JP5525228B2 - Glass ceramics and manufacturing method thereof - Google Patents

Description

  The present invention relates to a glass ceramic and a manufacturing method thereof.

Inorganic titanium compounds including titanium oxide (TiO ₂ ) are known to have high catalytic activity as a photocatalyst. In other words, the inorganic titanium compound generates electrons and holes when irradiated with light having energy higher than the band gap energy, so that the oxidation-reduction reaction is strongly promoted near the surface of the molded body containing the inorganic titanium compound. . Further, it is known that the surface of a molded body containing an inorganic titanium compound has a so-called self-cleaning action that is washed with water droplets such as rain because it exhibits hydrophilicity that allows water to easily get wet.

  Here, as a technique for forming a layer containing an inorganic titanium compound on the surface of the substrate, a technique for applying or coating the inorganic titanium compound on the surface of the substrate, or a technique for including the inorganic titanium compound in the substrate is given. It is done.

  Among these, as a coating agent used for forming an inorganic titanium compound layer on the surface of a substrate, a photocatalytic coating agent in which a high concentration inorganic titanium compound is contained in an aqueous emulsion having a synthetic resin as a dispersed phase is disclosed. (For example, Patent Document 1).

On the other hand, as a technique for including an inorganic titanium compound in a base material, glass for photocatalysts containing a predetermined amount of each component of SiO ₂ , Al ₂ O ₃ , CaO, MgO, B ₂ O ₃ , ZrO ₂ , and TiO ₂ is used. Is disclosed (for example, Patent Document 2).

JP 2008-81712 A Japanese Patent Laid-Open No. 9-315837

  However, when the inorganic titanium compound is applied or coated on the surface of the substrate, the durability of the coating film or coating layer is not sufficient, and the coating film or coating layer may be peeled off from the substrate. For example, when a coating film is formed using the photocatalytic coating agent disclosed in Patent Document 1, resin or organic binder remaining in the coating film is decomposed by ultraviolet rays or the like, or by the catalytic action of an inorganic titanium compound. As a result of oxidation or reduction, the durability of the coating film tends to deteriorate over time. In addition, the above-mentioned inorganic titanium compound requires nano-sized ultrafine particles in order to bring out sufficient photocatalytic activity. However, the nano-sized ultrafine particles have a problem that they are expensive to produce and easily aggregate. .

  Moreover, in the glass for photocatalysts disclosed in Patent Document 2, titanium oxide does not have a crystal structure and is present in the glass in an amorphous form, so that its photocatalytic properties are insufficient.

  In particular, anatase type, rutile type and brookite type are known as crystal forms of titanium oxide, but in order to provide high photocatalytic properties, anatase type, rutile type and / or It is considered important to have a brookite-type titanium oxide.

  The present invention has been made in view of the above circumstances, and has a glass having excellent durability on the surface and one or more types of titanium oxide crystals of the group consisting of anatase type, rutile type and brookite type on the surface. It aims at providing the manufacturing method of ceramics, and the photocatalyst functional molded object and hydrophilic molded object containing the glass ceramics manufactured by this manufacturing method.

In order to solve the above-mentioned problems, the present inventors have conducted intensive test studies, and as a result, one or more selected from the group consisting of TiO ₂ component and P ₂ O ₅ component, ZrO ₂ component and SnO component. In combination with the components, and suppressing the content of these components within a predetermined range, there is no need to use a nano-sized raw material, one or more members of the group consisting of anatase type, rutile type and brookite type It has been found that glass ceramics having fine crystals of inorganic titanium compounds including titanium oxide (TiO ₂ ) can be obtained, and the present invention has been completed. Specifically, the present invention provides the following.

(1) 15.0% or more and 88.9% or less of TiO ₂ component and 11.0% or more and 84.9% of P ₂ O ₅ component in mol% with respect to the total amount of glass ceramics of oxide conversion composition. Glass ceramics containing 0.1% or more and 20.0% or less of at least one component selected from the group consisting of ZrO ₂ component and SnO component.

(2) SiO ₂ component 0 to 60.0% and / or GeO ₂ component 0 to 60.0% in mol% with respect to the total amount of glass ceramics having an oxide conversion composition
The glass ceramic according to (1), which further comprises

(3) the glass ceramic total material of the oxide composition in terms of, Li ₂ O component from 0 to 40.0% by mol%, and / or Na ₂ O component from 0 to 40.0%, and / or _{K 2} O components from 0 to 40.0%, and / or Rb ₂ O component from 0 to 10.0%, and / or Cs ₂ O component from 0 to 10.0%
The glass ceramic according to (1) or (2), further containing each component of

(4) MgO component 0-40.0% and / or CaO component 0-40.0% and / or SrO component 0-40. 0% and / or BaO component 0-40.0% and / or ZnO component 0-50.0%
The glass ceramic according to any one of (1) to (3), further comprising:

(5) the glass ceramic total material of the oxide composition in terms of, _B 2 _{O 3} component from 0 to 40.0% by mol%, and / or _Al 2 _{O 3} component from 0 to 30.0%, and / or Ga ₂ O ₃ component 0 to 30.0% and / or In ₂ O ₃ component 0 to 10.0%
The glass ceramic according to any one of (1) to (4), further comprising:

(6) Nb ₂ O ₅ component 0 to 50.0% and / or Ta ₂ O ₅ component 0 to 50.0% and / or mol% with respect to the total amount of glass ceramics having an oxide equivalent composition WO ₃ component 0-50.0% and / or MoO ₃ component 0-50.0%
The glass ceramic according to any one of (1) to (5), further comprising:

(7) the glass ceramic total material of the oxide composition in terms, _Bi 2 _{O 3} component from 0 to 20.0% by mol%, and / or TeO ₂ components from 0 to 20.0%, and / or Ln _a O _b component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, Ce, Nd, Dy, Yb and Lu, and for each component excluding Ce, a = 2 and b = 3, For Ce, a = 1 and b = 2) 0 to 30.0% in total, and / or M _x O _y component (wherein M is a group consisting of V, Cr, Mn, Fe, Co, Ni) And x and y are each the minimum natural number satisfying x: y = 2: (valence of M)) 0 to 10.0% in total and / or As ₂ O ₃ Component and / or Sb ₂ O ₃ component 0 to 5.0% in total
The glass ceramic according to any one of (1) to (6), further comprising:

  (8) Mass ratio of at least one nonmetallic element selected from the group consisting of F component, Cl component, Br component, S component, N component, and C component to the total mass of glass ceramics in terms of oxide The glass ceramic according to any one of (1) to (7), wherein 10.0% or less is contained.

  (9) At least one metal element component selected from the group consisting of Cu, Ag, Au, Pd, Pt, Ru, and Rh is 10.0% or less in terms of a mass ratio with respect to the total mass of the glass ceramic of the oxide conversion composition. The glass ceramic according to any one of (1) to (8), which is contained.

(10) TiO ₂ , TiP ₂ O ₇ , (TiO) ₂ P ₂ O ₇ , and any one of (1) to (9) including a crystal phase composed of one or more of these solid solutions Glass ceramics.

(11) The glass ceramic according to (10), wherein the crystalline phase contains one or more TiO ₂ crystals of the group consisting of anatase type, rutile type and brookite type.

  (12) The glass ceramic according to (10) or (11), wherein the crystal phase is contained in a volume ratio of 1.0% to 95.0% with respect to the total volume of the glass ceramic.

  (13) The glass ceramic according to any one of (1) to (12), wherein catalytic activity is expressed by light having a wavelength from the ultraviolet region to the visible region.

  (14) The glass ceramic according to (13), wherein the decomposition activity index of methylene blue based on JIS R 1703-2: 2007 is 3.0 nmol / L / min or more.

  (15) The glass ceramic according to any one of (1) to (14), wherein a contact angle between a surface irradiated with light having a wavelength from the ultraviolet region to the visible region and a water droplet is 30 ° or less.

  (16) A photocatalytic functional glass ceramic molded body comprising the glass ceramic according to any one of (1) to (15).

  (17) A hydrophilic glass-ceramic molded body comprising the glass-ceramic according to any one of (1) to (15).

  (18) The glass ceramic molded body according to (16) or (17), which has a fiber shape.

  (19) The method for producing a glass ceramic according to any one of (1) to (15), wherein the raw material composition mixture is maintained at a temperature of 1250 ° C. or higher to form a liquid phase at least partially, and then cooled. Of glass ceramics to be solidified by heating.

  (20) A method for producing a glass ceramic according to any one of (1) to (15), wherein a melting step of mixing raw materials to obtain a melt thereof, and cooling to obtain a glass body by cooling the melt. A reheating step of raising the temperature of the glass body to a temperature range exceeding the glass transition temperature, a crystallization step of generating crystals while maintaining the temperature within the crystallization temperature range, and the temperature And a recooling step of obtaining a crystal-dispersed glass by lowering it to outside the crystallization temperature region.

  (21) The method for producing a glass ceramic according to (20), wherein the temperature range of the crystallization step is 510 ° C. or higher and 1200 ° C. or lower.

  (22) The glass according to any one of (19) to (21), wherein the method further includes an etching step of performing dry etching and / or immersion in an acidic or alkaline solution on the glass body after the crystallization step. Manufacturing method of ceramics.

According to the present invention, the TiO ₂ component and the P ₂ O ₅ component and one or more components selected from the group consisting of the ZrO ₂ component and the SnO component are used in combination, and the content of these components is set to a predetermined value. By keeping it within the range, crystals of inorganic titanium compounds including one or more kinds of titanium oxide (TiO ₂ ) in the group consisting of anatase type, rutile type and brookite type are easily precipitated. Since these crystal phases are uniformly deposited on the inside and the surface of the glass, there is no problem of peeling of the surface, and even if the surface is scraped, the performance is not inferior, and the glass ceramic having excellent durability and its manufacturing method Can be obtained.

It is an XRD pattern about the glass ceramic molded object of the Example of this invention. It is a graph showing the decomposition activity index | exponent before and behind a crystallization process about the glass ceramic molded object of the Example of this invention. It is a graph showing the decomposition activity index | exponent before and behind an etching process about the glass ceramic molded object of the Example of this invention. It is a graph showing the relationship between the irradiation time of an ultraviolet-ray and the water contact angle calculated | required about the glass ceramic molded object of the Example of this invention. It is a graph showing the relationship between the crystallization temperature and the particle diameter of an anatase crystal about the glass-ceramic molded object of the Example of this invention. It is a graph showing the particle diameter of the anatase crystal formed by various crystallization conditions about the glass ceramic molded object of the Example of this invention.

In the glass ceramic of the present invention, the TiO ₂ component is 15.0% or more and 88.9% or less and the P ₂ O ₅ component is 11.0% in mol% with respect to the total amount of the glass ceramic having an oxide conversion composition. It contains 84.9% or less, and contains 0.1% or more and 20.0% or less of one or more components selected from the group consisting of ZrO ₂ component and SnO component. By using together the TiO ₂ component and the P ₂ O ₅ component and one or more components selected from the group consisting of the ZrO ₂ component and the SnO component, and suppressing the content of these components within a predetermined range In addition, crystals of inorganic titanium compounds including one or more types of titanium oxide (TiO ₂ ) in the group consisting of anatase type, rutile type and brookite type are likely to precipitate. Since these crystal phases are uniformly deposited on the inside and the surface of the glass, there is no problem of peeling of the surface, and even if the surface is scraped, the performance is not inferior and a glass ceramic excellent in durability can be obtained.

Further, the glass ceramic of the present invention can be produced using either of the following two production methods. One is a production method in which the raw material composition mixture is maintained at a temperature of 1250 ° C. or higher to form a liquid phase at least partially, and then cooled to solidify. The other is a melting step of mixing raw materials to obtain a melt, a cooling step of cooling the melt to obtain a glass body, and raising the temperature of the glass body to a temperature range exceeding the glass transition temperature. And a recrystallization process for maintaining the temperature within the temperature range to produce crystals. By using these manufacturing methods, the TiO ₂ crystal phase is uniformly deposited on the inside and the surface of the glass, so there is no problem of peeling of the surface, and even if the surface is scraped, the performance is not inferior and the durability is excellent. Glass ceramics can be obtained.

  Hereinafter, embodiments of the glass ceramic of the present invention and the method for producing the same will be described in detail. However, the present invention is not limited to the following embodiments, and may be appropriately changed within the scope of the object of the present invention. Can be added. In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the meaning of invention is not limited.

[Glass ceramics]
First, components and physical properties of the glass ceramic of the present invention will be described.

  Hereafter, the composition range of each component which comprises the glass ceramic of this invention 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 glass ceramics 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 glass by making the total substance amount of the said production | generation oxide into 100 mol%.

<About essential and optional components>
The TiO ₂ component is an indispensable and indispensable component that crystallizes to precipitate from the glass as a crystal of TiO ₂ or a compound of phosphorus and brings about photocatalytic properties. In particular, by setting the content of the TiO ₂ component to 15.0% or more, the TiO ₂ crystal phase is easily precipitated, and the concentration of TiO ₂ crystals in the glass ceramic is increased, so that desired photocatalytic characteristics are ensured. be able to. On the other hand, when the content of the TiO ₂ component exceeds 88.9%, vitrification becomes very difficult. Therefore, the content of the TiO ₂ component is preferably 15.0%, more preferably 25.0%, and most preferably 30.0% with respect to the total amount of glass ceramics having an oxide equivalent composition, preferably 88. 0.9%, more preferably 85.0%, and most preferably 80.0%. The TiO ₂ component can be contained in the glass ceramic using, for example, TiO ₂ as a raw material.

P ₂ O ₅ component is a component constituting the network structure of the glass. By making the glass ceramic of the present invention a phosphate glass in which the P ₂ O ₅ component is the main component of the network structure, more TiO ₂ component can be incorporated into the glass. Further, since it is possible to precipitate TiO ₂ crystals at a lower heat treatment temperature, one or more TiO ₂ crystals of the group consisting of anatase type, rutile type and brookite type having high photocatalytic activity, particularly anatase type TiO ₂ crystals. Can be easily formed. In particular, when the content of P ₂ O ₅ is less than 11.0%, vitrification is difficult, and when the content of P ₂ O ₅ exceeds 84.9%, the TiO ₂ crystal phase is difficult to precipitate. Accordingly, the content of the P ₂ O ₅ component with respect to the total amount of the glass ceramics in terms of oxide composition is preferably 11.0%, more preferably 15.0%, most preferably 20.0%, and preferably Is 84.9%, more preferably 70.0%, and most preferably 60.0%. The P ₂ O ₅ component is made of glass ceramics using, for example, Al (PO ₃ ) ₃ , Ca (PO ₃ ) ₂ , Ba (PO ₃ ) ₂ , Na (PO ₃ ), BPO ₄ , H ₃ PO _4, etc. as raw materials. Can be contained within.

The ZrO ₂ component is a component that enhances chemical durability, promotes the precipitation of TiO ₂ crystals, and contributes to the improvement of photocatalytic properties by solid solution of Zr ⁴⁺ ions in the TiO ₂ crystal phase, and can be arbitrarily added. It is an ingredient. 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 glass ceramics having an oxide equivalent composition. The ZrO ₂ component can be contained in the glass ceramic using, for example, ZrO ₂ , ZrF ₄ or the like as a raw material.

SnO component promotes the precipitation of TiO ₂ crystals, and easy to obtain a TiO ₂ crystal phase by suppressing the reduction of ^{Ti 4+,} and a solid solution to TiO ₂ crystal phase is effective components for improving the photocatalytic properties Yes, it is a component that acts as a reducing agent when added together with Ag, Au, or Pt ions, which will be described later, and has the effect of enhancing the photocatalytic activity, and indirectly contributes to the improvement of the photocatalytic activity. It is a component that can be 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. Therefore, the upper limit of the SnO component content is preferably 10.0%, more preferably 8.0%, and most preferably 5.0% with respect to the total amount of glass ceramics having an oxide equivalent composition. The SnO component can be contained in the glass ceramic using, for example, SnO, SnO ₂ , SnO ₃ or the like as a raw material.

The glass ceramic of the present invention preferably contains 20.0% or less of at least one component selected from a ZrO ₂ component and a SnO component. In particular, by setting the mass sum of at least one component selected from these components to 20.0% or less, the stability of the glass ceramic is ensured, so that a good glass ceramic can be formed. Accordingly, the upper limit of the mass sum (ZrO ₂ + SnO) with respect to the total amount of glass ceramics in terms of oxide composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%. In addition, although it is possible to obtain glass ceramics having high photocatalytic properties even if neither ZrO ₂ component nor SnO component is contained, the mass sum of at least one component selected from these components is 0.1. By setting it to at least%, the photocatalytic properties of the glass ceramic can be further improved. Therefore, the lower limit of the mass sum (ZrO ₂ + SnO) with respect to the total amount of glass ceramics in terms of oxide composition is preferably 0.1%, more preferably 0.2%, and most preferably 0.5%.

The SiO ₂ component is a component that constitutes a glass network structure and improves the stability and chemical durability of the glass, and is present in the vicinity of the TiO ₂ crystal phase on which Si ⁴⁺ ions are precipitated, thereby improving the photocatalytic activity. It is a component that contributes and can be optionally added. However, when the content of the SiO ₂ component exceeds 60.0%, the meltability of the glass is deteriorated and the TiO ₂ crystal phase is hardly precipitated. Accordingly, the content of the SiO ₂ component with respect to the total amount of the glass ceramic material in oxide equivalent composition is preferably 60.0%, more preferably 45.0%, and most preferably 30.0%. The SiO ₂ component can be contained in the glass ceramic using, for example, SiO ₂ , K ₂ SiF ₆ , Na ₂ SiF ₆ or the like as a raw material.

The GeO ₂ component is a component having a function similar to that of the above-mentioned SiO ₂ and can be arbitrarily added to the glass ceramic of the present invention. In particular, by making the content of the GeO ₂ component 60.0% or less, the use of an expensive GeO ₂ component can be suppressed, so that the material cost of the glass ceramic can be reduced. Therefore, the content of the GeO ₂ component with respect to the total amount of the glass ceramic material having an oxide conversion composition is preferably 60.0%, more preferably 45.0%, and most preferably 30.0%. The GeO ₂ component can be contained in the glass ceramic using, for example, GeO ₂ as a raw material.

The glass ceramic of the present invention preferably contains 60.0% or less of at least one component selected from a SiO ₂ component and a GeO ₂ component. In particular, by making the mass sum of at least one component selected from the SiO ₂ component and the GeO ₂ component 60.0% or less, the meltability, stability and chemical durability of the glass are improved, and after the heat treatment Since the glass ceramics are less likely to crack, glass ceramics with higher mechanical strength can be easily obtained. Therefore, the upper limit of the mass sum (SiO ₂ + GeO ₂ ) with respect to the total amount of the glass ceramic material of the oxide conversion composition is preferably 60.0%, more preferably 45.0%, and most preferably 30.0%. Although it is possible to obtain glass ceramics having photocatalytic properties without containing SiO ₂ component and GeO ₂ component, the properties are further improved by containing SiO ₂ component and / or GeO ₂ component. . If the total amount of these components is less than 0.1%, the effect is not sufficient, so addition of 0.1% or more is preferable, 3.0% or more is more preferable, and 5.0% or more is most preferable. .

The Li ₂ O component is a component that improves the meltability and stability of the glass and makes it difficult to cause cracks in the glass ceramic after heat treatment, and lowers the glass transition temperature to lower the heat treatment temperature, and has high photocatalytic activity. It is a component that facilitates the formation of one or more TiO ₂ crystals of the group consisting of anatase type, rutile type, and brookite type, particularly an anatase type TiO ₂ crystal, and can be optionally added. However, if the content of the Li ₂ O component exceeds 40.0%, the stability of the glass is deteriorated, and the precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the Li ₂ O component content is preferably 40.0%, more preferably 30.0%, and most preferably 15.0% with respect to the total amount of glass ceramics in oxide equivalent composition. The Li ₂ O component can be contained in the glass ceramic using, for example, Li ₂ CO ₃ , LiNO ₃ , LiF or the like as a raw material.

The Na ₂ O component is a component that improves the meltability and stability of the glass and makes it difficult to crack the glass ceramic after the heat treatment, and lowers the glass transition temperature to keep the heat treatment temperature lower, and has a high photocatalytic activity. It is a component that facilitates the formation of one or more TiO ₂ crystals of the group consisting of anatase type, rutile type, and brookite type, particularly an anatase type TiO ₂ crystal, and can be optionally added. However, if the content of the Na ₂ O component exceeds 40.0%, the stability of the glass is worsened, and precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the upper limit of the content of the Na ₂ O component with respect to the total amount of the glass ceramic material in oxide equivalent composition is preferably 40.0%, more preferably 30.0%, and most preferably 15.0%. The Na ₂ O component can be contained in the glass ceramic using, for example, Na ₂ O, Na ₂ CO ₃ , NaNO ₃ , NaF, Na ₂ S, Na ₂ SiF ₆ or the like as a raw material.

The K ₂ O component is a component that improves the meltability and stability of the glass and makes it difficult to crack the glass ceramic after the heat treatment, and lowers the glass transition temperature to keep the heat treatment temperature lower, and has high photocatalytic activity. It is a component that facilitates the formation of one or more TiO ₂ crystals of the group consisting of anatase type, rutile type, and brookite type, particularly an anatase type TiO ₂ crystal, and can be optionally added. However, when the content of the K ₂ O component exceeds 40.0%, the stability of the glass is deteriorated, and the precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the upper limit of the content of the K ₂ O component with respect to the total amount of the glass ceramic material having an oxide conversion composition is preferably 40.0%, more preferably 30.0%, and most preferably 15.0%. The K ₂ O component can be contained in the glass ceramic using, for example, K ₂ CO ₃ , KNO ₃ , KF, KHF ₂ , K ₂ SiF ₆ or the like as a raw material.

The Rb ₂ O component is a component that improves the meltability and stability of the glass and makes it difficult to cause cracks in the glass ceramic after the heat treatment, and lowers the glass transition temperature to lower the heat treatment temperature and has a high photocatalytic activity. It is a component that facilitates the formation of one or more TiO ₂ crystals of the group consisting of anatase type, rutile type, and brookite type, particularly an anatase type TiO ₂ crystal, and can be optionally added. However, when the content of the Rb ₂ O component exceeds 10.0%, the stability of the glass is deteriorated, and the precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the upper limit of the content of the Rb ₂ O component with respect to the total amount of the glass ceramic material in oxide equivalent composition is preferably 10.0%, more preferably 8.0%, and most preferably 5.0%. The Rb ₂ O component can be contained in the glass ceramic using, for example, Rb ₂ CO ₃ , RbNO ₃ or the like as a raw material.

The Cs ₂ O component is a component that improves the meltability and stability of the glass and makes it difficult to crack the glass ceramic after the heat treatment, and lowers the glass transition temperature to keep the heat treatment temperature lower, and has a high photocatalytic activity. It is a component that facilitates the formation of one or more TiO ₂ crystals of the group consisting of anatase type, rutile type, and brookite type, particularly an anatase type TiO ₂ crystal, and can be optionally added. However, when the content of the Cs ₂ O component exceeds 10.0%, the stability of the glass is deteriorated, and the precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the upper limit of the content of the Cs ₂ O component with respect to the total amount of glass ceramics in oxide conversion composition is preferably 10.0%, more preferably 8.0%, and most preferably 5.0%. The Cs ₂ O component can be contained in the glass ceramic using, for example, Cs ₂ CO ₃ , CsNO ₃ or the like as a raw material.

The glass ceramic of the present invention contains 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). % Or less is preferable. In particular, when the mass sum of at least one component selected from the Rn ₂ O component is 40.0% or less, the stability of the glass is improved and the TiO ₂ crystal phase is likely to be precipitated. The catalytic activity can be ensured. Therefore, the mass sum of at least one component selected from the Rn ₂ O components is preferably 40.0%, more preferably 30.0%, and most preferably, based on the total amount of glass ceramics having an oxide equivalent composition The upper limit is 20.0%.

The MgO component is a component that improves the meltability and stability of glass, and lowers the glass transition temperature to lower the heat treatment temperature, and is one of the group consisting of anatase type, rutile type and brookite type with high photocatalytic activity. It is a component that facilitates the formation of the above TiO ₂ crystals, in particular, anatase TiO ₂ crystals, and can be optionally added. However, if the content of the MgO component exceeds 40.0%, the stability of the glass is worsened, and precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the upper limit of the content of the MgO component with respect to the total amount of the glass ceramic material having an oxide conversion composition is preferably 40.0%, more preferably 30.0%, and most preferably 20.0%. The MgO component can be contained in the glass ceramic using, for example, MgCO ₃ , MgF ₂ or the like as a raw material.

The CaO component is a component that improves the meltability and stability of the glass, and lowers the glass transition temperature to lower the heat treatment temperature, and is one of the group consisting of anatase type, rutile type and brookite type with high photocatalytic activity. It is a component that facilitates the formation of the above TiO ₂ crystals, in particular, anatase TiO ₂ crystals, and can be optionally added. However, when the content of the CaO component exceeds 40.0%, the stability of the glass is deteriorated, and the precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the upper limit of the content of the CaO component with respect to the total amount of the glass ceramic material having an oxide conversion composition is preferably 40.0%, more preferably 30.0%, and most preferably 25.0%. The CaO component can be contained in the glass ceramic using, for example, CaCO ₃ , CaF ₂ or the like as a raw material.

The SrO component is a component that improves the meltability and stability of glass, and lowers the glass transition temperature to lower the heat treatment temperature, and is one of the group consisting of anatase type, rutile type and brookite type with high photocatalytic activity It is a component that facilitates the formation of the above TiO ₂ crystals, in particular, anatase TiO ₂ crystals, and can be optionally added. However, if the content of the SrO component exceeds 40.0%, the stability of the glass is worsened, and precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the upper limit of the SrO component content is preferably 40.0%, more preferably 30.0%, and most preferably 20.0% with respect to the total amount of glass ceramics having an oxide equivalent composition. The SrO component can be contained in the glass ceramic using, for example, Sr (NO ₃ ) ₂ , SrF ₂ or the like as a raw material.

The BaO component is a component that improves the meltability and stability of glass, and lowers the glass transition temperature to lower the heat treatment temperature, and is one of the group consisting of anatase type, rutile type and brookite type with high photocatalytic activity. It is a component that facilitates the formation of the above TiO ₂ crystals, in particular, anatase TiO ₂ crystals, and can be optionally added. However, if the content of the BaO component exceeds 40.0%, the stability of the glass is worsened, and precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the upper limit of the content of the BaO component with respect to the total amount of the glass ceramic material having an oxide conversion composition is preferably 40.0%, more preferably 30.0%, and most preferably 20.0%. The BaO component can be contained in the glass ceramic using, for example, BaCO ₃ , Ba (NO ₃ ) ₂ or the like as a raw material.

The ZnO component is a component that improves the meltability and stability of glass, and lowers the glass transition temperature to lower the heat treatment temperature, and is one of the group consisting of anatase type, rutile type and brookite type with high photocatalytic activity. It is a component that facilitates the formation of the above TiO ₂ crystals, in particular, anatase TiO ₂ crystals, and can be optionally added. However, if the content of the ZnO component exceeds 50.0%, the stability of the glass is worsened, and precipitation of the TiO ₂ crystal phase becomes difficult. Accordingly, the content of the ZnO component with respect to the total amount of the glass ceramic material having an oxide equivalent composition is preferably 50.0%, more preferably 40.0%, and most preferably 30.0%. The ZnO component can be contained in the glass ceramic using, for example, ZnO, ZnF ₂ or the like as a raw material.

The glass ceramic of the present invention contains 50.0% or less of at least one component selected from RO (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba, Zn). It is preferable to contain. In particular, when the mass sum of at least one component selected from RO components is 50.0% or less, the stability of the glass is improved, and the TiO ₂ crystal phase is easily precipitated. Activity can be ensured. Therefore, the mass sum of at least one component selected from the RO components is preferably 50.0%, more preferably 40.0%, and most preferably 30. The upper limit is 0%.

Further, the glass ceramic of the present invention has an RO (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba, and Zn) components and Rn ₂ O (wherein Rn is Li, Na). It is preferable to contain 50.0% or less of at least one or more components selected from one or more components selected from the group consisting of K, Rb, and Cs. In particular, by making the mass sum of at least one component selected from the RO component and the Rn ₂ O component 50.0% or less, the stability of the glass is improved, the glass transition temperature (Tg) is lowered, and cracks are generated. Thus, glass ceramics with high mechanical strength are more easily obtained. On the other hand, when the mass sum of at least one component selected from the RO component and the Rn ₂ O component is more than 50.0%, the stability of the glass is deteriorated and the precipitation of the TiO ₂ crystal phase becomes difficult. Therefore, the upper limit of the mass sum (RO + Rn ₂ O) with respect to the total amount of glass ceramics in terms of oxide composition is preferably 50.0%, more preferably 40.0%, and most preferably 30.0%. Although RO component and Rn 2 _O component is possible to obtain a glass ceramics having photocatalytic properties even without containing the mass sum of at least one or more components selected from the RO component and Rn 2 _O component 0 By setting the content to 1% or more, the TiO ₂ crystal phase is more easily precipitated, so that the photocatalytic properties are further improved. Therefore, the lower limit of the mass sum (RO + Rn ₂ O) with respect to the total amount of glass ceramics in terms of oxide composition is preferably 0.1%, more preferably 0.5%, and most preferably 1.0%.

Here, the glass ceramic of the present invention has an RO (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba, and Zn) components and Rn ₂ O (wherein Rn is Li, It is preferable to contain two or more types of components selected from the components selected from the group consisting of Na, K, Rb, and Cs. Thereby, the stability of the glass is greatly improved, the mechanical strength of the glass ceramic after the heat treatment is further increased, and the TiO ₂ crystal phase is more easily precipitated from the glass. Thus, glass-ceramics of the present invention preferably contain two or more of the components selected from the RO component and Rn 2 _O component, and more preferably contains three or more kinds.

The B ₂ O ₃ component is a component that constitutes a glass network structure and improves the stability of the glass ceramic, and can be optionally added. However, when the content exceeds 40.0%, the tendency that the TiO ₂ crystal phase is difficult to precipitate increases. Therefore, the content of the B ₂ O ₃ component is preferably 40.0%, more preferably 30.0%, and most preferably 20.0% with respect to the total amount of glass ceramics having an oxide equivalent composition. The B ₂ O ₃ component can be contained in the glass ceramic 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.

Al ₂ O ₃ component enhances the stability of glass and the chemical durability of glass ceramics, promotes the precipitation of TiO ₂ crystal phase from glass, and Al ³⁺ ions are dissolved in the TiO ₂ crystal phase as a photocatalyst. It is a component that contributes to the improvement of characteristics and can be optionally added. However, when the content exceeds 30.0%, the melting temperature is remarkably increased and vitrification becomes difficult. Therefore, the upper limit of the content of the Al ₂ O ₃ component with respect to the total amount of glass ceramics having an oxide conversion composition is preferably 30.0%, more preferably 20.0%, and most preferably 10.0%. The Al ₂ O ₃ component can be contained in the glass ceramic using, for example, Al ₂ O ₃ , Al (OH) ₃ , AlF ₃ or the like as a raw material.

The Ga ₂ O ₃ component is a component that enhances the stability of the glass, promotes the precipitation of the TiO ₂ crystal phase from the glass, and contributes to the improvement of the photocatalytic characteristics when Ga ³⁺ ions are dissolved in the TiO ₂ crystal phase. Yes, a component that can be optionally added. However, when the content exceeds 30.0%, 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 glass ceramics in terms of oxide composition is preferably 30.0%, more preferably 20.0%, and most preferably 10.0%. Ga ₂ O ₃ component may be contained in the glass ceramics used as the raw material for instance _Ga 2 _{O 3,} GaF 3, and the like.

The In ₂ O ₃ component is a component having an effect similar to that of the above Al ₂ O ₃ and Ga ₂ O ₃ and can be arbitrarily added. However, 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 In ₂ O ₃ component can be contained in the glass ceramic using, for example, In ₂ O ₃ , InF ₃ or the like as a raw material.

The glass ceramic of the present invention may contain 50.0% or less of at least one component selected from B ₂ O ₃ component, Al ₂ O ₃ component, Ga ₂ O ₃ component, and In ₂ O ₃ component. preferable. In particular, by making the mass sum of at least one component selected from these components 50.0% or less, the TiO ₂ crystal phase is more easily precipitated, contributing to further improvement of the photocatalytic properties of the glass ceramic. can do. Therefore, the mass sum (B ₂ O ₃ + Al ₂ O ₃ + Ga ₂ O ₃ + In ₂ O ₃ ) with respect to the total amount of glass ceramics in terms of oxide is preferably 50.0%, more preferably 40.0%, Most preferably, the upper limit is 30.0%. Although it is possible to obtain glass ceramics having high photocatalytic properties even if none of the B ₂ O ₃ component, Al ₂ O ₃ component, Ga ₂ O ₃ component, and In ₂ O ₃ component is contained, these By making the mass sum of at least one component selected from the above components 0.1% or more, precipitation of the TiO ₂ crystal phase is further promoted, which contributes to further improvement of the photocatalytic properties of the glass ceramic. Can do. Therefore, the mass sum (B ₂ O ₃ + Al ₂ O ₃ + Ga ₂ O ₃ + In ₂ O ₃ ) with respect to the total amount of glass ceramics in the oxide conversion composition is preferably 0.1%, more preferably 0.5%, Most preferably, the lower limit is 1.0%.

The Nb ₂ O ₅ component is a component that enhances the meltability and stability of the glass, and is a component that improves the photocatalytic properties by being dissolved in or in the vicinity of the TiO ₂ crystal phase. It is a component that can be added. However, when the content of the Nb ₂ O ₅ component exceeds 50.0%, the stability of the glass is remarkably deteriorated. Therefore, the content of the Nb ₂ O ₅ component is preferably 50.0%, more preferably 30.0%, and most preferably 20.0% with respect to the total amount of glass ceramics having an oxide equivalent composition. The Nb ₂ O ₅ component can be contained in the glass ceramic using, for example, Nb ₂ O ₅ as a raw material.

The Ta ₂ O ₅ component is a component that enhances the stability of the glass and is a component that improves the photocatalytic characteristics by being dissolved in the TiO ₂ crystal phase or in the vicinity thereof, and can be optionally added It is. However, when the content of the Ta ₂ O ₅ component exceeds 50.0%, the stability of the glass is remarkably deteriorated. Therefore, the content of the Ta ₂ O ₅ component is preferably 50.0%, more preferably 30.0%, and most preferably 20.0% with respect to the total amount of glass ceramics having an oxide equivalent composition. The Ta ₂ O ₅ component can be contained in the glass ceramic using, for example, Ta ₂ O ₅ as a raw material.

The WO ₃ component is a component that improves the meltability and stability of the glass, and is a component that improves the photocatalytic properties by being dissolved in the TiO ₂ crystal phase or in the vicinity thereof, and can be arbitrarily added. It is an ingredient. However, if the content of the WO ₃ component exceeds 50.0%, the stability of the glass is remarkably deteriorated. Therefore, the upper limit of the content of the WO ₃ component with respect to the total amount of glass ceramics having an oxide equivalent composition is preferably 50.0%, more preferably 30.0%, and most preferably 20.0%. The WO ₃ component can be contained in the glass ceramic using, for example, WO ₃ as a raw material.

The MoO ₃ component is a component that enhances the meltability and stability of the glass, and is a component that improves the photocatalytic properties by being dissolved in or in the vicinity of the TiO ₂ crystal phase, and can be arbitrarily added. It is an ingredient. However, when the content of the MoO ₃ component exceeds 50.0%, the stability of the glass is remarkably deteriorated. Therefore, the upper limit of the content of the MoO ₃ component with respect to the total amount of the glass ceramic material in oxide equivalent composition is preferably 50.0%, more preferably 30.0%, and most preferably 20.0%. The MoO ₃ component can be contained in the glass ceramic using, for example, MoO ₃ as a raw material.

The glass ceramic of the present invention preferably contains 50.0% or less of at least one component selected from Nb ₂ O ₅ component, Ta ₂ O ₅ component, WO ₃ component, and MoO ₃ component. In particular, by setting the mass sum of at least one component selected from these components to 50.0% or less, the stability of the glass ceramic is ensured, so that a good glass ceramic can be formed. Accordingly, the mass sum (Nb ₂ O ₅ + Ta ₂ O ₅ + WO ₃ + MoO ₃ ) with respect to the total amount of glass ceramics in terms of oxide composition is preferably 50.0%, more preferably 30.0%, and most preferably 20 0.0% is the upper limit. Although it is possible to obtain glass ceramics having high photocatalytic properties even when none of Nb ₂ O ₅ component, Ta ₂ O ₅ component, WO ₃ component and MoO ₃ component is contained, it is selected from these components. By setting the mass sum of at least one or more components to be 0.1% or more, the photocatalytic properties of the glass ceramic can be further improved. Therefore, the mass sum (Nb ₂ O ₅ + Ta ₂ O ₅ + WO ₃ + MoO ₃ ) with respect to the total amount of glass ceramics in terms of oxide composition is preferably 0.1%, more preferably 0.5%, most preferably 1. 0.0% is the lower limit.

The Bi ₂ O ₃ component is a component that increases the meltability and stability of glass, and the heat treatment temperature is lowered by lowering the glass transition temperature (Tg). Therefore, from anatase type, rutile type, and brookite type having high photocatalytic activity. It is a component that can easily form one or more types of TiO ₂ crystals, particularly an anatase TiO ₂ crystal, and can be optionally added. However, when the content of the Bi ₂ O ₃ component exceeds 20.0%, the stability of the glass is deteriorated and the precipitation of TiO ₂ becomes difficult. Accordingly, the content of the Bi ₂ O ₃ component with respect to the total amount of glass ceramics having an oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%. The Bi ₂ O ₃ component can be contained in the glass ceramic using, for example, Bi ₂ O ₃ as a raw material.

The TeO ₂ component is a component that enhances the meltability and stability of the glass, and the heat treatment temperature is lowered by lowering the glass transition temperature (Tg). Therefore, the group consisting of anatase type, rutile type and brookite type having high photocatalytic activity It is a component that can easily form one or more TiO ₂ crystals, particularly an anatase TiO ₂ crystal, and can be optionally added. However, if the content of the TeO ₂ component exceeds 20.0%, the stability of the glass is deteriorated and the precipitation of TiO ₂ becomes difficult. Therefore, the content of the TeO ₂ component with respect to the total amount of the glass ceramic material with an oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%. The TeO ₂ component can be contained in the glass ceramic using, for example, TeO ₂ as a raw material.

Ln _a O _b component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, Ce, Nd, Dy, Yb and Lu, and for each component excluding Ce, a = 2 and b = 3. For Ce, a = 1 and b = 2) are components that enhance the chemical durability of the glass ceramics, and are dissolved in or in the vicinity of the TiO ₂ crystal phase, so that the photocatalytic properties are improved. It is a component that improves and can be optionally added. However, when the total content of the Ln _a O _b component exceeds 30.0%, the stability of the glass is remarkably deteriorated. Therefore, the glass ceramic total material of the oxide composition in terms of, _Ln a _{O b} mass sum of at least one or more components selected from the component is preferably 30.0%, more preferably 20.0%, most preferably Has an upper limit of 10.0%. The Ln _a O _b 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 , Nd ₂ O ₃ , Dy ₂ O ₃ , Yb ₂ O ₃ , Lu ₂ O _{3, and the} like can be contained in the glass ceramic.

M _x O _y component (wherein M is one or more selected from the group consisting of V, Cr, Mn, Fe, Co, and Ni, and x and y are each x: y = 2: (valence of M Is the minimum natural number satisfying) by being dissolved in or in the vicinity of the TiO ₂ crystal phase, contributing to the improvement of the photocatalytic properties and absorbing visible light of some wavelengths. It is a component that imparts an appearance color to the glass ceramic, and is an optional component in the glass ceramic of the present invention. In particular, by making the mass sum of at least one component selected from M _x O _y components 10.0% or less, the stability of the glass ceramic is improved and the color of the appearance of the glass ceramic is easily adjusted. Can do. Therefore, the mass sum of at least one component selected from the M _x O _y components is preferably 10.0%, more preferably 8.0%, most preferably, based on the total amount of glass ceramics having an oxide equivalent composition. The upper limit is 5.0%.

As ₂ O ₃ component and Sb ₂ O ₃ component are components for clarifying and defoaming glass ceramics, 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 improving the activity of the photocatalyst and can be added arbitrarily. 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 As ₂ O ₃ component and / or Sb ₂ O ₃ component with respect to the total amount of glass ceramics in oxide equivalent composition is preferably 5.0%, more preferably 3.0%, most preferably The upper limit is 1.0%. 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. It can be used and contained in glass ceramics.

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

The glass ceramic of the present invention may contain at least one nonmetallic element component selected from the group consisting of an F component, a Cl component, a Br component, an S component, an N component, and a C component. These components are components in which the photocatalytic characteristics are improved by being dissolved in the TiO ₂ crystal phase or in the vicinity thereof, and can be arbitrarily added. However, when the content of these components exceeds 10.0% 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 content of the nonmetallic element component with respect to the total mass of the glass ceramic of the oxide conversion composition is preferably 10.0%, more preferably 5.0%, most preferably The upper limit is 3.0%. These non-metallic element components are preferably introduced into the glass ceramic in the form of alkali metal or alkaline earth metal fluoride, chloride, bromide, sulfide, nitride, carbide or the like. Note that the content of the non-metallic element component in this specification is assumed to be made of an oxide in which all of the cation components constituting the glass ceramic are combined with oxygen that balances the 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, but AlN ₃ , SiN ₄ or the like as the N component raw material, NaS, Fe ₂ S ₃ , CaS ₂ or the like as the S component raw material, ZrF ₄ or AlF ₃ as the F component raw material , NaF, CaF _2, etc., by using NaCl as a raw material for Cl component, AgCl, etc., NaBr or the like as a raw material of Br components, TiC as a raw material of component C, SiC or ZrC and the like, can be contained in the glass ceramic . In addition, these raw materials may be added integrally or may be added independently.

The glass ceramic of the present invention may contain at least one metal element component selected from Cu, Ag, Au, Pd, Pt, Ru, and Rh. Since these metal element components are present in the vicinity of the TiO ₂ crystal phase and the photocatalytic activity is improved, they can be arbitrarily added. However, if the total content of these metal element components exceeds 10.0%, the stability of the glass is remarkably deteriorated, and the photocatalytic properties tend to be lowered. Therefore, the upper limit of the total content of the metal element components with respect to the total mass of the glass ceramic having an oxide conversion composition is preferably 10.0%, more preferably 5.0%, and most preferably 1.0%. These metal element components can be contained in glass ceramics using, for example, Cu ₂ O, Ag ₂ O, AuCl ₃ , PtCl ₄ or the like as a raw material. In addition, the content of the metal element component in this specification is assumed to be made of an oxide in which all the cation components constituting the glass ceramic are combined with oxygen sufficient to balance 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).

<About ingredients that should not be included>
Next, components that should not be contained in the glass ceramic of the present invention and components that are not preferably contained will be described.

  If necessary, other components can be added to the glass ceramic of the present invention as long as the properties of the glass ceramic are not impaired.

  However, lead compounds such as PbO, and components of Th, Cd, Tl, Os, Be, Se, and Hg tend to refrain from being used as harmful chemicals in recent years. , And measures for environmental measures are required until 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 ceramics are substantially free of substances that pollute the environment. Therefore, the glass ceramics can be manufactured, processed, and discarded without taking any special environmental measures.

Although the composition of the present invention is expressed in mol% with respect to the total amount of glass ceramics in the oxide conversion composition, it cannot be expressed directly in the description of mass%. The composition expressed by mass% of each component present in the composition satisfying the characteristics generally takes the following values in terms of oxide conversion.
TiO ₂ component 13.0-80.0% by mass and P ₂ O ₅ component 12.0-85.0% by mass
ZrO ₂ component 0 to 30.0 mass% and / or SnO component 0 to 15.0 mass% and / or SiO ₂ component 0 to 45.0 mass% and / or GeO ₂ component 0 to 70.0 mass% and / or Li ₂ O component from 0 to 15.0% by weight and / or Na ₂ O component from 0 to 30.0% by weight and / or _{K 2} O ingredient from 0 to 45.0% by weight and / or Rb ₂ O component 0 25.0% by weight and / or Cs ₂ O component from 0 to 30.0% by weight and / or MgO component 0 to 20.0% by weight and / or CaO component from 0 to 25.0% by weight and / or SrO component 0 45.0% by mass and / or BaO component 0-60.0% by mass and / or ZnO component 0-45.0% by mass and / or B ₂ O ₃ component 0-35.0% by mass and / or Al ₂ O ₃ component from 0 to 35.0% by weight and / or _Ga 2 O ₃ component from 0 to 65.0% by weight and / or _In 2 _{O 3} component from 0 to 35.0% by weight and / or _Nb 2 _{O 5} component from 0 to 65.0% by weight and / or _Ta 2 _{O 5} component 0-70 0.0% by mass and / or WO ₃ component 0-55.0% by mass and / or MoO ₃ component 0-60.0% by mass and / or Bi ₂ O ₃ component 0-60.0% by mass and / or TeO ₂ component 0 to 20.0% by weight and / or _Ln a _{O b} components total from 0 to 50.0% by weight and / or _M x _{O y} 0 to 20.0% by weight sum of component and / or _As 2 _{O 3} ingredients and _Sb 2 _{O 3} component in total 0 to 10.0 wt%
Furthermore, with respect to 100% of the total mass of the glass ceramic of the oxide conversion composition,
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 0 to 10.0% by mass and / or Cu, Ag, Au, Pd , Pt, Ru, and Rh, at least one metal element component selected from the group consisting of 0 to 10.0% by mass

<Physical properties>
The glass ceramic of the present invention preferably contains a crystal phase. In particular, the crystal phase preferably contains TiO ₂ , TiP ₂ O ₇ , (TiO) ₂ P ₂ O ₇ , and crystals composed of one or more of these solid solutions, anatase type, rutile type More preferably, a crystal composed of one or more kinds of TiO _{2 in the} group consisting of a brookite type is included. By containing these crystals, glass ceramics can have a high photocatalytic function. Among them, anatase-type titanium oxide (TiO ₂ ) has a particularly high photocatalytic function as compared to a rutile type, and thus glass ceramics can have a higher photocatalytic function. As crystal phases other than the above, 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 _{Even if} titanium compounds such as ₄ (PO ₄ ) ₆ , BaTi ₄ (PO ₄ ) ₆ , ZnTi ₄ (PO ₄ ) ₆ coexist, there is no problem.

  In the glass ceramics of the present invention, the crystallization rate, which is the abundance ratio of particles showing a crystal phase, with respect to the whole glass ceramics is preferably 1.0% or more and 95.0% or less by volume. When the crystallization rate is 1.0% or more, the glass ceramic can have good photocatalytic properties. On the other hand, when the crystallization rate is 95.0% or less, the glass ceramic can obtain good mechanical strength. Therefore, the crystallization rate of the glass ceramic of the present invention is preferably 1.0%, more preferably 5.0%, most preferably 10.0% as the lower limit, preferably 95.0%, more preferably 90%. 0.0%, most preferably 85.0%.

At this time, as for the size (crystal grain size) of the anatase TiO ₂ crystal grains among the grains showing the crystal phase, the average diameter when approximated by a sphere is preferably 5 nm or more and 3 μm or less. In particular, from the viewpoint of extracting effective photocatalytic properties, the crystal grain size of the anatase TiO ₂ crystal is preferably in the range of 5 nm to 3 μm, more preferably 10 nm to 1 μm, and most preferably 10 nm to 600 nm. To do. Here, the crystal grain size and the average value are calculated from the half width of the diffraction peak of the X-ray diffractometer (XRD) according to 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 XRD diffraction peak is weak or the diffraction peak overlaps with other peaks, this is determined from the crystal particle area measured using a scanning electron microscope (SEM) or transmission electron microscope (TEM). It can also be estimated by obtaining the diameter assuming a circle. When calculating the average value of the crystal grain size using a microscope, it is preferable to measure 100 or more crystal diameters at random. Note that the size of the particles exhibiting the crystal phase can be controlled to a desired size by controlling the heat treatment conditions in the crystallization process described below.

The glass ceramic of the present invention preferably has an average coefficient of linear expansion of 70 × 10 ⁻⁷ / ° C. or less. Thereby, especially when used for a use with a severe temperature change like a building material and a solar cell panel, glass ceramics can maintain high durability. Accordingly, the average linear expansion coefficient of the glass ceramic of the present invention is preferably 70 × 10 ⁻⁷ / ° C., more preferably 60 × 10 ⁻⁷ / ° C., and further preferably 55 × 10 ⁻⁷ / ° C.

  In addition, the average linear expansion coefficient of the glass ceramic of this invention is not limited to the above-mentioned range, but is suitably set according to the use of glass ceramic. For example, when used in combination with other base materials, the average linear expansion coefficient of the glass ceramics may be a value substantially equal to the average linear expansion coefficient of the base material. Thereby, since peeling with glass ceramics and another base material is reduced, durability of the member formed by combining these can be improved.

The glass ceramic of the present invention preferably exhibits catalytic activity by light having a wavelength from the ultraviolet region to the visible region. 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 ceramics is irradiated with light of wavelengths from the ultraviolet region to the visible region, the catalytic activity is expressed, so that dirt substances and bacteria attached to the surface of the glass ceramics are decomposed by oxidation or reduction reaction. Therefore, glass ceramics can be used for antifouling applications and antibacterial applications. In addition, while TiO ₂ crystal shows a high catalytic effect for ultraviolet irradiation, its responsiveness to visible light is weaker than that of ultraviolet light. However, in the present invention, other ions are dissolved in the TiO ₂ crystal phase when glass ceramics are produced. Since the band gap energy of TiO ₂ becomes small, it is possible to obtain glass ceramics that show an effective response effect even for visible light. Here, the catalytic activity of the glass ceramic of the present invention is preferably 3.0 nmol / l / min, more preferably 4.0 nmol / l / min, and most preferably 5.0 nmol / l when expressed in terms of decomposition activity index. / Min is the lower limit. Here, the decomposition activity index of the glass ceramic of the present invention can be determined based on Japanese Industrial Standard JIS R 1703-2: 2007.

  In the glass ceramic of the present invention, the contact angle between the surface irradiated with light and the water droplet is preferably 30 ° or less. Thereby, since the surface of the glass ceramic exhibits hydrophilicity and has a self-cleaning action, the surface of the glass ceramic can be easily washed with water, and the deterioration of the photocatalytic properties due to dirt can be suppressed. The contact angle between the glass ceramic surface irradiated with light and the water droplet is preferably 30 ° or less, more preferably 25 ° or less, and most preferably 20 ° or less.

[Glass ceramic production method]
Next, the manufacturing method of the glass ceramic of this invention is demonstrated.

<First Embodiment>
1st Embodiment of the manufacturing method of the glass-ceramics of this invention hold | maintains a raw material composition mixture at the temperature of 1250 degreeC or more, produces a liquid phase in at least one part, and is then cooled and solidified. This is a method for producing ceramics. More specifically, a predetermined starting material is uniformly mixed, put into a container made of platinum or refractory, and heated and held at a predetermined temperature of 1250 ° C. or higher in an electric furnace to prepare a melt. Thereafter, the melt is poured into a mold and solidified to obtain a target crystallized glass. Here, generation and growth of crystal nuclei occur in the process of cooling the melt. This technique is effective, for example, when a desired crystal phase is richly precipitated and the state of the glass melt is relatively unstable.

  Here, a liquid phase may be produced | generated from at least 1 or more types of raw material composition, and the fall of the liquid phase production temperature by adding 2 or more types of compounds can also be considered. Accordingly, the temperature to be maintained is preferably appropriately changed according to the type and amount of the composition to be mixed, but is generally preferably 1250 ° C. or higher, more preferably 1300 ° C. or higher, and most preferably 1350 ° C. or higher.

  More specifically, a predetermined starting material is uniformly mixed, put into a container made of platinum or refractory, and heated and held at a predetermined temperature of 1250 ° C. or higher in an electric furnace to prepare a solution. Then, while controlling the cooling rate of the solution, it is poured into a mold and solidified to obtain the target glass ceramic. Here, generation and growth of crystal nuclei occur in the process of cooling the solution. Since the cooling speed and temperature greatly affect the formation of crystal phases and the crystal size, it is important to control them precisely.

Second Embodiment
The second embodiment of the glass ceramic manufacturing method of the present invention includes a melting step of mixing raw materials to obtain a melt, a cooling step of cooling the melt to obtain a glass body, and a temperature of the glass body. It is a manufacturing method of glass ceramics which has a reheating process which raises to the temperature range beyond a glass transition temperature, and a crystallization process which maintains the temperature in the temperature range and produces a crystal.

(Melting process)
The melting step is a step of obtaining a melt by mixing raw materials having the above-described composition. More specifically, the raw materials are prepared so that each component of the glass ceramic is within a predetermined content range, uniformly mixed, and the prepared mixture is put into a platinum crucible, a quartz crucible or an alumina crucible, and electric Melt in a furnace at a temperature range of 1200 to 1600 ° C. for 1 to 24 hours, and homogenize with stirring to prepare a melt. In addition, the conditions for melting the raw material are not limited to the above temperature range, and can be appropriately set according to the composition and amount of the raw material composition.

(Cooling process)
A cooling process is a process of producing a glass body by cooling and vitrifying the melt obtained at the melting process. Specifically, a vitrified glass body is formed by flowing out the melt and appropriately cooling it. Here, the conditions for vitrification are not particularly limited, and may be appropriately set according to the composition and amount of the raw material. Moreover, the shape of the glass body obtained at this process is not specifically limited, Although it may be plate shape, a granular form, etc., it is preferable that it is plate shape at the point which can produce a glass body rapidly and in large quantities.

(Crystallization process)
The crystallization process is a process in which the temperature of the glass body is raised to a temperature region exceeding the glass transition temperature and held at that temperature for a predetermined time. By holding a predetermined time at a predetermined temperature range in the crystallization step, the crystals of TiO ₂ having a desired size from nano to micron can be uniformly dispersed within the glass body, the TiO ₂ crystals It is possible to more reliably produce glass ceramics having

Although it is necessary to set a crystallization temperature according to a glass transition temperature for every glass composition in said crystallization process, it is preferable to heat-process in a temperature range specifically 10 degreeC or more higher than a glass transition temperature. Since the glass of the present invention has a glass transition temperature of 500 ° C. or higher, the lower limit of the preferable heat treatment temperature (crystallization temperature) is 510 ° C., more preferably 600 ° C., and most preferably 650 ° C. On the other hand, if the heat treatment temperature becomes too high, the tendency of the TiO ₂ crystal phase to decrease becomes strong and the photocatalytic properties tend to disappear, so the upper limit of the heat treatment temperature is preferably 1200 ° C, more preferably 1100 ° C, and more preferably 1050 ° C. Most preferred.

(Etching process)
The glass body after crystals are formed by performing the crystallization process can exhibit high photocatalytic properties as glass ceramics as it is, but the crystal phase is obtained by performing an etching process on the glass ceramics. The glass phase around is removed, and the specific surface area of the crystal phase exposed on the surface increases, so that the photocatalytic properties of the glass ceramic can be further enhanced. Further, it is possible to obtain a porous body in which the TiO ₂ crystal phase remains by controlling the solution used in the etching process and the etching time. Here, examples of the etching step include dry etching and / or immersion in a solution. The acidic or alkaline solution used for the immersion is not particularly limited as long as the surface of the glass ceramic can be corroded, and may be, for example, an acid containing fluorine or chlorine (hydrofluoric acid, hydrochloric acid). This etching step may be performed by spraying hydrogen fluoride gas, hydrogen chloride gas, hydrofluoric acid, hydrochloric acid, or the like on the surface of the glass ceramic.

[Glass ceramic compact]
The glass ceramic molded body thus produced is useful as a photocatalytic functional glass ceramic molded body and / or a hydrophilic glass ceramic molded body for various machines, devices, instruments, water purification, etc. Especially, it is preferable to use for uses, such as a tile, a window frame, and a building material. Thereby, since the photocatalytic function is exhibited on the surface of the glass ceramic molded body and the fungi attached to the surface of the glass ceramic molded body are sterilized, the surface can be kept hygienic when used in these applications. Moreover, since hydrophilicity is exhibited on the surface of the glass ceramic molded body, dirt attached to the surface of the glass ceramic molded body when used in these applications can be easily washed away with raindrops or the like.

In addition, among the above glass ceramic molded bodies, there are cases where it is more preferable to use a fiber shape depending on the application. Accordingly, since the exposed area of the TiO ₂ crystal phase is increased, it is possible to further enhance the photocatalytic activity of the glass ceramic compact.

  Table 1 shows the compositions and crystallization conditions of the glass ceramic molded articles of Examples (No. 1 to No. 28) and Comparative Example (No. 1) of the present invention, and types of precipitated crystal phases of these glass ceramic molded articles. Shown in 1-8. The following examples are merely for illustrative purposes and are not limited to these examples.

  The glass ceramic molded bodies of Examples (No. 1 to No. 28) and Comparative Examples (No. 1) of the present invention are all oxides, hydroxides, carbonates and nitrates corresponding to the raw materials of the respective components. , Fluorides, hydroxides, metaphosphoric acid compounds and other high-purity raw materials used for ordinary glass are selected and weighed so that the composition ratios of the examples and comparative examples shown in Tables 1 to 8 are obtained. And then uniformly mixed, then put into a platinum crucible, melted in an electric furnace at a temperature range of 1200 ° C to 1600 ° C for 1 to 24 hours according to the melting difficulty of the glass body composition, homogenized with stirring and blown out bubbles, etc. Then, the temperature was lowered to 1500 ° C. or lower, homogenized with stirring, cast into a mold, and slowly cooled to produce a glass. About the obtained glass, after heating to the crystallization temperature described in each Example and comparative example of Tables 1-8, holding for the described time and performing crystallization, it cooled from crystallization temperature. A glass ceramic having the desired crystal phase was obtained.

  Here, the kind of the precipitated crystal phase of the glass ceramic molded bodies of Examples (No. 1 to No. 28) and Comparative Examples (No. 1) is an X-ray diffractometer (manufactured by Philips, trade name: X'Pert). -MPD).

  In addition, the photocatalytic properties of some of the examples (No. 1 to No. 28) and the glass ceramic molded articles of the comparative example (No. 1) are the same as those of “Photocatalytic Performance Evaluation Method I” formulated by the Photocatalyst Product Technical Council. It evaluated according to it. That is, a methylene blue solution was dropped on the surface of a glass ceramic molded sample, the color after irradiation with ultraviolet rays was observed, and the performance of the photocatalyst was evaluated according to the degree of decolorization of methylene blue (methylene blue decolorization method). As a result of the evaluation, a sample in which the photocatalytic property was recognized was indicated by a mark, and a sample in which the photocatalytic property was not recognized was indicated by a mark.

  Moreover, about the sample of the Example, the decomposition activity index (nmol / l / min) of methylene blue was calculated | required based on Japanese Industrial Standard JISR1703-2: 2007. On the other hand, the decomposition activity index was similarly calculated | required about the glass before performing the crystallization process which consists of a composition of Example 1 for the comparison.

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)

  On the other hand, about the glass of the composition described in Example 28, it heated at 900 degreeC crystallization temperature for 12 hours, performed the crystallization process, and heated at 800 degreeC crystallization temperature for 60 hours. The glass ceramic formed by performing the crystallization process was immersed in a hydrofluoric acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) having an HF concentration of 46% (mass percentage) for 3 minutes to perform an etching process. The above-mentioned methylene blue decomposition test was performed on the glass ceramics before and after the etching step, and the decomposition activity index (nmol / l / min) before and after the etching step was obtained.

Further, the contact angle between the sample surface and water droplets is measured by the θ / 2 method for the hydrophilicity of part of the examples (No. 1 to No. 28) and the glass ceramic molded bodies of the comparative example (No. 1). It was evaluated by. That is, water is dripped onto the surface of the glass ceramic after the ultraviolet irradiation, and the height h from the surface of the glass ceramic molded body to the top of the water drop and the radius r of the surface in contact with the test piece of the water drop are determined as the Kyowa interface. It measured using the contact angle meter (CA-X) by a scientific company, and contact angle (theta) with water was calculated | required from the relational expression of (theta) = 2tan < ^-1 > (h / r).

Moreover, among the crystals formed in the glass ceramic molded bodies of the examples (No. 1 to No. 28), the particle size of the anatase TiO ₂ crystal is X-ray diffractometer (trade name: X ′, manufactured by Philips). From the half-value width of the diffraction peak of the chart obtained by Pert-MPD), it was determined using the Scherrer equation. At this time, the temperature and time of crystallization at the time of forming the glass ceramic formed body were changed, and the crystal grain size formed under each crystallization condition was determined.

  Moreover, the chemical durability (water resistance and acid resistance) of the glass ceramics of the examples (No. 1 to No. 28) was prepared by preparing glass ceramic samples that were crushed to a particle size of 425 to 600 μm and washed with methanol. It was measured according to the Optical Glass Industry Association Standard “Method for Measuring Chemical Durability of Optical Glass” JOGIS06-2008.

  Water resistance is obtained by placing a glass ceramic sample in a platinum basket, immersing the platinum basket in a quartz glass round bottom flask containing pure water (pH 6.5-7.5), and in a boiling water bath for 60 minutes. It measured using the weight loss rate (%) of the glass sample after processing. Here, when the weight loss rate (wt%) is less than 0.05, it is class 1, when the weight loss rate is less than 0.05 to 0.10, it is class 2, and when the weight loss rate is less than 0.10 to 0.25. Class 3, when the weight loss rate is less than 0.25 to 0.60, class 4, when the weight loss rate is less than 0.60 to 1.10, class 5, and when the weight loss rate is 1.10 or more, class 6 The smaller the number of classes, the better the water resistance of the glass.

On the other hand, the acid resistance is obtained by placing a glass ceramic sample in a platinum basket, immersing the platinum basket in a quartz glass round bottom flask containing a 0.01N nitric acid aqueous solution, and treating it in a boiling water bath for 60 minutes. It measured using the weight loss rate (%) of a glass sample. Here, when the weight loss rate (wt%) is less than 0.20, class 1, when the weight loss rate is less than 0.20 to 0.36, class 2, and when the weight loss rate is less than 0.35 to 0.65 Class 3, when the weight loss rate is less than 0.65 to 1.20, class 4 when the weight loss rate is less than 1.20 to 2.20, class 6 when the weight loss rate is 2.20 or more The smaller the number of classes, the better the acid resistance of the glass.

As shown in Tables 1 to 8, the precipitated crystal phases of the glass ceramic molded bodies of Examples (No. 1 to No. 28) all consist of anatase type, rutile type and brookite type with high photocatalytic activity. One or more TiO ₂ crystals of the group were included. This is a peak in the incident angle represented by “●” in the XRD pattern of the glass ceramic molded body of Example (No. 1) shown in FIG. It is clear from the fact that On the other hand, the precipitated crystal phase of the glass ceramic molded body of the comparative example (No. 1) did not contain anatase type, rutile type and brookite type TiO ₂ crystals. For this reason, it was guessed that the glass-ceramic molding of the Example of this invention has a high photocatalytic characteristic and hydrophilicity compared with the glass-ceramic molding of a comparative example.

  Among these, the photocatalytic properties of the glass ceramic molded bodies of the examples (No. 1, No. 4, No. 11, No. 17) were evaluated by the above-described methylene blue decolorization method. It was confirmed that the glass-ceramic molded article had photocatalytic properties since the decolorization phenomenon of methylene blue occurred. On the other hand, no decolorization of methylene blue was observed for the glass body before crystallization and the comparative example (No. 1).

  Among these, as shown in Table 10, the glass ceramic formed bodies of Examples (No. 1, No. 27, No. 28) have a decomposition activity index of 3.0 nmol / l / min or more, more specifically. It was 7.1 nmol / l / min or more. On the other hand, the glass before the crystallization step (before heat treatment) of the example (No. 1) had a decomposition activity index smaller than 3.0 nmol / l / min. For this reason, it became clear that the glass ceramic molded body of the Example of this invention has a desired photocatalytic characteristic, since a decomposition activity index | exponent is raised through a crystallization process. In addition, the decomposition activity index | exponent of the glass-ceramics molded object after the crystallization process in an Example (No.1, No.27, No.28), and decomposition | disassembly of the glass before the crystallization process in an Example (No.1). The activity index is shown in FIG.

  As shown in Table 11, the glass ceramic molded body of Example (No. 28) after the etching process had a higher value than the decomposition activity index before the etching process. Therefore, it became clear that the glass-ceramic molded body of the Example of this invention can obtain a higher photocatalytic characteristic, since a decomposition activity index | exponent is raised by performing an etching process.

  In particular, as shown in Table 11, the glass ceramic molded body of Example (No. 28) exhibited different decomposition activity indexes before and after performing the crystallization process and the etching process. Moreover, the glass ceramic molded body of Example (No. 28) exhibited different decomposition activity indexes even when the heat treatment conditions were different. In addition, about the glass ceramic molded object of an Example (No. 28), the decomposition activity index | exponent before and behind a crystallization process and an etching process is shown in FIG.

  Moreover, when hydrophilicity was evaluated about the glass-ceramic molded object of the Example (No.1, No.4, No.11, No.17), as shown in Table 9, two hours after the start of ultraviolet irradiation, It was confirmed that the contact angle with water was 30 ° or less. On the other hand, as for the comparative example (No. 1), the contact angle with water after 2 hours from the start of ultraviolet irradiation exceeded 60 °. Thereby, it became clear that the glass-ceramic molding of the Example of this invention has high hydrophilicity compared with the glass-ceramic molding of a comparative example. As an example, the relationship between the ultraviolet irradiation time and the water contact angle for the glass-ceramic molded body of Example 1 is shown in FIG. FIG. 4 also revealed that the water contact angle became 30 ° or less after 2 hours from the start of ultraviolet irradiation, and the water contact angle became 10 ° or less after 4 hours.

Moreover, among the glass-ceramic moldings of the examples (No. 1, No. 4, No. 28), the particle size of the anatase TiO ₂ crystal is 5 nm or more and 3 μm or less, as shown in Tables 12 and 13. Specifically, it was 30 nm or more and 88 nm or less, and was in a desired range. It was also confirmed that when a crystallization temperature was set to 700 ° C. or more and 1000 ° C. or less and a crystallization time was set to 2 hours or more and 60 hours or less, a glass ceramic formed body having a desired crystal grain size was obtained. Furthermore, as shown in FIGS. 5 and 6, it has been clarified that the crystal grain size of the glass ceramic formed body increases when the crystallization temperature is increased or when the crystallization temperature is increased.

  Moreover, the water resistance and acid resistance of the glass ceramics of the examples (No. 1 to No. 28) were both first grade.

Therefore, in the glass ceramic molded body of the example of the present invention, crystals of inorganic titanium compounds including one or more types of titanium oxide (TiO ₂ ) in the group consisting of anatase type, rutile type and brookite type easily precipitate. In addition, since the crystals of the inorganic titanium compound were uniformly dispersed in the glass, it was confirmed that there was no loss of the photocatalytic function due to peeling and a photocatalytic functional body excellent in durability could be obtained.

  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 (21)

Containing the glass ceramic total material of the oxide composition in terms of the following 88.9% 15.0% more than the TiO ₂ component in mol%, and _P 2 _{O 5} ingredient 11.0% or more 84.9% or less And
Containing 0.1% or more and 20.0% or less of one or more components selected from the group consisting of ZrO ₂ component and SnO component,
TiO ₂ , TiP ₂ O ₇ , (TiO) ₂ P ₂ O ₇ , and glass ceramics containing a crystalline phase composed of one or more of these solid solutions. The SiO ₂ component 0 to 60.0% and the GeO ₂ component 0 to 60.0% in mol% with respect to the total amount of the glass ceramics having an oxide conversion composition
The glass ceramic according to claim 1, further comprising: Li ₂ O component 0 to 40.0% in mol% with respect to the total amount of glass ceramics of oxide conversion composition,
Na ₂ O component from 0 to 40.0%,
K ₂ O component from 0 to 40.0%,
Rb ₂ O component 0 to 10.0% and Cs ₂ O component 0 to 10.0%
The glass ceramic according to claim 1, further comprising: MgO component 0 to 40.0% in mol% with respect to the total amount of glass ceramics of oxide conversion composition,
CaO component 0-40.0%,
SrO component 0-40.0%,
BaO component 0-40.0% and ZnO component 0-50.0%
The glass ceramic according to claim 1, further comprising: The glass ceramic total material of the oxide composition in terms of, _B 2 _{O 3} component from 0 to 40.0% by mole%,
Al ₂ O ₃ component 0 to 30.0%,
Ga ₂ O ₃ component 0 to 30.0% and In ₂ O ₃ component 0 to 10.0%
The glass ceramic according to any one of claims 1 to 4, further comprising: Nb ₂ O ₅ component 0 to 50.0% in mol% with respect to the total amount of glass ceramics in oxide conversion composition,
Ta ₂ O ₅ component 0 to 50.0%,
WO ₃ component 0-50.0% and MoO ₃ component 0-50.0%
The glass ceramic according to claim 1, further comprising: Bi ₂ O ₃ component 0 to 20.0% in mol% with respect to the total amount of glass ceramics of oxide conversion composition,
TeO ₂ component 0 to 20.0%,
Ln _a O _b component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, Ce, Nd, Dy, Yb and Lu, and for each component excluding Ce, a = 2 and b = 3. For Ce, a = 1 and b = 2) 0-30.0% in total,
M _x O _y component (wherein M is one or more selected from the group consisting of V, Cr, Mn, Fe, Co, and Ni, and x and y are each x: y = 2: (valence of M ) And 0 to 10.0% in total, and As ₂ O ₃ component and Sb ₂ O ₃ component in total 0 to 5.0%
The glass ceramic according to claim 1, further comprising:   10. 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 is 10. The glass ceramic according to any one of claims 1 to 7, which is contained in an amount of 0% or less.   At least one metal element component selected from the group consisting of Cu, Ag, Au, Pd, Pt, Ru, and Rh is included in an amount of 10.0% or less in terms of mass ratio with respect to the total mass of the glass ceramic of the oxide conversion composition. The glass ceramic according to any one of claims 1 to 8. The glass ceramic according to any one of claims 1 to 9, wherein the crystal phase includes one or more TiO ₂ crystals of the group consisting of anatase type, rutile type, and brookite type.   The glass ceramic according to any one of claims 1 to 10, wherein the crystal phase is contained in a volume ratio of 1.0% to 95.0% with respect to the total volume of the glass ceramic.   The glass ceramic according to any one of claims 1 to 11, wherein catalytic activity is expressed by light having a wavelength from an ultraviolet region to a visible region.   The glass ceramic according to claim 12, wherein the decomposition activity index of methylene blue based on JIS R 1703-2: 2007 is 3.0 nmol / L / min or more.   The glass ceramic according to any one of claims 1 to 13, wherein a contact angle between a surface irradiated with light having a wavelength from an ultraviolet region to a visible region and a water droplet is 30 ° or less.   A photocatalytic functional glass-ceramic molded body comprising the glass-ceramic according to any one of claims 1 to 14.   The hydrophilic glass-ceramics molded object which consists of glass ceramics in any one of Claim 1 to 14.   The glass ceramic molded body according to claim 15 or 16, which has a fiber shape. A method for producing a glass ceramic according to any one of claims 1 to 14,
A method for producing glass ceramics, in which a raw material composition mixture is maintained at a temperature of 1250 ° C. or higher to form a liquid phase at least partially, and then cooled and solidified. A method for producing a glass ceramic according to any one of claims 1 to 14,
A melting step of mixing raw materials to obtain a melt;
A cooling step of cooling the melt to obtain a glass body;
A reheating step of raising the temperature of the glass body to a temperature range exceeding the glass transition temperature;
A crystallization step of maintaining the temperature within the temperature range to produce crystals;
The manufacturing method of the glass ceramic which has this.   The temperature range of the said crystallization process is a manufacturing method of the glass ceramics of Claim 19 which are 510 degreeC or more and 1200 degrees C or less. The method The method according to claim 19 or 2 0 SL placing the glass-ceramic further comprises an etching step for immersion in dry etching and / or an acidic or alkaline solution to the glass body after the crystallization step.

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