not particularly limited, but the N component is AlN ₃ , SiN _4, etc., the S component is NaS, Fe ₂ S ₃ , CaS _2, etc., the F component is ZrF ₄ , AlF ₃ , etc. NaF, CaF _2, etc., Cl component NaCl, AgCl or the like, Br component NaBr etc., C component can be added using a TiC, SiC or ZrC and the like. In addition, the raw materials of these nonmetallic element components may be added in combination of two or more, or may be added alone.

(Addition of metal element components)
This manufacturing method may include a step of mixing one or more metal element components selected from the group consisting of Cu, Ag, Au, Pd, Pt, Ru, Re, and Rh into a powder or a mixture. . As described above, these components can be added to the glass body as a part of the glass body components in the batch or cullet stage before the glass body is produced. However, after preparing the glass body, mixing these metal element components into the powder body of the glass body is easier to introduce and more effective in its function. A glass ceramic layer having high photocatalytic properties can be easily obtained.

When adding a metal element component, the mixing amount may be appropriately set according to the composition of the glass body. From the viewpoint of sufficiently improving the photocatalytic function of the glass ceramic, the total amount of the metal element component to be added is preferably 0.001% or more, more preferably 0.005%, in terms of the mass ratio to the granular material or mixture thereof. Or more, and most preferably 0.01% or more. On the other hand, if added excessively, the photocatalytic properties are likely to deteriorate, so the upper limit of the total amount of the metal element component to be added is preferably 10.0% or less, more preferably, by mass ratio with respect to the granular material or mixture thereof. Is 5.0% or less, and most preferably 3.0% or less. The starting of the case of adding a metal element component, for example, _{Cu 2 O,} Ag 2 _O, can be used AuCl 3, PtCl _4, and the like. In addition, the raw materials for these metal element components may be added in combination of two or more, or may be added alone.

The particle size and shape of the metal element component may be appropriately set according to the composition of the glass body, the amount of the Ta ₂ O ₅ component and / or the Nb ₂ O ₅ component, the crystal type, etc., but the photocatalytic function of the glass ceramic layer In order to achieve the maximum, the average particle size of the metal element component should be as small as possible. Therefore, the upper limit of the average particle diameter of the metal element component is preferably 5.0 μm, more preferably 1.0 μm, and most preferably 0.1 μm.

[Slurry process]
In this manufacturing method, you may have the process (slurry process) which disperse | distributes a granular material in arbitrary fluids, and makes it a slurry state. Thereby, the process of arrange | positioning a granular material on a base material becomes easy. This step is an optional step that can be performed after the grinding step or the mixing step or simultaneously with the grinding step. Specifically, the slurry can be prepared by adding an organic / inorganic binder and / or a solvent to the granular material. Since the glass body particles melt and bond firmly in the firing process, the glass body itself plays a role as a binder for the glass ceramic layer, but when the degree of crystallinity of the powder when placed on the substrate is high Since the function of the glass itself as a binder tends to be weakened, an organic or inorganic binder can be added to compensate for this. In addition, a powder granule here is the concept including the above-mentioned mixture.

As the organic binder, commercially available binders widely used as molding aids for press molding, rubber press, extrusion molding, and injection molding can be used. Specific examples include acrylic resin, ethyl cellulose, polyvinyl butyral, methacrylic resin, urethane resin, butyl methacrylate, vinyl copolymer and the like. Examples of the inorganic binder include metal alkoxide, sodium silicate, and alumina (Al ₂ O ₃ .nH ₂ O). In view of durability against photocatalysis, an inorganic binder is preferable. The lower limit of the content of the organic binder with respect to the slurry is preferably 40% by mass, more preferably 30% by mass, and most preferably 20% by mass in that the molding can be facilitated sufficiently.

  As the solvent, known solvents such as polyvinyl alcohol (PVA), isopropyl alcohol (IPA), butanol, and water can be used, but alcohol or water is preferable from the viewpoint of reducing the environmental burden. In addition, an appropriate amount of a dispersant may be used in combination in order to obtain a more homogeneous molded body, and an appropriate amount of a surfactant may be used in combination in order to improve the foam removal efficiency during drying. The dispersant is not particularly limited, and examples thereof include hydrocarbons such as toluene, xylene, benzene, hexane, and cyclohexane, ethers such as cellosolve, carbitol, tetrahydrofuran (THF), dioxolane, acetone, methyl ethyl ketone, and methyl isobutyl ketone. And ketones such as cyclohexanone, and esters such as methyl acetate, ethyl acetate, n-butyl acetate and amyl acetate can be used, and these can be used alone or in combination of two or more.

[Baking process]
In the firing step, the powder body is placed on the substrate and then heated and fired to produce a composite. Thus, a glass ceramic layer containing crystals containing a niobium compound and / or a tantalum compound is formed on the substrate. Here, although the specific process of a baking process is not specifically limited, The process of arrange | positioning a granular material on a base material, The process of heating up gradually the granular material arrange | positioned on a base material to preset temperature. The step of holding the granular material at a set temperature for a predetermined time and the step of gradually cooling the granular material to room temperature may be included.

(Arrangement on the substrate)
In this manufacturing method, a granular material is arrange | positioned on a base material. Thereby, a photocatalytic characteristic can be provided with respect to a wider base material. The base material used here is not particularly limited, but it is preferable to use an inorganic material such as glass or ceramics, a metal, or the like because it is easily compounded with a crystal containing a niobium compound and / or a tantalum compound.

  In order to dispose the granular material on the substrate, it is preferable to dispose the slurry containing the granular material on the substrate with a predetermined thickness and size. Thereby, since the glass ceramic layer which has a photocatalytic characteristic is easily formed on a base material, the glass ceramic layer of a desired shape and thickness can be produced. Here, the thickness of the glass ceramic layer to be formed can be appropriately set according to the application of the composite. It is one of the features of the method of the present invention that the thickness of the glass ceramic layer can be set in a wide range. From the viewpoint of imparting sufficient durability so that the glass ceramic layer does not peel off, the thickness is preferably 500 μm or less, more preferably 200 μm or less, and most preferably 100 μm or less. As a means for disposing the slurry on the substrate, a doctor blade or calendar method, a coating method such as spin coating or dip coating, an inkjet, a bubble jet (registered trademark), a printing method such as offset, a die coater method, a spray method, Examples include an injection molding method, an extrusion molding method, a rolling method, a press molding method, and a roll molding method. In addition, the means for arranging the granular material on the base material is not limited to the above-described means using the slurry, and means for directly placing the powder of the granular material on the base material may be used.

(Degreasing)
In this manufacturing method, when the molded body contains an organic binder, the formed molded body is heated to a temperature of 350 ° C. or higher as an optional step before firing the granular material disposed on the substrate. Is preferred. Thereby, since the organic binder etc. which were contained in the molded object are decomposed | disassembled and gasified and discharged | emitted, organic substance can be removed from glass ceramics (it is called a degreasing process). The lower limit of the heating temperature in the degreasing step is preferably 350 ° C., more preferably 380 ° C., and most preferably 400 ° C. from the viewpoint that organic substances can be sufficiently removed. Although the degreasing step varies depending on the type of the organic binder, it is preferable to perform the degreasing step for about 2 hours, for example.

(Baking)
The firing conditions in the firing step may be appropriately set according to the composition of the glass body constituting the powder and the type and amount of the additive to be mixed. Specifically, the atmosphere temperature at the time of firing can be controlled in two ways, which will be described later, depending on the state of the granular material arranged on the substrate.

  The first firing method is a case where a crystal phase containing a desired niobium compound and / or tantalum compound has already been generated in the powder arranged on the substrate. For example, the glass body or the powder The case where the crystallization process is performed with respect to the body is mentioned. The firing temperature in this case can be appropriately selected within a temperature range of 1200 ° C. or less in consideration of the heat resistance of the substrate, but when the firing temperature exceeds 1200 ° C., the generated niobium compound and / or tantalum compound is included. The photocatalytic crystal is easily transferred to another crystal. Accordingly, the upper limit of the firing temperature is preferably 1200 ° C, more preferably 1100 ° C, and most preferably 1000 ° C.

  The second firing method is a case where the granular material arranged on the base material has not yet been crystallized and does not have a crystal phase containing a niobium compound and / or a tantalum compound. In this case, it is necessary to perform crystallization treatment of glass simultaneously with firing. If the firing temperature is too low, a fired body having a desired photocatalytic crystal cannot be obtained, and thus firing at a temperature higher than at least the glass transition temperature (Tg) of the glass body is required. Specifically, the lower limit of the firing temperature is the glass transition temperature (Tg) of the glass body, preferably Tg + 50 ° C., more preferably Tg + 100 ° C., and most preferably Tg + 150 ° C. On the other hand, if the firing temperature becomes too high, the photocatalytic crystal containing the niobium compound and / or the tantalum compound tends to decrease and the photocatalytic properties tend to disappear, so the upper limit of the firing temperature is preferably Tg + 600 ° C. of the glass body. Yes, more preferably Tg + 500 ° C., and most preferably Tg + 450 ° C.

  Moreover, it is necessary to set the baking time in a baking process according to a composition, baking temperature, etc. of a glass body. If the rate of temperature increase is slow, it may be only necessary to heat to the heat treatment temperature. However, as a guideline, it is preferable that the temperature is short when the temperature is high and long when the temperature is low. Specifically, the lower limit is preferably 3 minutes, more preferably 5 minutes, even more preferably 10 minutes, and most preferably 20 minutes, in that crystals can be grown to some extent and a sufficient amount of crystals can be precipitated. To do. On the other hand, if the heat treatment time exceeds 24 hours, the target photocatalytic crystal may become too large or other crystals may be formed, and sufficient photocatalytic properties may not be obtained. Therefore, the upper limit of the firing time is preferably 24 hours, more preferably 19 hours, and most preferably 18 hours. In addition, the baking time here refers to the length of the period during which the baking temperature is maintained at a certain level (for example, the set temperature) or more in the baking process.

  It is preferable to perform a baking process and a degreasing process, exchanging air in a gas furnace, a microwave furnace, an electric furnace, etc., for example. However, the present invention is not limited to this condition, and the above process may be performed in an inert gas atmosphere, a reducing gas atmosphere, or an oxidizing gas atmosphere.

[Surface treatment process]
In this manufacturing method, you may further have the surface treatment process which performs the process of performing surface treatments, such as an etching, to the baked composite body, especially the glass ceramic layer of a composite body. Etching can be performed, for example, by immersing the composite or the glass ceramic layer of the composite in an acidic or alkaline solution. If it does in this way, the surface of a glass-ceramics layer can be made into an uneven | corrugated state or a porous state because a glass phase melt | dissolves. As a result, since the exposed area of the photocatalytic crystal containing a niobium component or a tantalum component increases, higher photocatalytic properties can be obtained. The acidic or alkaline solution used for the immersion is not particularly limited as long as it can corrode the glass phase other than the photocatalytic crystal containing the niobium component or the tantalum component of the glass ceramic layer, and includes, for example, fluorine or chlorine. An acid (hydrofluoric acid, hydrochloric acid, etc.) can be used.

  As another etching method, etching may be performed by spraying hydrogen fluoride gas, hydrogen chloride gas, hydrofluoric acid, hydrochloric acid, or the like on the surface of the fired body.

  In addition, the manufacturing method which manufactures the composite_body | complex which concerns on this invention is not specifically limited as long as it is a method which can form the composite provided with the glass-ceramics layer and the base material, For example, the bulk-shaped glass sliced thinly A method may be used in which a self-supporting film of ceramics or glass ceramics is disposed on a substrate, and the glass ceramics are adhered or welded onto the substrate.

<Glass ceramic composite>
The composite of the present invention is a composite comprising a base material and a glass ceramic layer positioned on the base material, and the glass ceramic layer is an Nb ₂ O ₅ component based on an oxide basis. And one or more selected from Ta ₂ O ₅ components in total consisting of 5.0% or more and 95.0% or less, and composed of SiO ₂ component, B ₂ O ₃ component, P ₂ O ₅ component and GeO ₂ component. 1 or more types selected from a group are contained 10.0% or more and 85.0% or less in total. As a result, the photocatalytic crystal contained in the crystal phase of the glass ceramic layer has photocatalytic properties, and the adhesion between the glass ceramic layer and the substrate is enhanced by the binder effect of the glass phase contained in the glass ceramic layer. For this reason, it has high photocatalytic properties, more specifically, decomposition properties of organic substances caused by light irradiation, and high hydrophilicity, but there are few problems of surface peeling, and even if the surface is scraped, the performance is poor. In addition, a composite having excellent durability can be obtained.

  Here, the composition range of each component constituting the glass ceramic layer is preferably mol% of the oxide conversion composition, and is preferably within the same range as the composition range of each component constituting the glass body. Thereby, since it becomes easy to precipitate the photocatalytic crystal contained in the crystal phase of the glass ceramic layer, the photocatalytic crystal of the glass ceramic layer can be increased. In addition, content with respect to the total amount of substances of the glass ceramic layer of an oxide conversion composition is calculated | required from the composition and content of the component added to this granular material obtained from this glass body. Moreover, when the nonmetallic element component described below is not included in the raw material composition, the composition of the granular material is substantially equal to the composition of the glass body. That is, when the non-metallic element component is not included in the glass body and no other component is added to the powder body, the composition of the glass ceramic layer is substantially equal to the composition of the glass body.

[Physical properties of glass-ceramic composites]
The glass ceramic layer of the composite of the present invention has a crystal phase and a glass phase. More specifically, it is preferable that the crystal phase and the glass phase coexist as crystallized glass in which the crystal phase is precipitated from the glass phase in that the adhesion between the crystal phase and the glass phase can be improved. Here, it is preferable that the crystal phase contained in the glass ceramic layer contains crystals of a compound containing one or more components selected from Ti, W, Nb, and Ta. More specifically, TiO ₂ , TiP ₂ O ₇ , (TiO) ₂ P ₂ O ₇ , RnNbO ₃ , RnTaO ₃ and crystals composed of one or more of these solid solutions may be included. It is more preferable that one or more crystals of TiO ₂ are included in the group consisting of a rutile type, anatase type and brookite type (wherein Rn is an alkali metal) One or more of them). By including these crystals, glass ceramics can have a high photocatalytic function. Among them, anatase type titanium oxide (TiO ₂ ) has higher photocatalytic activity than the rutile type, and thus can impart higher photocatalytic properties to the glass ceramic layer.

  In addition, the solid solution in the present invention means a state in which two or more kinds of metal solids or non-metal solids are dissolved in each other at the atomic level, and the whole is in a uniform solid phase, sometimes referred to as a mixed crystal. is there. Depending on how the solute atoms permeate, there are interstitial solid solutions in which elements smaller than the gaps in the crystal lattice enter, substitutional solid solutions in which they replace the parent phase atoms, and the like.

The glass ceramic layer preferably contains a NASICON (Na super ionic conductor) type crystal or a solid solution thereof in the crystal phase. Thereby, since the band gap energy of the glass ceramic layer is adjusted to an appropriate magnitude, the response to light can be further improved. Further, when a NASICON type crystal and a TiO ₂ crystal are contained at the same time, the photocatalytic characteristics can be further improved. Here, the crystal of NASICON type structure is specifically a titanium phosphate compound such as alkali metal titanium phosphate complex salt or alkaline earth metal titanium phosphate complex salt, alkali metal niobium phosphate complex salt, alkaline earth metal niobate complex salt. And crystals of alkali metal tantalum phosphate composite salt, alkaline earth metal tantalum phosphate composite salt, alkali metal tungsten phosphate composite salt, alkaline earth metal tungsten phosphate composite salt, and the like. Among these, since the effect of RnTi ₂ (PO ₄ ) ₃ , RTi ₄ (PO ₄ ) ₆ or a solid solution thereof is particularly remarkable, it is preferable to contain at least one of these (wherein Rn is Li, One or more of Na, K, Rb, and Cs, and R is one or more of Mg, Ca, Sr, and Ba). By depositing these photocatalytic crystals from glass, higher photocatalytic properties can be developed. Here, the NASICON type crystals include LiTi ₂ (PO ₄ ) ₃ , NaTi ₂ (PO ₄ ) ₃ , KTi ₂ (PO ₄ ) ₃ , MgTi ₄ (PO ₄ ) ₆ , CaTi ₄ (PO ₄ ) _6. SrTi ₄ (PO ₄ ) ₆ , BaTi ₄ (PO ₄ ) _{6 and the} like. Further, as a solid solution of a NASICON type crystal, for example, Li _{1 + x} Ti _2−x A _x (PO ₄ ) ₃ (0 <x ≦ 0.5, A is a trivalent metal ion), Li _{1 + 3x} Ti ₂ (P _1-x Si _x O ₄ ) ₃ , LiTi _2-x A _x (PO ₄ ) ₃ (A is a tetravalent metal ion), and the like. In the present specification, these crystals having photocatalytic properties and solid solutions thereof are collectively referred to as “photocatalytic crystals”.

  The glass ceramic layer preferably contains a photocatalytic crystal in a volume ratio of 1.0% or more and 95.0% or less with respect to the total volume of the glass (wherein Rn is Li, Na, K, Rb). And at least one selected from Cs, and R is at least one selected from Mg, Ca, Sr, and Ba). When the content of the photocatalytic crystal is 1.0% or more, the glass ceramic layer can have good photocatalytic properties. On the other hand, when the content of the photocatalytic crystal is 95.0% or less, the glass ceramic layer can obtain good mechanical strength.

  The crystallization ratio, which is the abundance ratio of crystals with respect to the entire glass ceramic layer, is preferably 1.0%, more preferably 5.0%, and most preferably 10.0% as a lower limit, and preferably 95. The upper limit is 0%, more preferably 90.0%, and most preferably 85.0%. When the crystallization rate is 1.0% or more, the glass ceramic layer can have good photocatalytic properties. On the other hand, when the crystallization rate is 95.0% or less, the glass ceramic layer can obtain good mechanical strength.

At this time, as for the size of the crystals contained in the glass ceramic layer, the average diameter when approximated to a sphere is preferably 5 nm to 3 μm. It is possible to control the size of the deposited photocatalytic crystal by controlling the heat treatment conditions, but in order to extract effective photocatalytic properties, the crystal size is preferably in the range of 5 nm to 3 μm, and 10 nm. More preferably, it is in the range of ˜1 μm, and most preferably in the range of 10 nm to 300 nm. The average diameter of the crystal is, for example, from the half width of the diffraction peak of XRD, Scherrer's formula:
D = 0.9λ / (βcosθ)
Can be used to estimate. Here, D is the crystal size, λ is the X-ray wavelength, and θ is the Bragg angle (half the diffraction angle 2θ). In particular, when the diffraction peak of XRD is weak or the diffraction peak overlaps with other peaks, this is determined from the area of the crystal particles measured using a scanning electron microscope (SEM) or transmission electron microscope (TEM). It can also be estimated by obtaining the diameter assuming that is a circle. When calculating the average value of crystal grain sizes using a microscope, it is preferable to randomly measure the diameter of 100 or more crystals. Note that the size of the particles showing the crystal phase can be controlled to a desired size by controlling the heat treatment conditions in the crystallization step when forming the composite, for example.

  The glass ceramic layer preferably has irregularities on the surface. Thereby, since the exposed area of the crystal phase containing the photocatalytic crystal is increased, higher photocatalytic properties can be obtained. Here, the means for forming irregularities on the surface of the glass ceramic layer is appropriately selected from mechanical and / or chemical surface treatment means. In particular, it is preferable to perform etching by immersing the glass ceramic layer in an acidic or alkaline solution. Thereby, since the glass phase immersed in the solution melt | dissolves, the surface of a glass ceramic layer can be made into a more complicated and fine uneven | corrugated state and a porous state. The solution used for the immersion is not particularly limited as long as it can corrode glass phases other than the crystal phase including the photocatalytic crystal of the glass ceramic layer. For example, an acid containing fluorine or chlorine (hydrofluoric acid, Hydrochloric acid or the like). As another means of etching, etching may be performed by spraying hydrogen fluoride gas, hydrogen chloride gas, hydrofluoric acid, hydrochloric acid, or the like on the surface of the fired body.

  The glass ceramic layer preferably exhibits catalytic activity by light of any wavelength from the ultraviolet region to the visible region. For example, the decomposition activity index of methylene blue based on Japanese Industrial Standard JIS R 1703-2: 2007 of the glass ceramic layer is 3.0 nmol / L / min or more. Thereby, since the dirt substance, bacteria, etc. adhering to the surface of the glass ceramic layer are decomposed by oxidation or reduction reaction, the glass ceramic layer can be used for antifouling use or antibacterial use. In particular, the photocatalytic crystal contained in the composite of the present invention exhibits a high catalytic effect for irradiation with ultraviolet rays and / or visible light, and therefore, particularly for light of any wavelength from the ultraviolet region to the visible region. A glass ceramic layer having excellent responsiveness can be obtained. Here, the decomposition activity index of methylene blue of the glass ceramic layer is preferably 3.0 nmol / L / min or more, more preferably 3.5 nmol / L / min or more, and most preferably 4.0 nmol / L / min or more. Here, the light having a wavelength in the ultraviolet region referred to in the present invention is an invisible electromagnetic wave having a wavelength shorter than that of visible light and longer than that of soft X-ray, and the wavelength is in the range of approximately 10 to 400 nm. In addition, the light having a wavelength in the visible region referred to in the present invention is an electromagnetic wave having a wavelength that can be seen by human eyes among electromagnetic waves, and the wavelength is in a range of about 400 nm to 700 nm. When the surface of the glass ceramic layer is irradiated with light of any wavelength from the ultraviolet region to the visible region, or light of a wavelength that combines them, the surface of the glass ceramic layer is expressed. Since attached dirt substances and bacteria are decomposed by oxidation or reduction reaction, the glass ceramic layer can be used for antifouling use, antibacterial use and the like.

  Moreover, it is preferable that a glass ceramic layer has the high hydrophilicity brought about by light irradiation. For example, it is preferable that the contact angle between the water droplets and the surface irradiated with light having any wavelength from the ultraviolet region to the visible region or light having a combined wavelength thereof is 30 ° or less. Thereby, since the surface of the glass ceramic layer exhibits hydrophilicity and has a self-cleaning action, the surface of the glass ceramic layer can be easily washed with water, and a reduction in photocatalytic properties due to dirt can be suppressed. The contact angle between the surface of the glass ceramic layer irradiated with light and water droplets is preferably 30 ° or less, more preferably 25 ° or less, and most preferably 20 ° or less.

[Applications of glass-ceramic composites]
In the glass-ceramic composite produced by the method of the present invention, the photocatalytic crystal containing at least one of the group consisting of a niobium compound and a tantalum compound having photocatalytic activity is uniformly deposited on the inside and surface of the glass ceramic layer. Therefore, it has excellent photocatalytic properties and is excellent in durability. In addition, since the glass ceramic layer of the present invention is manufactured through the form of a granular material, it has a high degree of freedom when processing the size and shape according to the shape of the substrate, and requires photocatalytic properties. Can be processed into various articles.

(Photocatalyst functional member)
This glass-ceramic composite is useful as a photocatalyst functional member in machines, devices, instruments, etc. that are exposed to the external environment and contaminated by the adhesion of organic matter, etc., or used in an atmosphere where fungi easily float. is there. For example, by using the photocatalytic functional member of the present invention for constituent members such as tiles, window frames, lamps, and building materials, these constituent members can be provided with a photocatalytic function.

(Hydrophilic member)
The glass ceramic composite is also useful as a hydrophilic member. For example, by using the hydrophilic member of the present invention as a structural member such as a building panel, tile, or window, the member can have a self-cleaning function.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by the following Examples.

Examples 1 to 56:
Composition of glass bodies of Examples (No. 1 to No. 56) of the present invention, firing (sintering) temperature and time when producing glass ceramic layers using these glass bodies, and these glass bodies Tables 1 to 6 show the results of the types of precipitated crystal phases and the contact angles with water droplets in the glass ceramic layer produced using the above.

  In Examples (No. 1 to No. 56) of the present invention, all of the corresponding oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, metaphosphate compounds, etc. After selecting the high-purity raw materials used for the glass of the above, weighing them so as to have the composition ratio of each example and mixing them uniformly, and then putting them in a platinum crucible or a quartz crucible, Correspondingly, it melt | dissolved in the temperature range of 1250-1580 degreeC with an electric furnace for 1 to 24 hours, and after stirring and homogenizing, the glass melt was dripped in flowing water, and the granular or flaky glass body was obtained. The glass body was pulverized with a jet mill to obtain a powder body having a particle size of 10 μm or less.

  This powder was dispersed in methanol to prepare a slurry. Here, in Examples (No. 1 to No. 52), the obtained slurry was applied onto an alumina substrate, and methanol was dried to obtain a slurry layer. On the other hand, in the examples (No. 53 to No. 56), the obtained slurry was applied onto a tile, and methanol was dried to obtain a slurry layer. About this slurry layer, it heated up to the temperature of Table 1-Table 6, hold | maintained at this temperature for the time of Table 1-Table 6, and performed the baking process and the crystallization process simultaneously. After the firing step, the temperature was lowered to room temperature to obtain a composite having a glass ceramic layer having a thickness of 50 μm.

  Here, the kind of crystal phase produced | generated in the glass ceramic layer of the composite_body | complex using the glass body of the Example (No.1-No.56) is X-ray-diffraction apparatus (The Philips company make, brand name: X'Pert -MPD).

  As shown in Tables 1 to 6, the precipitated crystals of the glass ceramic layers using the glass bodies of the examples (No. 1 to No. 56) all have niobium components and tantalum components having photocatalytic activity. At least one of the included photocatalytic crystals was included.

Examples 57-70:
Table 7, in Example (No.57~No.63), mixed with glass body _A of Example 1 was ground _{(52% SiO 2 -20% Nb} 2 O 5 -28% Na 2 O 5) The other substances, their blending amounts, as well as the firing conditions and the crystalline phase produced are shown. Further, Table 8, Example in (No.64~No.70), vitreous _B of Example 13 was pulverized _{(52% SiO 2 -22% Ta} 2 O 5 -14% Li 2 O-12% Other substances to be mixed with Na ₂ O), their blending amounts, as well as the firing conditions and the crystalline phase produced are shown. Here, the powder of glass body A or glass body B having a particle size of 10 μm or less, the additive, and the mixture were further uniformly mixed, and then the mixture was dispersed in methanol to form a slurry. This slurry was applied on an alumina substrate to obtain a slurry layer. About this slurry layer, it heated up to the temperature of Table 7-Table 8, and hold | maintained at this temperature for the time of Table 7-Table 8, and performed the baking process and the crystallization process simultaneously. After the firing step, the temperature was lowered to room temperature to obtain a composite having a glass ceramic layer having a thickness of 50 μm. The composition of the composite at this time is as shown in Tables 7-8.

  Here, the kind of the crystal phase produced | generated in the glass ceramic layer of the Example (No.57-No.70) was identified with the X-ray-diffraction apparatus (The Philips company make, brand name: X'Pert-MPD). The results are shown in Tables 7-8.

  As shown in Tables 7 to 8, each of the precipitated crystal phases of the glass ceramic layers using the glass bodies of Examples (No. 57 to No. 70) has a niobium compound having photocatalytic activity and / or Alternatively, a photocatalytic crystal containing a tantalum compound was included. For this reason, it was guessed that the glass ceramic composite of the Example of this invention has a high photocatalytic characteristic, for example, the decomposition | disassembly characteristic of organic substance, and hydrophilicity.

Next, the XRD results of the glass ceramic molded bodies of Examples 1 and 31 are shown in FIGS. 1 and 2, respectively. In the XRD pattern of FIG. 1, in Example 1, a peak represented by “◯” occurred at an incident angle peculiar to NaNbO ₃ , and the presence of NaNbO ₃ crystal could be confirmed. On the other hand, in the XRD pattern of FIG. 2, in the XRD pattern of Example 31, a peak represented by “◯” was generated at the incident angle peculiar to NaTaO ₃ , and the presence of NaTaO ₃ crystal was confirmed. Further, in Example 31, a peak represented by “□” was generated at the incident angle peculiar to LiTaO ₃ , and the presence of LiTaO ₃ crystal could be confirmed. Therefore, it was considered that the glass ceramic molded bodies of Examples 1 and 31 have high photocatalytic properties.

  Next, the composites obtained in Examples 53 to 56 were put in water and irradiated with a 500 W high-pressure mercury lample to confirm the presence or absence of photocatalytic properties. At the same time, the methylene blue decomposition activity index (nmol / l / min) of the glass ceramic layers obtained in Examples 53 to 56 was determined based on Japanese Industrial Standard JIS R 1703-2: 2007.

More specifically, the decomposition activity index of methylene blue was determined by the following procedure.
A 0.020 mM methylene blue aqueous solution (hereinafter referred to as an adsorption solution) and a 0.010 mM methylene blue aqueous solution (hereinafter referred to as a test solution) were prepared.
Then, the surface of the sample of the example in which the photocatalytic characteristics were recognized and one opening of the quartz tube (inner diameter 10 mm, height 30 mm) were fixed with high vacuum silicone grease (manufactured by Dow Corning Toray). The adsorbing liquid was injected from the other opening of the quartz tube to fill the test cell with the adsorbing liquid. Thereafter, the other opening of the quartz tube and the liquid surface of the adsorbing liquid are covered with a cover glass (manufactured by Matsunami Glass Industry Co., Ltd., trade name: white edge polished frost No. 1), and the light is not exposed to the glass. The adsorbed liquid was sufficiently adsorbed to the sample over 24 hours. About the adsorption liquid after adsorption | suction, the light absorbency with respect to the light of wavelength 664nm was measured using the spectrophotometer (The JASCO Corporation make, model number: V-650), and the light absorbency of this adsorption liquid was similarly measured about the test liquid. Adsorption was completed when the absorbance was greater.
At this time, from the values of absorbance (Abs (0)) and methylene blue concentration (c (0) = 10 [μmol / L]) measured for the test solution, the conversion coefficient K [μmol / L].
K = c (0) / Abs (0) (1)
Next, after removing the cover glass and replacing the liquid in the quartz tube with the test solution, the other opening of the quartz tube and the liquid surface of the adsorbing liquid were covered again with the cover glass and irradiated with ultraviolet rays of 1.0 mW / cm ² . . And the light absorbency with respect to the light of wavelength 664nm after irradiating an ultraviolet-ray for 60 minutes, 120 minutes, and 180 minutes was measured.
From the value of absorbance Abs (t) measured t minutes after the start of ultraviolet light irradiation, the concentration C of the methylene blue test solution t minutes after the start of ultraviolet light irradiation using the following formula (2) (T) [μmol / L] was determined. Here, K is the conversion factor described above.
C (t) = K × Abs (t) (2)
A plot was created with C (t) determined as described above on the vertical axis and the irradiation time t [min] of ultraviolet rays on the horizontal axis. At this time, the slope a [μmol / L / min] of the straight line obtained from the plot was determined by the least square method, and the decomposition activity index R [nmol / L / min] was determined using the following equation (3).
R = | a | × 1000 (3)

  As a result, the glass ceramic layers of Examples 53 to 56 were confirmed to have photocatalytic properties because gas generation was observed when irradiated with high-pressure mercury lample. Moreover, the decomposition activity index of the glass ceramic layers of Examples 53 to 56 was 3.0 nmol / l / min or more, and was generally in the range of 7.6 to 13.2 nmol / l / min. For this reason, it became clear that the glass ceramic layer of the Example of this invention has a desired photocatalytic characteristic.

  Next, the hydrophilicity of the glass ceramic composites of Examples 2 and 12 was evaluated by measuring the contact angle between the sample surface and water droplets by the θ / 2 method. That is, water is dropped on the surface of the glass ceramic layer after the ultraviolet irradiation, and the height h from the surface of the glass ceramic layer to the top of the water droplet and the radius r of the surface in contact with the test piece of the water droplet are determined as the Kyowa interface. It measured using the contact angle meter (CAX) by a scientific company, and contact angle (theta) with water was calculated | required from the relational expression of (theta) = 2tan-1 (h / r). The contact angle was measured by immersing in a hydrofluoric acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) having an HF concentration of 46% (mass percentage) for 1 minute.

  As a result, it was confirmed that the hydrophilicity of the glass ceramic layers of Examples 2 and 12 was such that the contact angle with water became 30 ° or less after 2 hours from the start of irradiation with ultraviolet rays. Thereby, it became clear that the glass-ceramic layer of this invention has high hydrophilicity.

  Therefore, it was confirmed that the glass-ceramic composite of the example of the present invention is excellent in durability and easily forms a crystal phase containing a niobium compound and / or a tantalum compound.

  Although the present invention has been described in detail for the purpose of illustration, this embodiment is only for the purpose of illustration, and many modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention. Will be understood.

Claims (19)

A composite comprising a base material and a glass ceramic layer positioned on the base material,
The glass ceramic layer has a crystal phase and a glass phase;
The glass ceramic layer is mol% based on oxides, and includes at least one selected from Nb ₂ O ₅ component and Ta ₂ O ₅ component in a total amount of 5.0% to 95.0%, and SiO ₂ A composite containing one or more selected from the group consisting of a component, a B ₂ O ₃ component, a P ₂ O ₅ component, and a GeO ₂ component in a total of 10.0% to 85.0%.   The composite according to claim 1, wherein the glass ceramic layer exhibits catalytic activity by light having a wavelength from an ultraviolet region to a visible region.   The composite according to claim 1 or 2, wherein a contact angle between a surface of the glass ceramic layer irradiated with light having a wavelength from an ultraviolet region to a visible region and a water droplet is 30 ° or less. A method for producing a composite comprising a substrate and a glass ceramic layer having photocatalytic activity located on the substrate,
The manufacturing method which has a baking process which heats and bakes after arrange | positioning the granular material which consists of a glass body containing a niobium component and / or a tantalum component on a base material. 5. The glass body contains 5.0 to 95.0% in total of at least one selected from the group consisting of Nb ₂ O ₅ component and Ta ₂ O ₅ component in mol% based on oxide. The manufacturing method as described. The glass body, in mole percent on the oxide basis, SiO _{2 component,} P 2 _{O 5 component,} B a 2 _{O 3} 1 or more selected from the ingredients and the group consisting of GeO ₂ component in total 10.0 to 85 The manufacturing method of Claim 4 or 5 containing 0.0%.   The manufacturing method according to any one of claims 4 to 6, wherein the granular material is made of pulverized glass obtained by pulverizing the glass body.   The manufacturing method according to any one of claims 4 to 7, further comprising a crystallization step in which heat treatment is performed on the glass body or the powder body to precipitate crystals therein.   The manufacturing method according to claim 4, wherein the baking is performed at a temperature of 1200 ° C. or less.   The manufacturing method according to any one of claims 4 to 9, wherein the firing is performed at an atmospheric temperature that is equal to or higher than a glass transition temperature (Tg) of the glass body and is equal to or lower than a temperature 600 ° C higher than Tg. One or more selected from the group consisting of crystalline TiO ₂ , niobium compound, tantalum compound and WO ₃ are mixed at a mass ratio of 95.0% or less with respect to the total amount of the powder and the mixture to obtain a mixture. The manufacturing method according to claim 4, further comprising a step of manufacturing.   An additive containing at least one selected from the group consisting of an N component, an S component, an F component, a Cl component, a Br component, and a C component is mixed at a mass ratio of 20.0% or less with respect to the powder or the mixture. The manufacturing method according to claim 4, further comprising a step of:   5. A step of mixing 10.0% or less of a metal element component composed of one or more selected from the group consisting of Cu, Ag, Au, Pd, and Pt in a mass ratio with respect to the granular material or the mixture. The manufacturing method in any one of 12 to 12.   The manufacturing method in any one of Claim 4 to 13 which has the process of disperse | distributing the said granular material or the said mixture in a solvent, and making it a slurry state.   The manufacturing method according to claim 4, wherein the firing is performed for 3 minutes to 24 hours.   The manufacturing method according to any one of claims 4 to 15, further comprising a step of immersing or etching the composite in an acidic or alkaline solution. The glass body is in mol% based on oxide,
TiO ₂ component 0-60.0% and / or
Alkali metal oxide component and / or alkaline earth metal oxide component 0-50.0%, and / or
M _a O _b (wherein M is one or more selected from the group consisting of W and Mo. a and b are the smallest natural numbers satisfying a: b = 2: (valence of M)) .) Component 0-50.0% and / or
M ¹ _c O _d (wherein, M ¹ is at least one selected from the group consisting of Zr and Sn. C and d are the minimum satisfying c: d = 2: (valence of M ¹ )) A natural number) component 0-30% and / or
M ² ₂ O ₃ (wherein M ² is one or more selected from the group consisting of B, Al, Ga, and In) component 0 to 50.0%, and / or
Ln ₂ O ₃ (wherein Ln is selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. One or more) component 0-30.0% and / or
M ³ _e O _f (wherein M ³ is at least one selected from the group consisting of V, Cr, Mn, Fe, Co, and Ni. E and f are e: f = 2: (M ³ ), the smallest natural number satisfying 0) to 10.0%, and / or
Bi ₂ O ₃ component + TeO ₂ component 0 to 20.0%, and / or
As ₂ O ₃ component + Sb ₂ O ₃ component 0-5.0%
Each component of,
In mass% with respect to the total mass of the oxide equivalent composition of the glass body,
15.0% or less of at least one nonmetallic element component selected from the group consisting of F component, Cl component, Br component, S component, N component, and C component, and / or
The manufacturing method according to any one of claims 4 to 16, which contains 10.0% or less of at least one metal element component selected from the group consisting of Cu, Ag, Au, Pd, and Pt.   The photocatalyst functional member containing the composite_body | complex manufactured with the manufacturing method in any one of Claim 4 to 17.   The hydrophilic member containing the composite_body | complex manufactured with the manufacturing method in any one of Claim 4 to 17.

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