JP2003275600A - Visible ray responsive and adsorptive composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide apatite coated titanium oxide having a visible ray responsive property, further having apatite coating in far larger quantity compared with a conventional one and being excellent in adsorption property and hydrophilicity. <P>SOLUTION: The composite material consists of visible ray responsive titanium oxide coated with calcium phosphate at least at a part of the surface thereof. A coating material and a fibrous material containing each the composite material are provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite material in which a surface of a titanium oxide photocatalyst having visible light responsiveness is coated with or coated with calcium phosphate, and organic and inorganic coating materials and fibrous substances containing the composite material.

[0002]

2. Description of the Related Art In order to improve the photocatalytic function of a photocatalyst, for example, a fine powder of porous titanium oxide and a water-soluble glucan are dispersed or dissolved in water in a treatment liquid or a fine powder of porous titanium oxide. There is known an air cleaning material obtained by immersing a carrier in a treatment liquid in which water-soluble glucan and fine powder of apatite are dispersed and dissolved, dried and heat-set (Japanese Patent Laid-Open No. 11-347407). Gazette). There is also known a spherical apatite composite particle (JP-A-7-31964) in which the surface of the spherical resin particle is coated with an apatite composite particle composed of calcium phosphate and titanium oxide. Furthermore, in Japanese Patent Laid-Open No. 11-256472,
A technique is disclosed in which a thin film made of calcium phosphate is provided on the surface of a fiber, a synthetic resin-made continuous foam type porous film, a porous hollow fiber membrane, and the like, and titanium oxide is supported on the surface of the thin film.

Apatite (a type of calcium phosphate)
Is highly adsorbable, it is expected that the photocatalytic function of the photocatalyst can be improved by combining it with titanium oxide. However, in the conventionally known apatite-coated titanium oxide, the apatite coating amount is 0.4% to less than 1% of titanium oxide. This is because the technology for coating apatite rapidly is not known, and since the coating amount is small, it is not possible to exhibit the adsorbing capacity as expected, and the photocatalytic function improving effect is also remarkable. It was not a thing.

Further, conventionally known apatite-coated titanium oxide is an ultraviolet responsive type, and when it is used indoors, it does not show visible activity or is extremely weak, so that it is practically possible to obtain sufficient efficacy. There wasn't.

Therefore, an object of the present invention is to have visible light responsiveness, and the apatite coating is remarkably large in number as compared with the conventional one.
It is to provide an apatite-coated titanium oxide having excellent adsorption performance and hydrophilicity.

The present invention which solves the above problems is as follows. [Claim 1] A composite material in which calcium phosphate is coated on at least a part of the surface of visible light responsive titanium oxide. [Claim 2] The composite material according to claim 1 or 2, wherein the visible light responsive titanium oxide is titanium dioxide having stable oxygen defects. [Claim 3] The visible light responsive titanium oxide is titanium oxide containing at least anatase titanium oxide, and g value in ESR measured in vacuum under irradiation of light having a wavelength of 420 nm or more at 77K. Is 2.0
The main signal is 04 to 2.007 and the g value is 1.985.
Two side signals, ˜1.986 and 2.024, are observed, and these three signals are
K, the composite material according to claim 1, which is a visible light responsive photocatalyst that is minutely or substantially not observed in the dark. [Claim 4] The visible light responsive titanium oxide has a wavelength of 42
The composite material according to any one of claims 1 to 3, which is responsive to the action of light having a wavelength of 0 nm or more. [Claim 5] The composite material according to any one of claims 1 to 4, which is in the form of particles. [Claim 6] In the X-ray crystal diffraction test method, when the intensity of the peak due to the anatase type titanium dioxide between 23 ° and 27 ° is 100, it is 30 ° to 35 °.
The composite material according to any one of claims 1 to 5, wherein the intensity of a peak due to calcium phosphate between 1 and 2 is 1 to 30. [Claim 7] In the X-ray crystal diffraction test method, when the intensity of the peak due to anatase type titanium dioxide between 23 ° and 27 ° is 100, it is due to calcium phosphate between 30 ° and 35 °. The composite material according to any one of claims 1 to 5, wherein the intensity of the peak is 1.5 to 10. [Claim 8] In the X-ray crystal diffraction test method, when the intensity of the peak due to anatase-type titanium dioxide between 23 ° and 27 ° is 100, it is due to calcium phosphate between 30 ° and 35 °. The peak intensity is 2
10. The composite material according to any one of claims 1 to 5, which is 10. [Claim 9] In the measurement by X-ray electron spectroscopy, Ti and
The area attributed to 2p of Ca and 2p of P is 1 to 30, and the area attributed to 2p of Ti is 100, when the element amount ratio of Ca and P is 100. The composite material according to the item. [Claim 10] The composite material according to any one of claims 1 to 9, wherein at least a part of the calcium phosphate coated on the surface of titanium oxide is in the form of submicron particles or columns. [Claim 11] A coating material containing the composite material according to any one of claims 1 to 10. [Claim 12] The paint according to claim 11, wherein the paint contains an organic binder or an inorganic binder. [Claim 13] A fibrous substance containing the composite material according to any one of claims 1 to 10.

In the composite material of the present invention, visible light responsive titanium oxide is used as a base material coated with calcium phosphate, and at least a part or all of the surface of the base material is coated with calcium phosphate.

The visible light responsive titanium oxide can be, for example, titanium dioxide having stable oxygen defects. More specifically, it can be a visible light photocatalyst described in WO 00/10706, which comprises titanium dioxide having a stable oxygen defect and has activity under visible light irradiation. This photocatalyst is obtained, for example, by using ST-01 manufactured by Ishihara Sangyo Co., Ltd., which is known as an ultraviolet photocatalyst, as a raw material and subjecting this to plasma treatment with hydrogen or argon. Its activity is not limited to around 420 nm6
It can photo-oxidize NO even with light having a wavelength exceeding 00 nm.

Further, the visible light responsive titanium oxide contains at least anatase titanium dioxide, and is 7
In ESR measured under irradiation with light having a wavelength of 420 nm or more at 7 K, g value is 2.004 to 2.0.
The main signal is 07 and the g value is 1.985 to 1.986.
, And two side signals of 2.024 are observed, and these three signals are minutely observed in vacuum at 77K in the dark, or may be a material which is not substantially observed. .

The visible light responsive titanium oxide used in the present invention preferably contains anatase titanium dioxide as a main component, and may further contain rutile titanium dioxide and / or amorphous titanium dioxide. Good. Further, the anatase type titanium dioxide does not necessarily have to have high crystallinity.

FIG. 1 shows a typical spectrum of ESR of the visible light-responsive titanium oxide used in the present invention measured at 77K in vacuum. In the figure, the upper part is a spectrum in the dark, and the middle part is a spectrum under irradiation with light having a wavelength of 420 nm or more (cutoff of light of less than 420 nm of light of a mercury lamp). The lower part is a spectrum when light of a mercury lamp is irradiated without cutting off light of less than 420 nm. The upper, middle, and lower rows are the results measured under the same gain (GAIN).

Comparing the upper and middle spectra of FIG. 1 clearly shows that the g value is 2.0 in the middle spectrum.
The main signal is from 04 to 2.007, and the g value is 1.
The two side signals, 985 to 1.986 and 2.024, are more intense than in the upper spectrum.
Also, comparing the spectra in the middle and bottom of FIG. 1, it is clear that the main signal with a g-value of 2.004 to 2.007 and the g-values of 1.985 to 1.986 and 2.02.
The intensity of the two side signals of 4 is substantially the same regardless of whether or not the irradiation light contains light of 420 nm or less.

Further, as shown in FIG. 2, the visible light responsive titanium oxide used in the present invention has the three signals in vacuum, at room temperature, in the dark and under ESR under light irradiation having a wavelength of 420 nm or more. It can be the object to be measured. In FIG. 2, the upper part is a spectrum in the dark, and the middle part is a spectrum under irradiation with light having a wavelength of 420 nm or more (cutoff of light of less than 420 nm among lights of a mercury lamp). The lower row is 420n
It is a spectrum when light of a mercury lamp is irradiated without cutting off light of less than m. The upper, middle, and lower rows are the results measured under the same gain (GAIN).

Further, it is considered that the above three signals in the visible light responsive titanium oxide used in the present invention are attributed to radicals resulting from hole trapping. this is,
As shown in the reference example, it is clear from the ESR spectrum in the atmosphere of isopropanol which is the electron donor molecule and the ESR spectrum in the atmosphere of oxygen which is the electron acceptor molecule.

The visible light responsive titanium oxide used in the present invention has a g value of 2.009 to 0 in addition to the above signals in ESR measured under irradiation with light having a wavelength of 420 nm or more at 77K in vacuum. It can also have a side signal that is 2.010. g value is 2.00
The secondary signals of 9 to 2.010 are ES in the middle of FIG.
This is shown in the R spectrum.

The visible light responsive titanium oxide used in the present invention is
The bond ratio of Ti (titanium) and O (oxygen) may be less than 2 and may be oxygen-defective titanium oxide. Whether or not it is an oxygen-deficient titanium oxide can be measured by X-ray photoelectron spectroscopy (XPS). In order to determine the bond state of titanium and oxygen and the stoichiometric ratio of elements that can be measured and specified by X-ray photoelectron spectroscopy (XPS), it is attributed to Ti-O of titanium oxide having close bond energy. It is preferable to separate 530 ± 0.5 eV and 532 ± 0.5 eV attributed to the OO bond of adsorbed oxygen and obtain it by calculation. From the results of measurement and calculation by this method, it is found that the visible light responsive titanium oxide described in Reference Example is an oxygen deficiency type. Commercially available titanium oxide catalysts such as ST-01 (manufactured by Ishihara Sangyo) and other JRC-ITO3 (catalyst Society of Japan reference catalyst), P-25 (manufactured by Nippon Aerosil), etc., have an O / Ti ratio even if errors are taken into consideration. Is 2.0 ± 0.0
It has a value of 5. Although there is an aspect that cannot be unambiguously defined for oxygen defects, it is preferably 1.5 to 1.95.

The visible light responsive titanium oxide used in the present invention can be produced by using amorphous or incompletely crystalline titanium dioxide as a raw material.
It can be obtained by a sulfuric acid method, a chloride method, or a wet method using titanium alkoxide as a raw material. More specifically, the raw material titanium dioxide can be obtained by hydrolyzing titanium chloride with ammonium hydroxide. This hydrolysis is suitably performed by adjusting the addition amount of ammonium hydroxide so that the pH of the reaction solution becomes 6 or more. The titanium chloride may be any of titanium trichloride, titanium tetrachloride, titanium oxychloride, etc., and a mixture thereof may be used. The hydrolysis can be performed, for example, under cooling or at a temperature in the range of room temperature to 90 ° C., but the hydrolysis at room temperature gives titanium dioxide having relatively low crystallinity or amorphous. From the viewpoint, it may be preferable. Further, the hydrolyzate of titanium chloride with ammonium hydroxide is preferably used as raw material titanium dioxide after washing with an ammonium hydroxide aqueous solution. The washing with the aqueous ammonium hydroxide solution can be carried out so that the residual amount of ammonium chloride produced during the hydrolysis is reduced to an appropriate amount, and preferably it can be carried out plural times. Further, as the amorphous or incompletely crystalline titanium dioxide, a commercially available product may be used,
For example, it may be incompletely crystalline titanium dioxide such as ST-01 or C-02 manufactured by Ishihara Sangyo.

Alternatively, in the production of visible light-responsive titanium oxide, the hydrolyzate obtained by hydrolyzing titanium sulfate or titanyl sulfate is washed with water and at least one of the sulfate ions contained in the hydrolyzate is washed. Heating in the presence of ammonia or a derivative thereof after removing the part,
It can also be carried out by a method comprising titanium oxide containing at least anatase type titanium oxide.

The above hydrolyzate can be washed with water or ammonia water, but as a result of subsequent studies, it is found that a product having a higher BET specific surface area can be obtained by washing with water as compared with washing with ammonia water. Okay, in the present invention,
Uses water cleaning. More specifically, when the heating conditions are the same, the product obtained by washing with water can obtain a product having a BET specific surface area almost twice as large as that obtained by washing with ammonia water. Since a product having a higher BET specific surface area can be expected to be excellent in terms of adsorption performance, it is extremely advantageous when the material obtained by the production method of the present invention is used as a photocatalyst.

Further, in the above-mentioned manufacturing method, it is preferable that the washing with water is carried out until the concentration of sulfate ion in the washing filtrate becomes 2000 ppm or less. It is more preferable that the washing with water is performed until the concentration of sulfate ion in the washing filtrate becomes 1500 ppm or less. When the titanium sulfate or titanyl sulfate is hydrolyzed with ammonia, the washing with water is performed so that the ammonium ion concentration in the washing filtrate is 20% or less.
It is preferable to carry out until it becomes 0 ppm or less.

The visible light responsive titanium oxide used in the present invention can be produced, for example, as follows, in addition to the above method. Amorphous or incompletely crystalline titanium dioxide is heated in the presence of ammonia or its derivatives.
Ammonia may be liquid or gas. When using ammonia gas, the raw material titanium dioxide is heated in an ammonia gas atmosphere. Examples of the ammonia derivative include ammonium salts such as ammonium chloride. For example, titanium dioxide as a raw material is heated in the presence of ammonium chloride.

The heating of the raw material titanium dioxide in the presence of ammonia or its derivative is carried out when the absorption of light at a wavelength of 450 nm of the material produced by heating is larger than the absorption of light of the raw material titanium dioxide at a wavelength of 450 nm. This is done by terminating. Normally, the raw material titanium dioxide is white, and the absorption of light at a wavelength of 450 nm is 10%.
Before and after. On the other hand, when the raw material titanium dioxide is heated in the presence of ammonia or its derivative, it gradually becomes yellow. However, this coloring has a peak at a certain point and finally fades to a level similar to that of the raw material titanium dioxide. The maximum absorption of light at a wavelength of 450 nm is 60, although it depends on the type of raw material titanium dioxide, the type and amount of coexisting ammonia (derivative), heating temperature and time.
It may reach around%. The characteristics of visible light-responsive titanium oxide are not uniquely determined by the absorption intensity of light at a wavelength of 450 nm, but when the absorption of light at a wavelength of 450 nm is 20% or more (reflectance of 80% or less), it is clear It becomes a material showing visible light response.

Although the above heating conditions cannot necessarily be specified only by temperature, the temperature used is, for example, 300 to 500 ° C.
Can range in temperature. Moreover, this heating can be performed under normal pressure. Further, the heating time can be appropriately determined by taking into consideration the light absorption at the wavelength of 450 nm of the material produced by heating as a standard.

For the above heating, a rotary kiln, a tunnel kiln, a muffle furnace, etc. which are commonly used in this field can be used. When individual particles of titanium oxide are aggregated or sintered by heating, they may be pulverized by a pulverizer, if necessary.

The material obtained by heating as described above can be washed with water or an aqueous solution if necessary.
This washing may improve the visible light responsiveness of the visible light responsive titanium oxide obtained in some cases. For example, amorphous or incompletely crystalline titanium dioxide (material before heating)
However, when titanium chloride is obtained by hydrolyzing titanium chloride with ammonium hydroxide, a considerable amount of ammonium chloride remains in the hydrolyzate, and as a result, as described above, amorphous or incomplete. It becomes possible to convert crystalline titanium dioxide into visible light responsive titanium oxide. However, a considerable amount of ammonium chloride may remain in the obtained material even after the heat treatment. In such a case, ammonium chloride may be removed by washing with water or an appropriate aqueous solution, and the visible light responsiveness of the visible light responsive titanium oxide may be improved in some cases. In this case, wash the material obtained by heating with water or an aqueous solution, and adjust the pH of the water or aqueous solution after washing.
Can be performed, for example, in a range of 5 or more.

The visible light responsive titanium oxide used in the present invention has silicon, aluminum, tin, zirconium, antimony, phosphorus, on its surface and / or inside, depending on the application.
An element such as platinum, gold, silver, copper, iron, niobium, tungsten, tantalum, or a compound containing them can be coated, supported, or doped.

In the composite material of the present invention, the visible light responsive titanium oxide is coated with calcium phosphate, and in the present invention, "calcium phosphate" means hydroxyapatite, carbonate apatite, fluoroapatite, triphosphate. It means any one of calcium and octacalcium phosphate, or a mixture of two or more thereof.

In the composite material of the present invention, the coating amount of calcium phosphate is 30 when the peak intensity due to anatase type titanium dioxide between 23 ° and 27 ° is 100 in the X-ray crystal diffraction test method. The intensity of the peak due to calcium phosphate between 1 ° and 35 ° is 1
It can be set to not less than 1, preferably not less than 1.5, more preferably not less than 2, and there is no particular upper limit, but it is not more than 30, preferably not more than 10, and more preferably not more than 5.

In the composite material of the present invention, the coating amounts of calcium phosphate and Ti were measured by X-ray electron spectroscopy.
When the elemental ratio of Ca and P is 100, Ca and P
Is 1 or more, preferably 1.5 or more, and more preferably 2 or more. The upper limit is Ti and Ca
When Ti and P are elemental ratios of 100, both Ca and P are 30 or less, preferably 10 or less, and more preferably 5 or less.

The form of calcium phosphate coated on the surface of titanium oxide is not particularly limited, but for example, at least a part thereof may be submicron particles or may be columnar. It is clear from the SEM photograph (FIG. 6) that the shape of the apatite (calcium phosphate) in the composite material of the present invention includes particles or columnar particles, and the size thereof is submicron. From the shape, a porous photocatalyst, which has rose flower-shaped calcium phosphate supported in an island shape, and titanium oxide particles, which have rose flower-shaped calcium phosphate supported in an island shape, disclosed in JP 2001-232206 A, Kaihei 10-244166
It is a substance whose properties are obviously different from those of an environment-purifying material or the like in which the surface of a base material having a surface made of titanium oxide described in Japanese Patent Laid-Open Publication No. 9-242242 is coated with a porous calcium phosphate film. Further, the composite material of the present invention may have an amount of apatite (calcium phosphate) supported up to about 10% of titanium oxide, and hydrophilicity and other physical properties are also different from those of the conventional apatite-coated titanium oxide. Further, it was revealed that the composite material of the present invention has strong light absorption in the visible region.

A method for manufacturing the composite material of the present invention will be described. Visible light-responsive titanium oxide imitating human body fluid 2
It is more preferable to be in the simulated body fluid of 5 ° C to 60 ° C for about 1 second to 1 hour, and when immersed in the simulated body fluid of 30 ° C to 40 ° C for about 1 minute to 10 minutes, the reaction between calcium hydroxide and phosphate ions will occur. The calcium phosphate that forms can be deposited. When immersed in the simulated body fluid for a certain period of time or more, calcium phosphate adheres to the entire surface of the titanium oxide particles. For the first time, it was discovered that when visible light-responsive titanium oxide is used as the base material for depositing calcium phosphate, a large amount of calcium phosphate is unexpectedly and rapidly deposited compared to the conventional surface deposition of photocatalyst. .

In the present specification, the "pseudo body fluid" refers to an isotonic aqueous solution containing at least Na and P ions. "Na", "K", "Cl", "Ca", "P",
Those containing ions such as "Mg" and having a pH of 7 to 8 are preferable, and those having a pH of 7.3 to 7.7 are particularly preferable.

The present invention also includes a paint (coating composition) containing the composite material of the present invention. The coating material of the present invention contains at least the above composite material, a binder and a solvent. The binder may be either an organic binder or an inorganic binder.

Examples of the inorganic binder include products obtained by hydrolyzing hydrolyzable silicon compounds such as alkyl silicates, silicon halides and partial hydrolysates thereof, silica, colloidal silica, water glass and organo. Silicon compounds such as polysiloxane, polycondensates of organic polysiloxane compounds, phosphates such as zinc phosphate and aluminum phosphate, polyphosphates, cement,
Inorganic binders such as lime, gypsum, frit for enamel, glaze for glass lining, plaster and the like can be mentioned. Also, as the organic binder,
Examples thereof include organic binders such as fluoropolymers, silicone polymers, acrylic resins, epoxy resins, polyester resins, melamine resins, urethane resins and alkyd resins. Conventionally, since the binder may be deteriorated or decomposed by the photocatalytic function of the photocatalyst, it is necessary to appropriately select the kind of the binder depending on the use scene, the degree of the photocatalytic function, and the application. But,
In the present invention, since the composite material is used as the photocatalyst, the deterioration due to the photocatalytic function is significantly less than that of the coating material using the conventional ultraviolet type photocatalyst, or when it is used in a room where there is almost no ultraviolet light, the photocatalytic function is used. Almost no deterioration.
Therefore, an organic binder such as an acrylic resin, an epoxy resin, a polyester resin, a melamine resin, a urethane resin or an alkyd resin, which cannot be used in a coating material using an ultraviolet photocatalyst, can be favorably used. In the present invention, these binders may be used alone or in combination of two or more.

Examples of the alkyl silicate include compounds represented by the general formula: Si _n O _n-1 (OR) _{2n +2} (where Si is silicon, O is oxygen, and R is an alkyl group). The above n may be, for example, 1 to 6, and R may be, for example, an alkyl group having 1 to 4 carbon atoms. However, it is not limited to these. Examples of the cement include early-strength cement, ordinary cement, moderate heat cement, sulfate resistant cement, white (white) cement, oil well cement, portland cement such as geothermal well cement, fly ash cement, high sulfate cement, silica cement, A mixed cement such as blast furnace cement or alumina cement can be used. As plaster, for example, gypsum plaster, lime plaster, dolomite plaster, etc. can be used. Examples of the fluorine-based polymer include polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, ethylene-polytetrafluoroethylene copolymer, ethylene. -Crystalline trifluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer or other crystalline fluororesin, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer or other amorphous fluororesin,
Various kinds of fluorine rubber can be used. In particular,
Fluorine-based polymers containing a vinyl ether-fluoroolefin copolymer and a vinyl ester-fluoroolefin copolymer as a main component are preferable because they are less likely to be decomposed and deteriorated and are easy to handle. As the silicon-based polymer, straight-chain silicone resin, acrylic modified silicone resin,
Various silicone rubbers can be used.

The organic polysiloxane compound used for the polycondensation product of the organic polysiloxane compound is a substance known as a hydrolyzate of an organic silicon compound, and is disclosed in, for example, JP-A-8-
No. 164334, No. 8-67835, No. 8-155308, and No. 10-66830.
Those described in Japanese Patent Publication No. 2756474, etc. can be used as they are. The organic polysiloxane compound is a hydrolyzate of an organic silicon compound, and examples of the organic silicon compound include compounds having an alkyl group and an alkoxy group.

Hydrolyzates of organosilicon compounds having an alkyl group and an alkoxy group are also known, for example, R ¹ _n Si (OR
² ) Obtained by hydrolyzing an organosilicon compound represented by _4-n . R ¹ and R ² are each, for example, a carbon number.
It may be a lower alkyl group having 1 to 8 and considering the film strength of the resulting coating, R ¹ is suitably a lower alkyl group having 1 to 3 carbon atoms, preferably a methyl group. N in the above formula is an integer of 0 to 2, and specifically,
It is appropriate to use a hydrolyzate (three-dimensional crosslinked product) of a mixture of organosilicon compounds in which n is 1 or 2 in consideration of film strength and the like.

Examples of the above-mentioned organic silicon compound include methyltrimethoxysilane, methyltriethoxysilane,
Methyltriisopropoxysilane, methyltri-t-butoxysilane, methyltrichlorosilane, methyltribromosilane; ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane Silane; n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltrit-butoxysilane, n-propyltrichlorosilane, n-propyltribromosilane; n-hexyltri Methoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane; n- Sill trimethoxysilane,
n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltri-t-butoxysilane,
n-decyltrichlorosilane, n-decyltribromosilane; n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltrit-butoxysilane, n-octadecyltrichlorosilane, n-octadecyltribromosilane, tetramethoxysilane,
Tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltri Methoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane and the like can be mentioned.

The content of the binder is about 10 to 2000% by weight, preferably 25 to 1000% by weight, based on the solid content of the composite material particles, preferably 25 to 500% by weight.
% Is more preferable, and 25 to 250% is further preferable. By setting the compounding amount of the binder within the above range,
When the composite material is used as a coating film, the composite material is not detached and the visible light response function of the composite material can be maintained.

As the solvent, an inorganic solvent or an organic solvent,
Mixtures thereof can be used. Water is preferred as the inorganic solvent. As the organic solvent, alcohols such as methanol, ethanol, 2-propanol and ethylene glycol, ketones and the like can be used. From the viewpoints of handleability and coatability, those containing alcohol are preferable. The blending amount of the solvent can be appropriately set according to workability.

The visible light responsive coating composition of the present invention may optionally contain at least one compound selected from the group consisting of dicarboxylic acids and their derivatives. Dicarboxylic acid is a carboxyl group COO in the molecule.
Organic compounds having two H, for example, aliphatic saturated dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, maleic acid, fumaric acid. Aliphatic unsaturated dicarboxylic acids such as acids, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid can be used. A dicarboxylic acid derivative is a dicarboxylic acid ester, dicarboxylic acid salt, dicarboxylic acid anhydride, dicarboxylic acid azide, dicarboxylic acid amide, dicarboxylic acid imide or other dicarboxylic acid having a small structural change. It is a compound that can be, for example, methyl dicarboxylate, ethyl dicarboxylate, propyl dicarboxylate, butyl dicarboxylate, sodium dicarboxylate,
Ammonium dicarboxylate or the like can be used.

The content of dicarboxylic acid and its derivative is 0.5 with respect to the composite material particles in the visible light responsive coating material.
To about 500% by weight, preferably 5 to 500% by weight, more preferably 10 to 500% by weight, and 25 to 250
Weight percent is even more preferred. When the content of dicarboxylic acid and its derivative is less than the above range, the effect of addition is difficult to be exhibited, and even when it is more than the above range, a more remarkable effect is hardly recognized. Further, in the visible light responsive coating composition of the present invention, at least one compound selected from the group consisting of dicarboxylic acids and derivatives thereof, composite material particles, a binder, a solvent, a dispersant, a surfactant, a curing agent,
Various additives such as a crosslinking agent may be included.

The present invention can also provide an article formed with a coating film containing a composite material using the visible light responsive coating composition. As the article, an article made of an inorganic material such as ceramics and glass, an article made of an organic material such as plastic, rubber, wood, paper, a metal article such as aluminum and an alloy such as a rope can be used. The size and shape of the article are not particularly limited. The film thickness of the composite material-containing coating film formed on the article can be appropriately set depending on the application, and can be, for example, about 0.01 to 100 μm. The visible light responsive coating composition of the present invention can be used to form a composite material-containing film on an article by applying or spraying the visible light responsive coating composition onto the article. Specifically, the composite material particles and the binder are dispersed in a solvent to form a coating material, and then the coating material is applied or sprayed on the substrate to dispose the composite material particles and the binder on at least a part of the substrate. Is preferred. As the solvent, water or an organic solvent such as toluene or alcohol can be used. As a coating method, for example, an ordinary method such as an impregnation method, a dip coating method, a spinner coating method, a blade coating method, a roller coating method, a wire bar coating method, a reverse roll coating method, a brush coating method, a sponge coating method is used. Alternatively, it can be sprayed by a conventional method such as a spray coating method. After coating or spraying in this manner, the solvent is removed by drying or baking. The drying or firing temperature is preferably lower than 500 ° C, more preferably room temperature to 400 ° C. In this case, if the temperature is higher than 500 ° C., the visible light response function is likely to deteriorate, which is not preferable. Further, if necessary, a method such as ultraviolet irradiation may be used to solidify the binder used. Before applying or spraying the visible light responsive coating on the article, if necessary, the organic binder, an acrylic resin, an epoxy resin, a polyester resin, a melamine resin,
An organic binder such as a urethane resin or an alkyd resin or the above-mentioned inorganic binder may be applied or sprayed on the article in advance as a primer or a coating.

Conventional hydrophilic paints and coating films (for example, Japanese Patent Laid-Open No. 11-1659) contain silica and silicone in order to obtain weather resistance. On the other hand, in the present invention, a coating film having excellent weather resistance can be obtained without containing silica or silicone. Since it is possible to obtain a coating film having excellent weather resistance without containing silica or silicone, the degree of freedom in composition is improved.For example, it is possible to increase the amount of binder or the content of composite material. is there. However, the coating material and coating film of the present invention may contain silica or silicone.

After coating or spraying as described above, it is solidified to obtain the composite material body of the present invention. The solidification can be carried out by a method of drying, irradiating with ultraviolet rays, heating, cooling, or using a crosslinking agent, but the solidification temperature is lower than 400 ° C., preferably room temperature. Perform at a temperature of ~ 200 ° C. In this case, if the temperature is higher than 400 ° C., the binder is thermally deteriorated and the composite material particles are easily detached, which is not preferable.

The present invention can also provide an article having the coating film of the present invention on at least a part of the surface of a substrate.
As the base material, for example, the outer wall surface of the building, the roof outer surface of the roof, the outer surface of the window glass or the inner surface of the window glass, the wall surface of the room,
Floors or ceilings, blinds, curtains, road barriers, tunnel walls, exterior or reflective surfaces of lights,
It can be an interior surface of a vehicle, a mirror surface, an outside surface of a window glass or an inside surface of a window glass. By using a coating film containing the composite material of the present invention or an article having this coating film, sterilization and / or
Alternatively, an antifouling method can be provided. Further, by using the composite material of the present invention, it is possible to provide a method for purifying water and a method for purifying nitrogen oxides.

A coating film containing the composite material of the present invention can be decomposed and purified or sterilized by irradiating it with visible light to decompose harmful substances, malodorous substances, oils and the like existing around it. . Examples of the light to be applied include light containing visible light, such as sunlight, fluorescent lamps, halogen lamps, xenon flash lamps, mercury lamps, and L lamps.
Light such as ED and organic EL can be used. In particular,
Light containing visible light of 400 nm to 700 nm is preferred. The light irradiation amount and irradiation time can be appropriately set depending on the amount of the substance to be treated and the like.

The present invention also includes fibrous substances containing the above-mentioned composite material of the present invention. Examples of the fibrous substance include synthetic fibers such as polyester fibers, polyamide fibers, polyacrylonitrile fibers, polypropylene fibers, polyethylene fibers, polyvinyl chloride fibers, fluorine fibers, aramid fibers, and sulfone fibers. Fibers, rayon, semi-synthetic fibers such as acetate, natural fibers such as cotton, wool, silk, hemp, glass fibers, carbon fibers, ceramics fibers, etc., and woven fabrics, knitted fabrics, non-woven fabrics composed of these mixed fibers,
Threads, ropes, strings, etc. Such fibers may contain various additives that are usually used in order to improve the productivity and characteristics in the manufacturing process and the processing process of the raw yarns. For example,
A heat stabilizer, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a plasticizer, a thickener, a coloring agent, a leveling agent, an antibacterial agent, a fungicide, etc. can be contained. The fibrous substance containing the composite material of the present invention can exhibit a particular effect even in a fiber made of an organic polymer which is easily deteriorated by a photocatalytic reaction.

The composite material of the present invention has the above-mentioned physical characteristics, and can continuously perform, for example, malodorous components in the air, environmental pollutants such as NOx, wastewater treatment and water purification treatment, As an environmental purification material, it has excellent ability to decompose and eliminate environmental pollutants and antibacterial activity. Moreover, it is an object of the present invention to provide a photocatalyst having excellent properties in terms of economy and safety and a method for producing the same, and to provide a coating material and a fiber using the photocatalyst.

[0050]

EXAMPLES The present invention will now be described in more detail with reference to examples. Example 1 Titanium oxide having a visible activity produced in Reference Example 8 was suspended in 1 liter of simulated body fluid and allowed to stand at 37 ° C. for 1 hour,
It was separated by decantation and centrifugation, and then dried at the same temperature of 37 ° C. As simulated body fluid, sodium chloride 8000 mg and potassium chloride 200 in 1 liter of water.
mg, sodium monohydrogen phosphate 1150 mg, potassium dihydrogen phosphate 200 mg, and calcium chloride 200 mg were used. Thus, a composite material was obtained in which the titanium oxide film surface was uniformly covered and columnar and crystalline submicron apatite particles were deposited. The SEM photograph of the obtained composite material is shown in Fig. 6 (5000 times and 2000 times).
0 times). For comparison, a commercially available apatite-coated titanium oxide (manufactured by Showa Denko) SEM photograph is shown in FIG. 7 (5000 times and 20000 times), and a visible SEM photograph of titanium oxide produced in Reference Example 8 is shown in FIG. 8 (5000 times). Double and 20
000 times).

Example 2 10 g of the titanium oxide having visible activity produced in Reference Example 8 was suspended in 1 liter of simulated body fluid, allowed to stand at 37 ° C. for 10 minutes, separated by decantation and centrifugation, Then, it was dried at the same temperature of 37 ° C. As a simulated body fluid, in 1 liter of water, sodium chloride 8000 mg, potassium chloride 200 mg, sodium monohydrogen phosphate 1150 mg,
200 mg potassium dihydrogen phosphate, 40 calcium chloride
The one containing 0 mg was used. In this way, a composite material was obtained in which the titanium oxide film surface was covered and columnar and crystalline submicron apatite particles were deposited.

Further, the composite material obtained in Example 1 was measured by the X-ray crystal diffraction test method and the X-ray electron spectroscopy method. Results of X-Ray Crystal Diffraction Test Method The X-ray crystal diffraction test results of the composite material obtained in Example 1 (upper part) and the titanium oxide with visible activity (lower part) produced in Reference Example 8 used as a raw material are shown in FIG. Shown in. Figure 9
As shown in (upper row), the intensity of the peak between 23 and 27 degrees due to the anatase crystal of titanium oxide is 100.
If you say, 30 to 35 due to calcium phosphate
The intensity of the peak between degrees was about 20. Results of X-ray electron spectroscopy For the composite material obtained in Example 1, FIG. 10 shows Ti, FIG. 11 shows Ca, and FIG. 12 shows results of P measurement by X-ray electron spectroscopy. As shown in these figures, the element amount ratio of Ti, Ca, and P was about 11 and 10, respectively, when Ti was 100. From the above results, it was clarified that about 10% of calcium phosphate (apatite) was present with respect to titanium oxide. Absorption spectrum FIG. 13 shows the absorption spectra of the composite material obtained in Example 1 (upper part) and the titanium oxide with visible activity (lower part) produced in Reference Example 8 used as a raw material.

Further, the performance evaluation of the composite materials obtained in the above examples was carried out. The results are shown in Table 1 below. For comparison, it was compared with a commercially available apatite-coated titanium oxide (manufactured by Showa Denko).

[0054]

[Table 1]

The removal ability of NO by oxidation was determined by the following method. Test Example Oxidizing activity of NO (removal rate) The composite material produced in Example 1 was prepared using a Pyrex (registered trademark) glass reaction container (inner diameter 160 mm, thickness 25 m).
m). A 300 W xenon lamp was used as a light source, and light was emitted as monochromatic light having a half width of 20 nm by an irradiation device manufactured by JASCO Corporation. Simulated polluted air (NO: 1 ppm) having a humidity of 0% RH was continuously supplied to the reaction container at a flow rate of 1.5 liter / min, and a change in NO concentration at the reaction outlet was monitored. The NO concentration was measured by a chemiluminescence method using ozone. The NOx removal rate was calculated from the cumulative value of the monitor values for 1 hour. The NO removal rate (%) of each sample at 470 nm and 360 nm is shown in Table 1 above.

Example 3 Results of Evaluation of Visible Light Activity of Apatite Sample Experimental Method: After 0.2 g of the sample was collected, it was uniformly applied to a 6 cm × 6 cm glass plate while adding distilled water. Then, the sample was dried and placed in a 550 mL glass reaction vessel. The reaction vessel is degassed to 5 Torr, and high-purity air (manufactured by Nippon Oxygen, CO
(2, 0.5 ppm or less) was returned to 760 Torr. Acetone was poured in a liquid state so that the amount of acetone was about 550 ppm. After vaporization, it was adsorbed for about 4 hours, and after adsorption equilibrium, Blue-LED (23 NSPB500S, manufactured by Nichia, center wavelength 470 nm, array of 23) was irradiated for 12 hours. The results are shown in Table 2. The CO ₂ concentration was measured by gas chromatography (TCD). Measurement sample: (1) Composite material obtained in Example 1 (2) Commercially available apatite-coated titanium oxide (manufactured by Showa Denko) (3) Titanium oxide with visible activity produced in Reference Example 8

[0057]

[Table 2]

From these results, it can be seen that the composite material (1) obtained in Example 1 can photo-oxidize acetone even by the light of the LED, which is mostly visible light. On the other hand, in the commercially available apatite-coated titanium oxide (2), no CO ₂ formation was observed even after 12 hours, and the acetone concentration was almost the same as that at light-on. Therefore, this sample (2)
Therefore, it is considered that the adsorption has hardly occurred. Also, the difference between the results of (1) and (3) (difference in the amount of CO ₂ produced)
In Example 1, the coating amount of the sample was 0.2 g, which was a constant amount.
In the case of the composite material (1) obtained in 1., it is considered that the total amount of 0.2 g is not a photocatalyst.

Reference Example 1 500 g of titanium tetrachloride (special grade, manufactured by Kanto Chemical Co., Inc.) was added to ice-water (2 liters of water) of pure water and stirred,
It melt | dissolved and the titanium tetrachloride aqueous solution was obtained. This aqueous solution 200
While stirring g with a stirrer, about 50 ml of ammonia water (containing 13 wt% as NH ₃ ) was added as quickly as possible. The amount of ammonia water added was adjusted so that the pH of the aqueous solution was about 8. As a result, the aqueous solution became a white slurry. After stirring for another 15 minutes,
It was filtered with a suction filter. The precipitate collected by filtration was dispersed in 20 ml of ammonia water (containing 6 wt% as NH ₃ ), stirred with a stirrer for about 20 hours, then suction-filtered again,
A white hydrolyzate was obtained. The obtained white hydrolyzate was transferred to a crucible and heated in an electric furnace at 400 ° C. for 1 hour in an electric furnace to obtain a yellow product.

The XRD measurement result of the obtained product is shown in FIG.
Shown in the upper row. In addition, the XRD measurement results of the white hydrolyzate dried at 50 ° C. are also shown in the lower part of FIG. From this result, it can be seen that the product obtained by drying the white hydrolyzate at 50 ° C. is amorphous, and the obtained product is anatase type titanium dioxide. The product obtained and the white hydrolyzate were dried at 50 ° C., and the absorption spectrum of the product was analyzed by a Hitachi self-recording spectrophotometer (U-32) equipped with an integrating sphere.
According to 10), it was measured under the following conditions. scan speed: 120 nm / min, response: MEDIUM, band pass: 2.00 nm, reference: barium sulfate As a result, the reflectance at 450 nm is 6 when the reflectance at 700 nm of the obtained product is 100%.
While the white hydrolyzate was dried at 50 ° C., the reflectance at 450 nm was 95% when the reflectance at 700 nm was 100%, whereas it was 1%.

The ESR spectrum of the obtained product was measured. Measurement is performed in vacuum (0.1 Torr), 77
K or at room temperature. The measurement conditions are as follows. [Basic parameters] Measurement temperature 77K or room temperature field 324mT ± 25mT Scan time 4 minutes Mod. 0.1mT Receiver gain 10 to 100 (measurement sensitivity) Time constant 0.1 seconds Light source High pressure mercury lamp 500W filter L-42 [Sample preparation] Vacuum degassing for 1 hour or more [Calculation of g value] Mn ²⁺ marker (g _mn = 1.981) as a reference, g = g _mn × H _mn / (H _mn + ΔH) H _mn : Mn ²⁺ marker magnetic field, ΔH: change amount of magnetic field from H _mn

In FIG. 1 (measurement temperature 77K) and FIG. 2 (measurement temperature normal temperature), the upper part shows the ESR spectrum in the dark, and the middle part shows the filter (L) that cuts light of 420 nm or less (using a 500 W high-pressure mercury lamp). -42) ESR spectrum measured under light irradiation, 420 in the lower row
The ESR spectrum measured in the state irradiated with light using a 500-W high pressure mercury lamp without using the filter (L-42) which cuts light below nm is shown, respectively.

Comparing the upper and middle spectra of FIG. 1, it is clear that the g value is 2.0 in the middle spectrum.
The main signal is from 04 to 2.007, and the g value is 1.
The two side signals, 985 to 1.986 and 2.024, were more intense in the upper spectrum. Further, when comparing the spectra in the middle and lower rows of FIG. 1, it is clear that the main signal having a g-value of 2.004 to 2.007 and the g-values of 1.985 to 1.986 and 2.0.
The intensities of the two side signals of 24 were substantially the same even when the irradiation light contained light of 420 nm or less.

Further, as shown in FIG. 2, the visible light responsive material of Reference Example 1 is also measured by ESR under the conditions where the above three signals are in the air, at room temperature, in the dark, and under irradiation with light having a wavelength of 420 nm or more. It was a thing. In addition, even if the white hydrolyzate was dried at 50 ° C., the g value was 2.00.
The main signal is 4 to 2.007, and the g value is 1.9.
Two side signals of 85 to 1.986 and 2.024 were not observed under any of the ESR measurement conditions.

A filter (L-4) that cuts light of 420 nm or less (using a high-pressure mercury lamp of 500 W) with air or isopropanol as a measurement atmosphere that was a vacuum
In the same manner as above under the condition of irradiating light through 2), ESR
The spectrum was measured. The result is shown in FIG. In the figure,
The upper graph shows the measurement results in vacuum, the middle graph shows the results in air, and the lower graph shows the results in isopropanol. Both the main signal and the two sub-signals are smallest in vacuum, slightly larger in isopropanol than in vacuum, but largest in middle air. Since isopropanol is an electron donor molecule, while oxygen in the air becomes an electron acceptor molecule, the above results suggest that the three signals are attributed to radicals resulting from hole trapping. It is a thing.

Reference Example 2 The white hydrolyzate obtained in Reference Example 1 was heated under the same conditions as in Reference Example 1 except that the heating time was 20 minutes or 3 hours to obtain a yellow product. . The absorption spectra of these products were measured as in Reference Example 1. The sample having a heating time of 20 minutes has a reflectance of 67% at 450 nm when the reflectance at 700 nm is 100%, and the sample having a heating time of 3 hours has a reflectance of 700 nm of 100%.
%, The reflectance at 450 nm was 67%.

Reference Example 3 A white hydrolyzate was obtained under the same conditions as in Reference Example 1 except that titanium tetrachloride was replaced with titanium trichloride, and the white hydrolyzate was heated at 400 ° C. for 1 hour, A yellow product was obtained. For this product, light below 420 nm (500
ESR measured under the condition of light irradiation through the filter (L-42) that cuts the W high-pressure mercury lamp)
The spectrum (measurement temperature 77K) showed a major signal and two minor signals with g-values similar to those shown in the middle of FIG.

Reference Example 4 Anatase type titanium dioxide powder (C-manufactured by Ishihara Sangyo Co., Ltd.)
02) 1.6 kg was filled in a heating container having an inner wall having an inner volume of 25 liters and a baffle plate on the inner wall, and was mounted in an external heat type rotary kiln device. Purging the inside of the heating container with nitrogen gas,
After that, ammonia gas was circulated at 1.5 l / min in terms of nitrogen gas. At the same time, the temperature inside the container was adjusted to 400 ° C. by an external heater, and the container was heated for 90 minutes while rotating. After heating, it was cooled to room temperature to obtain a yellow product.
FIG. 5 shows an ESR spectrum (measurement temperature 77K) measured in a state of being irradiated with light through a filter (L-42) that cuts light of 420 nm or less (using a 500 W high-pressure mercury lamp).

Reference Example 5 3 g of the powder obtained in Reference Example 1 was suspended in 100 ml of pure water and stirred for 1 hour using a magnetic stirrer. The obtained solution was suction filtered. The sample remaining on the filter paper was again stirred in pure water and suction-filtered. Filtration was repeated 3 times until the filtrate was pH test paper 6-7. The obtained powder was left to stand overnight in a dryer set at 110 ° C. and dried to obtain a material showing a main signal and two sub-signals having the same g value as shown in the middle part of FIG.

Reference Example 6 Titanium tetrachloride (23 k) was added to 207 kg of water having a temperature of 0 ° C. filled in a 300-liter reaction vessel (which can be cooled and stirred).
g was added slowly. At this time, the maximum temperature of the aqueous solution is 6 ° C
Met. Titanium chloride was stirred for 2 days to prepare a transparent titanium tetrachloride aqueous solution. 12.5% ammonia water was dropped while stirring the prepared titanium tetrachloride aqueous solution, and this solution gradually became cloudy. The amount of ammonia water was adjusted so that the cloudy solution had a pH of 8. The cloudy solution was subjected to suction filtration. The white precipitate remaining on the filter paper was 131 kg. 200 kg of white precipitate
After dispersing in ammonia water (6% as NH ₃ ) of
After stirring for 24 hours, suction filtration was performed. The white precipitate after filtration was 108 kg. The white precipitate was put in a forced air type shelf dryer set at 50 ° C. and dried for 4 days. The sample after drying was 17 kg. 1 kg of the dried sample was put into an alumina crucible (20 × 20 × 5 cm), placed in a gas furnace, a thermocouple was placed on the surface of the sample, and the sample was baked at a temperature of 400 ° C. for 1 hour. After cooling
A deep yellow material with a major signal and two minor signals with g-values similar to those shown in the middle of Figure 1 was obtained. This material was ground in a mortar and used for the evaluation described below.

Reference Example 7 3 g of the powder prepared in Reference Example 6 was suspended in 100 ml of pure water and stirred for 1 hour using a magnetic stirrer. The obtained solution was suction filtered. The sample remaining on the filter paper was again stirred in pure water and suction-filtered. Filtration was repeated 3 times until the filtrate became 6 to 7 with pH test paper. The obtained powder was left to stand in a dryer set at 110 ° C. for a whole day and night to be dried, and shown in the middle part of FIG. 1. A material was obtained showing a major signal and two minor signals with a g value similar to.

Reference Example 8 240 mL of pure water was prepared in a 1 L beaker. To this, 60 g of Kishida Chemical Titanyl Sulfate (product number 020-78905) was added, and dissolved by stirring with a lab mixer. Next, 55 mL of Kanto Kagaku (special grade) ammonia water was added to this aqueous solution to obtain a hydrolyzed precipitate. The obtained precipitate was suction filtered to separate a white solid content (precipitation cake). Furthermore, this cake was rinsed with 1.0 L of pure water three times (by the procedure of adding just before breaking the cake) with a total of 3.0 L, and filtered and washed. Finally, filter cake until the filtrate does not come out at 110 ℃, 12
Dried in time and ground in a mortar. The white powder was calcined in air at 400 ° C. for 1 hour to obtain a yellow material showing a main signal and two sub-signals having the same g value as shown in the middle part of FIG.

[0073]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a novel photoresponsive composite material which responds to visible light and has adsorptivity, and a coating material and a fibrous substance containing the composite material. A coating film formed using a coating material containing the visible light responsive composite material of the present invention and an article having this visible light responsive coating film, and a fibrous substance is a photocatalyst, an optical sensor, a material for a photovoltaic cell, a photofouling material. It is also useful as a photo-hydrophilic material, photo-bacteriostatic material, photo-hydrophilic material and the like.

[Brief description of drawings]

FIG. 1 is an ESR spectrum of a visible light responsive titanium oxide used in the present invention (Reference Example 1) measured at 77K in vacuum. The upper part is the spectrum in the dark, and the middle part is 420.
Light having a wavelength of not less than nm (of the light of the mercury lamp, 42
It is a spectrum under irradiation with light of less than 0 nm (cutoff), and the lower part is a spectrum when irradiation with light of a mercury lamp is performed without cutting off light of less than 420 nm.

FIG. 2 is an ESR spectrum of the visible light-responsive titanium oxide (Reference Example 1) used in the present invention measured in vacuum at room temperature.
The upper part is the spectrum in the dark, and the middle part is 420 nm.
Light having the above wavelength (420n of the light of the mercury lamp)
The spectrum under irradiation with light of less than m is cut off), and the lower part is the spectrum under irradiation with light of a mercury lamp without cutting off light of less than 420 nm.

FIG. 3 shows the product of Reference Example 1 (upper row) and a hydrolyzate (5).
It is the measurement result of XRD of 0 degreeC dry) (lower part).

[Fig. 4] Measurement atmosphere in vacuum (upper), in air (middle)
Alternatively, it is an ESR spectrum measured under the condition that light is irradiated through a filter (L-42) that cuts light of 420 nm or less (using a 500 W high-pressure mercury lamp) with isopropanol (lower stage).

FIG. 5: ESR spectrum of the product obtained in Reference Example 4 measured under light irradiation through a filter (L-42) that cuts off light of 420 nm or less (using a 500 W high-pressure mercury lamp) ( The measurement temperature is 77K).

FIG. 6 is an SEM photograph of the composite material obtained in Example 1 (50
00 times and 20000 times).

FIG. 7 is an SEM photograph (5,000 times and 20,000 times) of commercially available apatite-coated titanium oxide (manufactured by Showa Denko).

FIG. 8 is an SEM photograph (5,000 times and 20,000 times) of titanium oxide having a visible activity produced in Reference Example 8.

9 is an X-ray crystal diffraction test result of the composite material obtained in Example 1 (upper part) and the titanium oxide having visible activity (lower part) produced in Reference Example 8 used as a raw material. FIG.

FIG. 10 shows the measurement results of Ti of the composite material obtained in Example 1 by X-ray electron spectroscopy.

11 shows the measurement results of Ca of the composite material obtained in Example 1 by X-ray electron spectroscopy.

FIG. 12 shows the measurement results of P 2 of the composite material obtained in Example 1 by X-ray electron spectroscopy.

FIG. 13 shows absorption spectra of the composite material obtained in Example 1 (upper part) and the titanium oxide with visible activity (lower part) produced in Reference Example 8 used as a raw material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09C 3/06 C09C 3/06 4L031 C09D 1/00 C09D 1/00 201/00 201/00 D06M 11/46 D06M 11/12 (72) Inventor Kintaka Ando 2-8-4 Nishishinbashi, Minato-ku, Tokyo F-term (reference) within Eco Device Co., Ltd. (reference) 4F100 AA04B AA04H AA20B AA20H AS00B AT00A BA02 BA10A BA10B CC00B DE01B DE01H GB90 JL08 J02 YY00B 4G066 AA11B AA23D AA50B BA31 BA36 CA02 CA28 DA03 DA08 FA11 FA28 GA18 4G069 AA03 BA04A BA04B BA48A BB14A BB14B BC09A BC09B CA07 CA13 HA4562 001 001 221 KA08 NA19 4L031 BA09 BA18 CA00 DA00

Claims (13)

[Claims] 1. A composite material in which at least a part of the surface of visible light responsive titanium oxide is coated with calcium phosphate. 2. The composite material according to claim 1, wherein the visible light responsive titanium oxide is titanium dioxide having stable oxygen defects. 3. The visible light responsive titanium oxide is titanium oxide containing at least anatase titanium oxide, and g value in ESR measured under vacuum at 77K under irradiation with light having a wavelength of 420 nm or more. Is 2.0
The main signal is 04 to 2.007 and the g value is 1.985.
Two side signals, ˜1.986 and 2.024, are observed, and these three signals are
K, the composite material according to claim 1 or 2, which is a visible light responsive photocatalyst that is minutely observed or substantially not observed in the dark. 4. The visible light responsive titanium oxide has a wavelength of 42.
The composite material according to any one of claims 1 to 3, which is responsive to the action of light having a wavelength of 0 nm or more. 5. The composite material according to claim 1, which is in the form of particles. 6. In the X-ray crystal diffraction test method, when the intensity of the peak due to anatase type titanium dioxide between 23 ° and 27 ° is 100, it is 30 ° to 35 °.
The composite material according to any one of claims 1 to 5, wherein the intensity of a peak due to calcium phosphate between 1 and 2 is 1 to 30. 7. In the X-ray crystal diffraction test method, when the intensity of the peak due to anatase type titanium dioxide between 23 ° and 27 ° is 100, it is due to calcium phosphate between 30 ° and 35 °. The composite material according to any one of claims 1 to 5, wherein the intensity of the peak is 1.5 to 10. 8. In the X-ray crystal diffraction test method, when the intensity of the peak due to anatase type titanium dioxide between 23 ° and 27 ° is 100, it is due to calcium phosphate between 30 ° and 35 °. The peak intensity is 2
10. The composite material according to any one of claims 1 to 5, which is 10. 9. In the measurement by X-ray electron spectroscopy, Ti and
The area attributed to 2p of Ca and 2p of P is 1 to 30 when the area ratio of Ca and P to the element 2p of Ti is 100. 9. The composite material according to the item. 10. The composite material according to claim 1, wherein at least a part of the calcium phosphate coated on the surface of titanium oxide is submicron particles or columns. 11. A coating material containing the composite material according to claim 1. 12. The paint according to claim 11, wherein the paint contains an organic binder or an inorganic binder. 13. A fibrous substance containing the composite material according to any one of claims 1 to 10.