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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/39—Photocatalytic properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8926—Copper and noble metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0215—Coating
  • B01J37/0219—Coating the coating containing organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G23/00—Compounds of titanium
  • C01G23/04—Oxides; Hydroxides
  • C01G23/047—Titanium dioxide
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/10—Heat treatment in the presence of water, e.g. steam
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/50—Solid solutions
  • C01P2002/52—Solid solutions containing elements as dopants
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
  • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/80—Compositional purity
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
  • Y10S502/50—Stabilized
  • Y10S502/501—Stabilized for multi-regenerability

Definitions

• the present invention relates to a photocatalytic titanium oxide sol that exhibits antibacterial properties in some places, and in particular, even when silver is contained, a stable photocatalytic titanium oxide sol that does not cause discoloration by light, and a coating composition using the same. It relates to objects and members.
• Titanium oxide is known to have a photocatalytic effect that exhibits a redox action when irradiated with ultraviolet rays, decomposes harmful substances, exhibits antibacterial properties, and superhydrophilic phenomena. Development of industrial products using them is actively underway. Since the photocatalytic reaction is a reaction in the vicinity of the surface of titanium oxide, a titanium oxide sol composed of fine particles of titanium oxide, which is often used in the form of a thin film, is widely used as a thin film forming material. By the way, since the photocatalytic effect of titanium oxide is manifested by the energy of light as the name suggests, the effect is limited only when irradiated with light such as sunlight or an ultraviolet lamp!
• the antifouling property due to the superhydrophilicity even if the ultraviolet ray is not continuously irradiated, the external contamination on the film surface having the photocatalytic function can be removed by intermittent irradiation. Also, in the decomposition of harmful substances, if the substance does not increase naturally, the decomposition gradually proceeds by intermittent light irradiation. However, with regard to antibacterial and deodorizing effects, the fungus odor grows and expands while the photocatalytic effect is not manifested, so continuous UV irradiation is necessary to maintain the effect.
• an antibacterial agent other than a photocatalyst is used as a photocatalyst. It is the easiest and simplest method to use together.
• antibacterial agents include metals such as silver, copper, and zinc, and many industrial products have been developed that exhibit antibacterial properties by causing them to exist on the surface of the substrate.
• the effect of such an antibacterial metal can also be used in a photocatalyst.
• a photocatalytic film containing titanium oxide is prepared in advance, and a photocatalytic effect is obtained by applying an antibacterial metal-containing compound, such as an aqueous solution of various salts of silver and copper, to the surface, followed by heat treatment or reduction treatment. It is possible to form a film imparted with antibacterial properties by metal ions and to exert antibacterial properties at certain places. However, it is clear that this method increases the number of coating and drying steps, which increases costs.
• a coating film is obtained by applying and drying one kind of chemical solution containing a photocatalyst and an antibacterial metal at a time.
• the ability to mix antibacterial metals such as silver and copper into a film-forming material containing a photocatalyst is exempted.
• titanium oxide sol is preferably used as the coating film forming material, and silver and copper may be mixed in the form of a nitrate aqueous solution.
• an aqueous solution of silver nitrate is added to the trade name titanium oxide sol STS-01 (Ishihara Sangyo Co., Ltd.) stabilized with nitric acid, it is apparently stable for a while after the addition of silver nitrate.
• the silver component is reduced and the sol turns from yellow to brown, and eventually the silver component is precipitated. If precipitation occurs in the sol, the coating film cannot be formed stably, and the precipitate may cause defects in the appearance after application, or the antibacterial effect may vary.
• the present inventors have intensively studied a method for producing a titanium oxide sol having a photocatalytic ability containing an antibacterial metal having excellent storage stability.
• an inorganic colloid antibacterial agent one or more types of antibacterial properties selected from the colloidal particles of negatively charged inorganic oxides selected from silver, copper, zinc, tin, lead, bismuth, cadmium, chromium and mercury
• An antibacterial agent comprising an antibacterial inorganic oxide colloid solution to which a metal component is attached is disclosed. (See Patent Document 2)
• Patent Document 2 the description of TiO is an example of a support for an antibacterial agent, which is not intended to impart a certain force photocatalytic activity. Further, in Patent Document 2, when a combination of titanium, zirconium, and zinc components is used, these components act as an ultraviolet absorber, and there is an effect of preventing discoloration of the silver component. The force described is exactly the opposite when the titanium is a photocatalytic titanium oxide sol, which is much faster than the amorphous titanium oxide sol without photocatalytic activity due to the strong redox power of the photocatalyst. Discoloration is observed.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2002-68915
• Patent Document 2 JP-A-6-80527
• the photocatalytic titanium oxide sol of the present invention is characterized by containing silver and copper, and quaternary ammonium hydroxide.
• the photocatalytic titanium oxide sol is characterized by a color quality index A L value of 10 or less by light irradiation with a wavelength threshold of 300 to 400 nm.
• silver is added as Ag O / TiO to titanium oxide.
• the ratio of copper to silver is 1 to 30 as CuO / AgO (mass ratio).
• tetramethyl ammonium hydroxide is used as the quaternary ammonium hydroxide.
• the amount of quaternary ammonium hydroxide is titanium oxide (Ti
• O is characterized by 0 ⁇ 01-0.1 mole per mole.
• a preferred embodiment of the photocatalytic coating composition of the present invention is to disperse the photocatalytic titanium oxide sol in a binder.
• the surface of the base material is coated with the photocatalyst coating composition.
• the photocatalytic titanium oxide sol of the present invention is characterized by little discoloration due to light irradiation and very little gelation or thickening despite containing photocatalyst titanium oxide and silver as an antibacterial metal. It is.
• the use of the photocatalytic titanium oxide sol of the present invention in combination with these ultraviolet sterilizers, etc. can be achieved with the ability S to obtain a more effective antibacterial effect.
• Titanium oxide of the photocatalytic titanium oxide carre of the present invention comprises anatase-type or rutile-type crystals having a photocatalytic effect and a mixture thereof, and at least the sol is dried. What the powder X-ray diffraction of the resulting powder is clearly identified as anatase or rutile! Such an anatase-type or rutile-type titanium oxide is indispensable as a titanium oxide constituting the sol of the present invention because it exhibits high photocatalytic performance.
• the concentration of the photocatalytic titanium oxide sol can be adjusted by an ordinary operation such as concentration, but is preferably in the range of 3 to 15% by mass as TiO.
• the coating tends to become too thin when applied to a substrate, and the effect tends to be low. In some cases, multiple applications are required, which is not productive.
• the upper limit is exceeded, the operability tends to deteriorate due to, for example, an increase in the sol viscosity.
• non-ionized forms such as oxides and hydroxides are preferred.
• silver content in the sol of the present invention it is recommended that silver is in the range of 0.;! To 5% by mass, more preferably in the range of ! to 3% by mass as Ag O / TiO with respect to titanium oxide. The Below the lower limit, the antibacterial effect of silver cannot be expected, and above the upper limit, it becomes difficult to stably disperse in the sol.
• the quaternary ammonium hydroxide is one of the essential components for stabilizing the photocatalytic titanium oxide sol of the present invention.
• alkaline compounds such as ammonia and primary-tertiary amines are all known to be a component that stabilizes the sol of strong titanium oxide itself, while these alkaline compounds such as silver There is a tendency to dissolve antibacterial metals.
• quaternary ammonium hydroxide As a result of intensive studies, the present inventors have solved the above problem by using quaternary ammonium hydroxide as a sol dispersion stabilizer. That is, it was found that quaternary ammonium hydroxide hardly dissolves the antibacterial metal, and thus tends to suppress discoloration of the antibacterial metal while stabilizing the titanium oxide sol.
• the quaternary ammonium hydroxide used in the present invention include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetraptylammonium hydroxide. In particular, tetramethylammonium hydroxide is stable per se and can be easily obtained, so that it is suitable as a stabilizer for the sol of the present invention.
• the content of the quaternary ammonium hydroxide is preferably in the range of 0.01 to 0.1 mol per mol of titanium oxide (TiO 2) in order to stabilize the sol.
• Hydroxy quaternary ammonium can stabilize the titanium oxide sol as long as it is above the lower limit, while adding more than the upper limit will not significantly degrade the sol stability! / Since the fourth ammonium dissolves a little antibacterial metal, it is not preferable to use it in large quantities.
• the discoloration of silver in the photocatalytic titanium oxide sol is further suppressed in the presence of copper in addition to the above-mentioned fourth ammonium hydroxide.
• the form of copper in the sol is unknown, but the added material form does not contain nitrate ions or chloride ions that destabilize the sol, such as oxides and hydroxides! .
• the ratio of copper to silver is in the range of 1 to 30, preferably 1 to 10 as CuO / Ag 2 O (mass ratio). In other words, copper must be used at least in the same amount as silver, and if it falls below the lower limit, the copper discoloration suppressing effect is extremely reduced. Moreover, even if copper is added exceeding the upper limit, there is no corresponding discoloration suppressing effect.
• the photocatalytic titanium oxide sol of the present invention is a titanium oxide sol containing silver and copper and quaternary ammonium hydroxide, and can greatly suppress the discoloration of silver.
• the present invention is characterized in that the color quality index AL value by light irradiation with a wavelength threshold of 300 to 400 nm is 10 or less.
• the color quality index A L value if the A L value exceeds 10, the discoloration is large and the commercial value is significantly reduced.
• titanium salt used in the present invention examples include titanium chloride and titanium sulfate.
• the sol of the present invention uses a titanic acid gel obtained by neutralizing and decomposing these titanium salts with aqueous ammonia as a starting material. Can be used. Although the applicants have already disclosed that these gels can be hydrothermally treated at a temperature of 100 ° C. or higher to obtain titanium oxide sols having anatase-type crystallites, the production of the photocatalytic titanium oxide sol of the present invention has been already disclosed. With respect to the method, (1) a method in which silver and copper oxides or hydroxides are added to titanic acid gel, followed by hydrothermal treatment, followed by addition of quaternary ammonium hydroxide.
• Quaternary ammonium hydroxide on titanic acid gel A method in which silver and copper oxides or hydroxides are added after hydrothermal treatment after adding only nitrogen. (3) A method in which an oxide or hydroxide of silver and copper and a quaternary ammonium hydroxide are simultaneously added to a titanic acid gel, followed by hydrothermal treatment. (4) A method of adding silver and copper oxides or hydroxides and quaternary ammonium hydroxide after hydrothermally treating the titanic acid gel. It is possible to illustrate S etc. As in (1) and (3), it is possible to suppress discoloration of silver by hydrothermal treatment in the presence of silver and copper oxides or hydroxides.
• the photocatalytic titanium oxide sol of the present invention is a sol composed of titanium oxide with greatly reduced discoloration, and is a sol that exhibits an excellent effect as a thin film forming material for interior materials with an emphasis on designability. It can be used not only in certain places but also in various applications that expect photocatalytic effects
• a photocatalytic member can be produced by applying the photocatalytic titanium oxide sol of the present invention as it is to the surface of various substrates. Further, a photocatalytic member can be produced by arbitrarily adding a binder as necessary to obtain a photocatalytic coating composition and applying it to the surface of various substrates.
• the binder material added to the photocatalytic titanium oxide sol of the present invention is not particularly limited, and may be an organic binder or an inorganic binder.
• organic binder examples include polyester resin, PVA resin, polyethylene PVA copolymer resin, butyl acetate resin, urethane resin, acrylic resin, acrylic urethane resin, acrylic styrene resin, acrylic silicone resin, and chlorinated vinyl resin. It is done.
• inorganic binders include zirconium compounds, silicon compounds, and aluminum compounds.
• zirconium compounds include zirconium tetrachloride, zirconium zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium acetate, carbon Zirconium salts such as zirconium acid, zirconium alkoxides such as tetraethoxyzirconium, tetra-i-propoxyzirconium, tetra- n -butoxyzirconium, tetra-t-butoxyzirconium, and the like.
• silicon compound examples include alkali silicates such as sodium silicate, potassium silicate, lithium silicate, cesium silicate, and rubidium silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltrichlorosilane, methyltriisopropoxysilane. , Methyltri-t-butoxysilane, etyltrimeth
• Examples include silanol which is a product.
• Aluminum compounds include aluminum lactate, aluminum phosphate, aluminum salts such as aluminum chloride, triethoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum, tri-t-butoxyaluminum.
• aluminum alkoxides such as aluminum alkoxides.
• additives other than the binder include a pigment component for coloring the coating composition, a silica component for imparting hydrophilic performance to the coating film, storage stability of the coating composition, and the like.
• examples of additives that can be added to the coating composition include a pigment component for coloring the coating composition, a silica component for imparting hydrophilic performance to the coating film, storage stability of the coating composition, and the like.
• examples include thickeners, antifoaming agents, and dispersants for maintaining good workability.
• the substrate to which the photocatalyst coating composition is applied is not particularly limited, but when the substrate is a heat-resistant substrate such as metal or ceramics, for example, tile, the photocatalyst coating composition is applied to the surface. It can be heated and dried after coating, and the photocatalyst-containing film formed on the surface of the substrate strongly adheres to the substrate. Further, when the base material is a heat-sensitive material or an existing wall surface, it is preferable to apply a photocatalyst coating composition containing a binder curable at room temperature to the surface.
• % means “% by mass”.
• the method of measuring the color quality index ⁇ L value and the method of the antibacterial test are defined as follows.
• Adjust the concentration of silver-containing photocatalytic titanium oxide sol so that Ag 0 0.05%, and dispense 30 g into a 50 ml glass sample bottle.
• the sample bottle was set on a shaker and set so that the surface of the container was lmW / cm 2 (365 nm) under 20 W type black light irradiation.
• a) Normal bouillon medium with 1/500 concentration (hereinafter referred to as 1 / 500NB) To 1000ml of purified water, extract 3g of meat extract, 10g of peptone, 5g of sodium chloride and 5g of sodium chloride in a flask. Mix well and dissolve the contents sufficiently, then adjust to pH 7.1 ⁇ 0.1 (25 ° C) with sodium hydroxide solution or hydrochloric acid solution. Dilute it 500 times with purified water, adjust with sodium hydroxide solution or hydrochloric acid solution to pH 6.7 to 7.2 (25 ° C), and dispense into test tubes or Erlenmeyer flasks as necessary. Then, put on a cotton plug and pasteurize with high-pressure steam.
• 1 / 500NB Normal bouillon medium with 1/500 concentration
• the ultraviolet irradiation intensity is measured by installing the UV illuminometer light receiving unit on the floor of the light irradiation device, placing the film and glass plate used for the test on the light receiving unit, and reading the indicated value. Determine the position where the specified UV illuminance can be obtained, and set it as the test piece installation position.
• the test specimen inoculated with the test bacterial solution is irradiated with the test petri dish containing the test bacterial solution covered with a moisturizing glass or a cover of the storage dish and kept at a temperature of 25 ⁇ 5 ° C. Illuminate with light.
• test piece use a flat part of a flat sample cut into a square of 50 ⁇ 2 mm square (within 10 mm in thickness). (9 test specimens that have not been photocatalytically antibacterial processed and 6 test specimens that have been photocatalyzed antibacterial processed are prepared.) Washing of the test specimens can be accomplished by using a local gauze or ethanol gauze that absorbs ethanol on the entire surface of the test specimen. Lightly wipe with absorbent cotton 2-3 times and dry thoroughly.
• 1 platinum ear is transferred from a stock strain to a nutrient agar medium and cultured at a temperature of 37 ⁇ 1 ° C for 16 to 24 hours.
• 1 platinum loop of this culture is transferred to a new nutrient agar medium and cultured at 37 ⁇ 1 ° C for 16-20 hours.
• the amount of 1 platinum loop of the pre-cultured test strain is uniformly dispersed in a small amount of 1 / 500NB, and the number of bacteria is measured by direct observation with a microscope.
• This bacterial solution is appropriately diluted with 1 / 500NB and prepared so that the number of bacteria is about 6.7 x 10 5 to about 2.6 x 10 6 cells / ml.
• To do. [0036]
• For inoculation of the test bacterial solution accurately collect the test bacterial solution with a pipette and drop it on each test piece. Cover the dropped test bacteria solution with a sticky film and lightly press the test solution so that it does not spill from the edge of the sticky film so that it reaches the entire adherent film. Place the glass.
• the number of bacteria is measured by a pour plate culture method using a 10-fold dilution method. Remove 1 ml of the washing solution with a sterilized pipette, add it to a test tube containing 9 ⁇ 0.1 ml of physiological saline, and stir well. In addition, take 1 ml from this tube with a new pipette, add it to another tube containing 9 ⁇ 0. 1 ml of physiological saline, and stir well. Repeat this procedure one after another to prepare a dilution series by the 10-fold dilution method. Remove 1 ml of each dilution series from a test tube into two separate dishes with a new pipette and keep it at 45 to 48 degrees.
• the viable cell count can be obtained from the formula (Equation 2) from the bacterial concentration obtained from the equation (Equation 1).
• V Volume of SCDLP medium used for washing (ml)
• the number of colonies is ⁇
• the number of viable bacteria is displayed as ⁇ 10 (when V is 10ml) and the average value is calculated as "10". Also, when the number of colonies is less than 30 Calculate the number of viable bacteria using the measured number of colonies.
• the antibacterial activity values R and R and the effect of light irradiation are based on the number of viable bacteria determined by the formula (Equation 2) and
• RL Antibacterial activity value of photocatalyst antibacterial processed product under UV irradiation condition
• A Average number of viable bacteria immediately after inoculation of test piece not processed with photocatalyst antibacterial (individual)
• B L Test piece not processed with photocatalyst Average number of viable bacteria after light irradiation for a predetermined time under UV irradiance condition L
• A Average number of viable bacteria immediately after inoculation of test pieces not processed with photocatalytic antibacterial
• ⁇ Average number of viable bacteria after keeping test specimens without photocatalytic antibacterial treatment in the dark for a specified time (individual: '
• C D The average value of the number of pieces after storing the photocatalyst antibacterial processed specimen in the dark for a predetermined time
• tetramethylammonium hydroxide is 0.03 mol per 1 mol of titanium oxide (Ti ⁇ ).
• Example 2 the test was conducted under exactly the same conditions except that 0.6 g of copper hydroxide was not added, and the color quality index AL value of the obtained sol was determined to be 12.33.
• Example 2 the test was conducted under exactly the same conditions except that 0.6 g of copper hydroxide was not added, and the color quality index AL value of the obtained sol was determined to be 12.33.
• the color quality index ⁇ L value was calculated to be 2 ⁇ 24.
• each sol of the present invention was observed after being allowed to stand at room temperature for 1 month. In all cases, no precipitation was observed, and the sols were stable.
• Ag ′ 2 0 (%;) and Cu 2 O (%) indicate the ratio to Ti 0 2 .
• the photocatalytic titanium oxide sol obtained in Example 1 was mixed and stirred with an alkali silicate and water to obtain a photocatalytic coating composition.
• the composition of the photocatalyst coating composition is as follows.
• the ratio of TiO to SiO in the coating composition should be 1 to 3, and the coating composition should be solid.
• the form concentration was 0.5%.
• This coating composition was spray-applied to glazed tiles, dried by heating at 800 ° C. for 1 minute, and cut into 50 mm squares as antibacterial test samples.
• the antibacterial test was conducted under the conditions shown in Table 2, the antibacterial activity value was 4.3 for R and 2.5 for R.
• the ratio of TiO and acrylic resin in the coating composition should be 1: 200.
• the solid content concentration of the product was 50%.
• One roller of this coating composition was applied to an aluminum substrate, dried at room temperature for 7 days, and cut into 50 mm squares as antibacterial test samples. When the antibacterial test was conducted under the conditions shown in Table 2, R was 4.0.

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