WO2003068871A1 - Compositions servant a creer un film photocatalytique et substrat pourvu de ce film photocatalytique - Google Patents

Compositions servant a creer un film photocatalytique et substrat pourvu de ce film photocatalytique Download PDF

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Publication number
WO2003068871A1
WO2003068871A1 PCT/JP2003/001508 JP0301508W WO03068871A1 WO 2003068871 A1 WO2003068871 A1 WO 2003068871A1 JP 0301508 W JP0301508 W JP 0301508W WO 03068871 A1 WO03068871 A1 WO 03068871A1
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WO
WIPO (PCT)
Prior art keywords
composition
forming
photocatalyst
photocatalyst film
substrate
Prior art date
Application number
PCT/JP2003/001508
Other languages
English (en)
Japanese (ja)
Inventor
Takashige Yoneda
Yasuhiro Sanada
Manami Miyamoto
Akemi Kato
Original Assignee
Asahi Glass Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Priority to JP2003567988A priority Critical patent/JP4292992B2/ja
Priority to AU2003211967A priority patent/AU2003211967A1/en
Publication of WO2003068871A1 publication Critical patent/WO2003068871A1/fr

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Classifications

    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates

Definitions

  • the present invention relates to a photocatalyst film-forming composition capable of forming a photocatalyst film on the surface of various substrates, a photocatalyst film formed from the composition, and a substrate with a photocatalyst film having the photocatalyst film.
  • a method of forming a photocatalyst film using a coating composition containing a photocatalyst and silica is also known (for example, Japanese Patent No. 2756474).
  • the film using the above-described method using the silicon force has problems that the hydrophilicity is inferior and the soil decomposability is low.
  • the present invention has been made to solve the above problems, and provides a composition for forming a photocatalyst film capable of imparting excellent hydrophilicity to the surface of a substrate, and in particular, forming a photocatalyst film having excellent soil decomposability.
  • An object is to provide a photocatalyst film formed and a substrate with the photocatalyst film.
  • the present invention provides a photocatalyst film-forming composition capable of forming a photocatalyst film having a long hydrophilicity duration and excellent abrasion resistance on the surface, a photocatalyst film formed from the composition, and a substrate with the photocatalyst film. Aim. Disclosure of the invention
  • the present invention provides a composition for forming a photocatalytic film, which essentially includes photocatalytic semiconductor fine particles, the following silica precursor and a medium.
  • Silica precursor a silicate compound containing 0.001-1 to 1 part by mass of an alkali metal ion with respect to 100 parts by mass of a silicate.
  • the present invention provides a photocatalyst film formed on a surface of a substrate from a composition for forming a photocatalyst film, and a substrate with a photocatalyst film having the photocatalyst film.
  • FIG. 1 is a schematic cross-sectional view showing an example of a substrate with a photocatalytic film of the present invention.
  • the photocatalytic semiconductor fine particles according to the present invention are such that when irradiated with light having an energy larger than the energy difference between the valence band and the conduction electron band of the photocatalyst, the conduction electrons and the positive electrons are excited by the excitation of the electrons in the valence band.
  • Preferred examples of such photocatalytic semiconductor fine particles include anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, tungsten trioxide, ferric oxide, and strontium titanate.
  • the average particle diameter of the photocatalytic semiconductor fine particles in the present invention is obtained by measuring the agglomerated particle size of the fine particles in the composition using light scattering using a Microtrac UPA particle size distribution meter (manufactured by HONE YWE LL), It is preferably from 5 to 90 nm, particularly preferably from 40 to 70 nm. If the average particle size is too small, various effects of the photocatalyst are hardly exhibited because the photocatalyst fine particles are buried in the formed photocatalytic film. If the average particle diameter is too large, the mechanical strength of the formed photocatalyst film may be insufficient, and transparency may not be ensured.
  • the silica precursor in the present invention is a silicic acid compound containing 0.001 to 1 part by mass of an alkali metal ion with respect to 100 parts by mass of a citric acid. It is preferably contained in an amount of from 0.2 to 0.2 parts by mass, and particularly preferably from 0.01 to 0.15 parts by mass.
  • the alkali metal ion concentration was measured by ICP emission spectrometry using, for example, SPS400 manufactured by Seiko Instruments Inc. There is no particular limitation on the alkali metal ion, and one type may be used or two or more types may be used.
  • alkali a As the metal ion a sodium ion or a lithium ion is preferable.
  • the silicate compound means a compound that forms a silica film by performing a post-treatment as described below.
  • the silylation precursor is preferably a product obtained by removing a portion of the metal ion from the alkali metal salt of caieic acid.
  • the product can be obtained, for example, by a method of reducing the alkali metal ion from the alkali metal salt of keic acid using a cation exchange resin. By controlling the amount of cation exchange resin used, contact time, contact method, etc., the amount of metal ions to be reduced can be adjusted.
  • the cation exchange resin a strongly acidic cation exchange resin (RS0 3 H type), although weakly acidic cation exchange resin (RCOOH type), and the like can be used, the use of strongly acidic cation exchange resin is a reaction rate It is preferred in that respect.
  • the concentration of metal ions is preferably 1 to 80 ppm in terms of mass relative to the composition for forming a photocatalyst, and particularly preferably 1 to 40 ppm. More preferably, it is 1 to 20 ppm. If the concentration of the alkali metal ion is too low, the stability and hydrophilicity of the composition decrease, and if it is too high, the stability of the composition remarkably decreases.
  • alkali metal salt of the caiic acid examples include one or more selected from the group of sodium silicate, lithium silicate, potassium silicate, and the like, with sodium silicate and Z or lithium gayate being particularly preferred.
  • the sodium gay acid, S i O 2 ZN a 2 ⁇ composition ratio are known different materials can be used without particular limitation. Among them, a material having a small content ratio of Na 2 O is preferable.
  • Examples of commercially available sodium silicate include sodium silicate 1 (molar ratio of Si 2 / Na 20 : 2.0 to 2.3) (sodium silicate 1 is a trade name of Nippon Chemical Industry Co., Ltd.) Hereinafter, the same applies to Nos. 2 to 4.), Sodium gayate No. 2 (equivalent molar ratio: 2.4 to 2.7), Sodium silicate No. 3 (equivalent molar ratio: 3.0 to 3. 3) and Sodium Gayate No. 4 (equivalent molar ratio: 3.7-3.9).
  • sodium silicate 3 or 4 having a small content ratio of Na 2 ⁇ is particularly preferable.
  • lithium Kei acid Ri Contact known S I_ ⁇ 2 i 2 O composition ratios of different materials, it can be used without particular limitation. Among them, a material having a small Li 2 O content ratio is preferable.
  • Commercially available lithium silicates include lithium gayate 35 (S i 0 2 ZL i 2 ⁇ ⁇ molar ratio: 3.5) (Lithium silicate 35 is a trade name of Nippon Chemical Industry Co., Ltd., and the same applies to 45 and 75 hereinafter.), lithium silicate 45 ( Equimolar ratio: 4.5) and lithium silicate 75 (equimolar ratio: 7.5). In particular, L i 2 0 containing ratio smaller again Kei lithium 7 5 are particularly preferred.
  • the composition for forming a photocatalyst film of the present invention preferably contains a surfactant.
  • the surfactant has two main functions, the first is to ensure the wettability of the composition to the substrate, and the second is to make the photocatalytic film formed using the composition hydrophilic. It is to make sex higher.
  • the type of surfactant is not particularly limited, but a nonionic surfactant is preferably used from the viewpoint of liquid dispersion stability.
  • surfactant Q average molecular weight 800
  • a compound in which the hydrophilic part is polyoxyalkylene and the hydrophobic part is methylpolysiloxane (for example, product name: "L-177" manufactured by Nippon Tunicer Co., Ltd.) is preferable.
  • the silica precursor is preferably contained in an amount of 25 to 900 parts by mass, more preferably 50 to 400 parts by mass, based on 100 parts by mass of the photocatalytic semiconductor fine particles. Preferably, it is included.
  • the surfactant is preferably contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the photocatalytic semiconductor fine particles. The durability of the hydrophilicity of the obtained photocatalyst film is reduced, and if it is too small, the obtained photocatalyst film is not provided with hydrophilicity. Also, if the proportion of the surfactant is too large, the appearance of the obtained photocatalyst film is impaired, and the durability of the hydrophilicity is reduced. I do.
  • the composition for forming a photocatalyst film of the present invention contains a medium.
  • the medium is not particularly limited, is preferably a medium containing water, and may contain a solvent.
  • the solvent is used mainly for dilution, and the composition is preferably in the form of a solution.
  • the solvent is preferably a polar solvent such as a lower alcohol, a nitrogen-containing solvent, and a zeolite-containing solvent, and particularly preferably a lower alcohol. Two or more solvents may be used. Water is particularly preferred as the medium.
  • the total amount is preferably 0.5 to 50 parts by mass, more preferably 0. 0 to 50 parts by mass, per 100 parts by mass of the photocatalyst-forming composition, in consideration of the stability, economy and the like of the composition.
  • the amount is preferably from 5 to 15 parts by mass, particularly preferably from 0.5 to 5 parts by mass.
  • the composition for forming a photocatalyst film of the present invention may contain a functional additive.
  • the functional additive include coloring dyes, pigments, ultraviolet absorbers, antioxidants, and fine particles of oxide particles other than the photocatalytic semiconductor particles of the present invention (phosphorus pentoxide, magnesium oxide, etc., average particle diameter. Is preferably 20 O nm or less.) Are preferable.
  • the composition for forming a photocatalyst film of the present invention is applied to the surface of a substrate, a photocatalytic film is formed, and a substrate with a photocatalytic film is produced.
  • the silica precursor has been converted to silica, but a silanol group may remain partially.
  • a composition for forming a photocatalyst film is applied to the surface of a substrate using a known wet method, and as shown in FIG. 1, a photocatalyst film having a photocatalyst film 30 formed on a substrate 20 is provided.
  • a substrate 10 can be formed.
  • Preferred examples of the wet method include spray coating, brush coating, hand coating, spin coating, dip coating, coating by various printing methods, curtain flow, die coating, and flow coating.
  • the post-treatment After applying the composition for forming a photocatalytic film, it is preferable to perform a post-treatment for the purpose of removing the medium and increasing the hardness of the photocatalytic film.
  • the post-treatment include drying and heating at room temperature, irradiation with electromagnetic waves such as ultraviolet rays and electron beams, and heating.
  • the heating is preferably carried out at a temperature of 50 to 700 ° (in particular, at a temperature of 100 to 350 ° C for 5 to 60 minutes in consideration of the heat resistance of the base material.
  • a material having low heat resistance such as resin.
  • irradiation of electromagnetic waves such as ultraviolet rays and electron beams is performed. It is preferred to do so.
  • the thickness of the obtained photocatalyst film can be controlled by adjusting the concentration of the composition for forming a photocatalyst film, the type of solvent, the application conditions, the post-treatment conditions, and the like. If the photocatalytic film is too thick, the film may crack, create interference fringes, or be scratched. There is a disadvantage that the scratch is conspicuous, and if it is too thin, the desired photocatalytic performance may not be exhibited.
  • the thickness of the photocatalyst film is preferably from 10 to 30 nm, more preferably from 10 to 150 nm, in view of economy.
  • the substrate used in the present invention is not particularly limited.
  • the shape of the substrate is not limited to a flat plate, and may have a curvature over the entire surface or a part thereof.
  • the substrate used in the present invention is preferably a transparent substrate such as a glass or an organic resin.
  • the glass include soda lime glass mainly used for plate glass and automotive glass
  • the organic resin include resins such as polyacrylonitrile, acrylic, polyethylene, polypropylene, and polyethylene terephthalate. Is mentioned.
  • a silicone hard coat may be applied to the surface of the resin.
  • the visible light transmittance JISR 3106 (19 98 years)
  • the visible light transmittance is preferably 70% or more.
  • the substrate may be pretreated.
  • the pretreatment include a plasma treatment, a corona discharge, a UV treatment, a discharge treatment such as an ozone treatment, a chemical treatment using an acid or an alkali, a physical treatment using an abrasive, and the like.
  • pretreatments and posttreatments as described above greatly affect the performance of the obtained film, it is necessary to optimize each treatment condition.
  • the dehydration-condensation polymerization reaction can be advanced to promote the curing of the film, and the adhesion between the substrate surface and the composition can be improved.
  • the post-treatment can improve the adhesion to the substrate as described above, the pre-treatment is not essential. In some cases, pretreatment more than necessary may deteriorate the base material and lead to a decrease in performance.
  • the substrate with a photocatalyst film of the present invention is preferably used as an article for transportation equipment, an article for construction, and the like because its surface is excellent in hydrophilicity and excellent in transparency.
  • articles for transportation equipment include bodies of trains, automobiles, ships, and aircraft, window glasses, mirrors, cover plates for various display elements, and the like.
  • Building materials include exterior walls, sealants, window glass, Structures such as bridges and tunnels are exemplified.
  • Other uses include a cover glass for lighting, a sound insulating wall, and the like.
  • the substrate with a photocatalytic film of the present invention has an antifogging property such that water droplets adhering to the surface spread because the surface is excellent in hydrophilicity and the surface is not clouded.
  • organic soil is decomposed on the surface.
  • irradiation of the surface with light further improves the decomposition performance of organic soil.
  • dirt also flows down at the same time (self-cleaning effect).
  • the substrate with a photocatalytic film of the present invention can also be expected to have effects such as securing visibility, protecting aesthetics, and reducing maintenance costs.
  • the photocatalyst film formed from the composition for forming a photocatalyst film of the present invention is obtained by hydrolyzing S i (OR) 4 (R: alkyl group), which is a conventional alkoxysilane, to obtain S i O P (OH).
  • S i (OR) 4 R: alkyl group
  • another film may be provided between the substrate and the photocatalyst film.
  • the another film include, for example, an alkali barrier layer (when the substrate is an alkali metal-containing glass, a layer for preventing diffusion of the alkali metal into the photocatalyst film).
  • the contact angle is preferably 20 ° or less, more preferably 10 ° or less, from the viewpoint of maintaining hydrophilicity.
  • Oleic acid is applied to the sample immediately after preparation to form a dirty surface with a water contact angle of about 70 °, and a black light (center wavelength: 365 nm) of 0.5 mWZc is applied to the surface. After irradiation for 6 hours at an intensity of m 2 , the contact angle of water was measured. The contact angle is preferably 10 ° or less, more preferably 6 ° or less from the viewpoint of antifouling properties.
  • the sample was subjected to a Taber abrasion test (number of wear: 100, load: 4.9N.), And the haze value before and after the abrasion test was measured (measurement instrument name: Directly read haze computer manufactured by Suga Test Instruments Co., Ltd.). I asked.
  • the amount of change is preferably 3% or less from the viewpoint of wear resistance.
  • a soda-lime glass plate (10 OmmX 100 mm, thickness 3.5 mm) was prepared, its surface was polished with cerium oxide, washed with distilled water, and dried to obtain a pre-treated glass plate.
  • Kei sodium No.4 to 37. 5 g of water (trade name:. Nippon Chemical Industrial Co., Ltd. S i 0 2:. 23 35 wt%, Na 2 O:. 6. 29 wt% S i 0 2 / Na 2 The molar ratio of O: 3.83.;) was added, and a strongly acidic cation exchange resin (manufactured by Mitsubishi Chemical Corporation, trade name)
  • Example 3 To 32. lg of 2-propanol, add 10.5 g of photocatalyst A and 6.69 g of the desalted sodium silicate solution in Example 1, and further add "L-77" to 10 Op pm to obtain a coating solution 3 (sodium ion concentration: 7 ppm). A sample having a photocatalytic film having a thickness of 82 nm was obtained in the same manner as in Example 1 using the obtained coating liquid 3.
  • Example 1 instead of baking at 200 ° C for 60 minutes in air atmosphere, A sample was obtained by baking for 30 minutes at 3 o or: medium.
  • Example 1 instead of firing at 200 in the air atmosphere for 60 minutes, the sample was fired at 650 ° C for 5 minutes in the air atmosphere to obtain a sample.
  • Example 8 Using the obtained coating solution 8, a sample having a photocatalytic film having a thickness of 80 nm was obtained in the same manner as in Example 1.
  • a polycarbonate resin plate with a silicone hard coat (10 Omm X 10 Omm, thickness 5. Omm) was prepared, and the surface of the hard coat was washed with distilled water and then dried to obtain a pre-treated polycarbonate plate.
  • UV-C high-energy ultraviolet rays
  • Example 10 the polycarbonate resin plate with the silicone hard coat was washed and dried, and then irradiated with UV-C for 2 minutes using the low-pressure UV irradiator described above. A sample was obtained in the same manner as in Example 10, except that the substrate was a nate plate.
  • Example 10 instead of irradiating UV-C for 5 minutes, using a metal halide lamp (M03-L31, manufactured by FG Co., Ltd.) and setting the distance between the lamp and the resin plate to 10 cm, ultraviolet rays was irradiated for 5 minutes to obtain a sample having a photocatalyst film having a thickness of 80 nm.
  • the metal halide lamp here refers to a lamp with a wavelength of 300 to 450 nm, which emits longer wavelength ultraviolet light than a low-pressure mercury lamp.
  • the composition for photocatalyst film formation which can provide the outstanding hydrophilicity to the surface of a base material is obtained.
  • the photocatalytic film-forming composition of the present invention can be used to form a photocatalytic film having excellent hydrophilicity at a low temperature, and the surface of the substrate provided with the photocatalytic film has excellent hydrophilicity.
  • the photocatalyst film formed using the composition for forming a photocatalyst film of the present invention is particularly excellent in soil decomposability and has a long hydrophilicity duration. For this reason, the surface is always kept clean.
  • the surface of the substrate provided with excellent hydrophilicity, formed using the composition for forming a photocatalytic film of the present invention has excellent dripability, antifogging property, antifouling property, and abrasion resistance.
  • hydrophilicity by imparting hydrophilicity to the surface of the base material, water droplets adhering to the surface of the base material wet and spread, and the surface becomes cloudy.
  • the decomposition of dirt is further promoted by irradiation with light such as sunlight.
  • the dirt on the organic material also flows down (self-cleaning effect).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Compositions servant à créer un film photocatalytique, ce qui permet de conférer un caractère hydrophile excellent à la surface d'un substrat, en particulier, compositions servant à créer un film photocatalytique exerçant une action efficace de décomposition des taches et présentant une durée hydrophile optimisée. L'invention concerne également un substrat pourvu de ce film photocatalytique possédant des caractéristiques hydrophiles excellentes. Ces compositions contiennent en tant que constituants essentiels, un photocatalyseur (oxyde de titane), un précurseur spécifique de silice (composé d'acide silicique contenant 0,001 à une partie en masse d'un ion de métal alcalin pour 100 parties en masse d'acide silicique, par exemple, silicate de sodium, dans lequel la teneur en ions sodium a été réduite au moyen d'une résine échangeuse d'ions), et un véhicule.
PCT/JP2003/001508 2002-02-15 2003-02-13 Compositions servant a creer un film photocatalytique et substrat pourvu de ce film photocatalytique WO2003068871A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2003567988A JP4292992B2 (ja) 2002-02-15 2003-02-13 光触媒膜形成用組成物および光触媒膜付き基材
AU2003211967A AU2003211967A1 (en) 2002-02-15 2003-02-13 Compositions for forming photocatalytic film and substrate provided with photocatalytic film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002038409 2002-02-15
JP2002-38409 2002-02-15

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WO2003068871A1 true WO2003068871A1 (fr) 2003-08-21

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JP (1) JP4292992B2 (fr)
CN (1) CN1315955C (fr)
AU (1) AU2003211967A1 (fr)
WO (1) WO2003068871A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006070141A (ja) * 2004-09-01 2006-03-16 Asahi Glass Co Ltd 光触媒膜形成用組成物および光触媒膜付き基材
WO2006088022A1 (fr) * 2005-02-15 2006-08-24 Mitsui Chemicals, Inc. Photocatalyseur, procédé servant à produire celui-ci, dispersion liquide contenant le photocatalyseur et composition de revêtement de photocatalyseur
WO2007039984A1 (fr) * 2005-09-30 2007-04-12 Mitsui Chemicals, Inc. Matiere organique contenant un photocatalyseur

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100423832C (zh) * 2005-09-16 2008-10-08 长兴化学工业股份有限公司 复合光催化剂、其制造方法和含其的组合物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56149465A (en) * 1980-04-21 1981-11-19 Mitsui Toatsu Chem Inc Paint composition
JP2000303027A (ja) * 1998-12-04 2000-10-31 Toto Ltd 光触媒性親水性コーティング組成物
JP2000303055A (ja) * 1999-04-22 2000-10-31 Toto Ltd 光触媒性親水性被膜の親水性回復剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56149465A (en) * 1980-04-21 1981-11-19 Mitsui Toatsu Chem Inc Paint composition
JP2000303027A (ja) * 1998-12-04 2000-10-31 Toto Ltd 光触媒性親水性コーティング組成物
JP2000303055A (ja) * 1999-04-22 2000-10-31 Toto Ltd 光触媒性親水性被膜の親水性回復剤

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006070141A (ja) * 2004-09-01 2006-03-16 Asahi Glass Co Ltd 光触媒膜形成用組成物および光触媒膜付き基材
WO2006088022A1 (fr) * 2005-02-15 2006-08-24 Mitsui Chemicals, Inc. Photocatalyseur, procédé servant à produire celui-ci, dispersion liquide contenant le photocatalyseur et composition de revêtement de photocatalyseur
US7863215B2 (en) 2005-02-15 2011-01-04 Mitsui Chemicals, Inc. Photocatalyst, method for producing same, liquid dispersion containing photocatalyst and photocatalyst coating composition
WO2007039984A1 (fr) * 2005-09-30 2007-04-12 Mitsui Chemicals, Inc. Matiere organique contenant un photocatalyseur

Also Published As

Publication number Publication date
CN1315955C (zh) 2007-05-16
CN1633480A (zh) 2005-06-29
JP4292992B2 (ja) 2009-07-08
JPWO2003068871A1 (ja) 2005-06-02
AU2003211967A1 (en) 2003-09-04

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