WO2015133316A1 - Liquide de revêtement photocatalytique et film photocatalyseur l'utilisant - Google Patents

Liquide de revêtement photocatalytique et film photocatalyseur l'utilisant Download PDF

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Publication number
WO2015133316A1
WO2015133316A1 PCT/JP2015/055085 JP2015055085W WO2015133316A1 WO 2015133316 A1 WO2015133316 A1 WO 2015133316A1 JP 2015055085 W JP2015055085 W JP 2015055085W WO 2015133316 A1 WO2015133316 A1 WO 2015133316A1
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Prior art keywords
photocatalyst
film
resin
coating liquid
particles
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PCT/JP2015/055085
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English (en)
Japanese (ja)
Inventor
隆治 藤井
行治 宮原
亜由美 野本
健人 公文
光夫 中村
Original Assignee
株式会社鯤コーポレーション
東曹産業株式会社
住友商事ケミカル株式会社
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Application filed by 株式会社鯤コーポレーション, 東曹産業株式会社, 住友商事ケミカル株式会社 filed Critical 株式会社鯤コーポレーション
Priority to JP2015512432A priority Critical patent/JPWO2015133316A1/ja
Priority to CN201580011555.9A priority patent/CN106133078A/zh
Priority to KR1020167026959A priority patent/KR20170016317A/ko
Publication of WO2015133316A1 publication Critical patent/WO2015133316A1/fr

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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • B01J21/063—Titanium; 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/33—Electric or magnetic 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group 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
    • 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
    • B01J23/72—Copper

Definitions

  • the present invention relates to a photocatalyst coating solution and a photocatalyst film using the same, and particularly to a visible light responsive photocatalyst coating solution and a photocatalyst film using the same.
  • Patent Document 1 discloses an antifouling photocatalytic film in which hydrophilicity and an organic substance decomposition function are imparted to the surface of a substrate.
  • This antifouling photocatalyst film is obtained by subjecting one side of a photocatalyst film base material to a hydrophilic treatment and applying an aqueous antifouling agent (second coating layer), preferably the above aqueous antifouling agent Is a photocatalyst made of anatase-type titanium oxide, and further, an intermediate layer (first coating layer) is provided between the surface of the photocatalyst film substrate subjected to hydrophilic treatment and the antifouling agent (second coating layer). Is provided. JP 2003-306563 A
  • an object of the present invention is to provide a photocatalyst coating liquid under conditions that avoid the above-mentioned problems and a photocatalyst film using the same.
  • the photocatalyst coating liquid of the present invention is Nano-order size photocatalyst particles, A negatively charged substance having a zeta potential of ⁇ 30 mV to ⁇ 70 mV repelling with each other in the solvent containing the photocatalyst particles; Uncured resin, including.
  • the photocatalyst coating liquid of the present invention has a photocatalytic activity due to light in a living environment, and is obtained by coating without a complicated process. It is a liquid. That is, the photocatalyst coating liquid of the present invention typically has a silica particle, a resin, and a photocatalyst that are hybridized to obtain adhesion when a photocatalyst film is formed.
  • the photocatalyst particles are 3 wt% to 70 wt% with respect to the photocatalyst film manufactured using the photocatalyst coating liquid, and the negatively charged substance is 19 wt% to 80 wt% with respect to the photocatalyst film manufactured using the photocatalyst coating liquid.
  • the resin may be selected from 3 wt% to 60 wt% with respect to the photocatalyst film produced using the photocatalyst coating solution.
  • the description location using the notation “wt%” with respect to the photocatalyst coating liquid in the present specification is a value converted into an amount when the photocatalyst film is dried.
  • the photocatalyst-containing body in the photocatalyst coating liquid is larger than the above.
  • the negatively charged substance has a pH of 7 or more and less than 9, an average primary particle diameter of 1 nm or more, an average secondary particle diameter of 4000 nm or less, and preferably contains silica.
  • the resin may include any of acrylic resin, silicon resin, silicone resin, and urethane resin.
  • the photocatalyst particles are preferably photocatalyst particles obtained by combining flat crystal particles and three-dimensional crystal particles having a thickness larger than that.
  • the photocatalytic film of the present invention can be produced by curing the photocatalyst coating solution.
  • the photocatalyst coating liquid of the present embodiment typically includes a photocatalyst-containing body such as TiO 2 described below, a resin such as an acrylic resin, and a negatively charged substance such as silica particles. For example, they are mixed at a ratio of 15 wt%: 30 wt%: 55 wt%. As will be described later, it should be noted that this mixing ratio is illustrative and is not limited to this.
  • the “photocatalyst-containing body” composing the photocatalyst coating liquid of the present embodiment refers to a compound that itself has a photocatalytic action, and not only that, but also a photocatalyst that can be converted to a photocatalyst through a required process. The thing containing a precursor is said.
  • the photocatalyst-containing body includes, for example, a so-called visible light responsive TiO 2 photocatalyst containing photocatalyst particles in which flat crystal particles and solid crystal particles having a thickness compared to the flat crystal particles are combined.
  • the body Specifically, but not limited to these, Sagan Court TOsol 85, TPX, TPX-HP, TPX-HL, TPX-VB, TPX-AD manufactured by Sakai Corporation, which is one of the present applicants. , TPX-ID, etc. can be used (all are product names).
  • the material of the photocatalyst-containing body according to the present embodiment not only the TiO 2, ZnO, SrTiO 3, CdS, CdO, InP, In 2 O 3, BaTiO 3, K 2 NbO 3, Fe 2 O 3, Ta 2 O 5 , WO 3 , Bi 2 O 3 , NiO, Cu 2 O, SiO 2 , MoS 2 , MoS 3 , InPb, RuO 2 , CeO 2 , GaP, ZrO 2 , SnO 2 , V 2 O 5 , KTaO 3 Nb 2 O 5 , CuO, MoO 3 , Cr 2 O 3 , GaAs, Si, CdSe, CdFeO 3 , RaRhO 3, or the like can be used.
  • the visible light responsive photocatalyst-containing body refers to a photocatalyst-containing body that can exhibit photocatalytic activity such as photocatalytic activity and hydrophilicity when irradiated with light having a wavelength of about 400 nm to about 800 nm, for example.
  • the photocatalyst coating liquid using this kind of photocatalyst-containing body has an advantage that an environmental purification effect and an antifouling effect can be obtained mainly in a place such as a room where ultraviolet rays contained in sunlight are not sufficiently irradiated.
  • the photocatalyst-containing body according to this embodiment is unique in that it contains photocatalyst particles in which two different types of crystal particles are combined, but a photocatalyst coating liquid containing photocatalyst particles composed of one type of crystal particles. It should be noted that is not excluded from the scope of the present invention.
  • the flat crystal particles have an average size in the range of about 3 nm to 40 nm in the plate surface direction, and an average of 10 nm. About 20 nm. Further, the thickness of the flat photocatalyst particles falls within the range of about 0.3 nm to 5.0 nm, and the average is about 1.0 nm to 3.0 nm.
  • One feature of the photocatalyst-containing body of the present embodiment is that it is nano-sized.
  • a flat shape is defined as a general term for a shape that is relatively wide in the surface direction and relatively thin in the thickness direction.
  • the surface includes not only a smooth surface but also a slightly uneven or curved surface.
  • the shape of the surface is not limited, and may be any shape such as a circle, an ellipse, a hexagon, or a polygon such as a quadrangle.
  • the flat crystal particles are manufactured as follows, for example. First, for example, about 10 mL of about 2.0 wt% to 2.5 wt% aqueous ammonia is dropped into a dispersion obtained by diluting about 10 mL of an aqueous solution of about 50 wt% to 70 wt% of titanium tetrachloride to about 1000 mL with distilled water. Thus, a precipitate of titanium hydroxide is produced.
  • the precipitate is extracted from the dispersion by centrifugation, filtration or the like, and then the titanium hydroxide gel itself is washed with pure water, ion-exchanged water, distilled water or the like to remove impurities. Pure water, ion-exchanged water, or distilled water is added to the titanium hydroxide gel to produce a titanium hydroxide suspension having a volume of 100 mL to 500 mL.
  • the peroxo group is modified on the surface of the titanium oxide. For this reason, in the stock solution of photocatalyst, electric repulsion between particles works due to the polarization of the peroxo group, and titanium oxides repel each other so that they do not aggregate. Note that ammonium ions and the like in the photocatalyst stock solution also contribute to the dispersion. For this reason, the photocatalyst stock solution is a liquid in which titanium oxide is uniformly dispersed. In addition, the titanium oxide thus produced has one or more OH groups.
  • the three-dimensional crystal particles mean various three-dimensional shapes such as a substantially spherical shape, a substantially elliptical cross section, a circular shape, a square shape, and a polygonal shape thereof.
  • the three-dimensional crystal particle is defined as a generic name of a shape having a small relative difference between the plane direction and the thickness direction, unlike the above-described flat crystal particle.
  • the average size of the flat crystal particles is set to be equal to or larger than the average size of the three-dimensional crystal particles. If it carries out like this, a solid-shaped crystal particle will enter into the clearance gap between flat crystal particles, and also both titanium oxides will mutually be mixed so that it may mention later.
  • the solid crystal particles are manufactured, for example, as follows. First, a sulfate is produced by reacting ilmenite ore whose main components are iron oxide and titanium oxide with sulfuric acid. Next, after removing impurities from the sulfate, the sulfate is hydrolyzed to precipitate insoluble white hydrous titanium oxide. At this time, one or more OH groups are formed.
  • the titanium oxide produced in this way will have one or more OH groups.
  • the above production method is a so-called sulfuric acid method, but is not limited to this, and other production methods such as chlorine method, hydrofluoric acid method titanium potassium chloride method, titanium tetrachloride aqueous solution method, alkoxide hydrolysis method, etc. A method may be used.
  • the photocatalyst-containing body according to the present embodiment introduces various dopants with respect to titanium oxide, the high temperature of titanium oxide so as to obtain a band gap capable of absorbing visible light so that a photocatalytic action can be obtained by irradiation with visible light. Reduction, irradiation with high energy such as X-rays with respect to titanium oxide may be performed.
  • three-dimensional crystal particles are mixed with a photocatalyst stock solution containing flat crystal particles, and the photocatalyst stock solution is agitated to combine them as necessary.
  • the flat crystal particles are modified with peroxo groups and dispersed in the photocatalyst stock solution, it is preferable to add the three-dimensional crystal particles while maintaining this state.
  • the concentration of peroxotitanic acid is, for example, 5 wt% or less in order to avoid a decrease in peroxo groups or to avoid a decrease in impurities such as ammonium ion concentration contributing to the dispersion in the photocatalyst stock solution. It is preferable that impurities such as ammonium ions do not become 100 ppm or less.
  • both the flat crystal particles and the three-dimensional crystal particles have one or more OH groups. Therefore, both crystal grains are hydrogen-bonded at the OH group portion of each other.
  • the resin according to the present embodiment is such that when the photocatalyst film is produced, the use of the photocatalyst film is not limited when the photocatalyst film is produced, and preferably, when the photocatalyst film has a highly transparent finish. There are advantages in terms.
  • the resin according to this embodiment may be a water-based resin or a solvent-based resin, but it is preferable to use a water-based resin from the viewpoint of environmental considerations.
  • water-based resins include acrylic resin, acrylic urethane (acrylic polyol), acrylic silicone resin, aqueous silicone, block polymer of silicone resin and acrylic resin, acrylic styrene resin, sorbitan fatty acid ethylene oxide, sorbitan fatty acid
  • examples include ester, urethane acetate, polycarbonate diol and / or polyisocyanate cross-linked urethane, urethane dispersion, and cross-linked polyacrylic acid acrylic ester.
  • the negatively charged substance for example, colloidal silica in which silica particles are colloidally dispersed in water or an organic solvent, sodium silicate (for example, high molar sodium silicate), silica compound (for example, ammonium silicate), or the like.
  • a material containing silica can be used.
  • a substance that also functions as a binder with the coating surface of the photocatalyst coating liquid may be used. If it carries out like this, when sticking the photocatalyst film manufactured using the photocatalyst coating liquid to the sticking object, there exists an advantage that it becomes unnecessary to form an adhesive layer etc. between the coating surfaces of a photocatalyst coating liquid.
  • the negatively charged substance of this embodiment one having a zeta potential (electrokinetic potential) of about ⁇ 30 mV to ⁇ 70 mV is used.
  • the negatively charged substance according to this embodiment repels the photocatalyst particles in the photocatalyst-containing body that is negatively charged in the liquid containing the photocatalyst-containing body.
  • the resin has a positively charged substance and a negatively charged substance. and which, but for the photocatalyst particles Ti-O - If you are a stabilizing while repel is, Si-O for negatively charged substances - - and Ti-O is stabilized while the can repel - and Si-O .
  • the resin has a light hydrogen bond with a negatively charged substance having a relatively low molecular weight, and these bonds repel each other because the negatively charged substance has negative ions when the photocatalyst particles are in the vicinity. Stabilizes and slows down the photocatalytic particles decomposing the resin.
  • the resin layer that has been subjected to easy adhesion treatment on the PET layer has an electric double layer, and valence electrons form a stern layer near the interface. To do. Thereby, many negatively charged substances and photocatalyst particles are present on the surface of the photocatalyst film in a state of repulsion.
  • the photocatalytic activity that fully utilizes the photocatalytic ability is obtained.
  • many photocatalytic particles will be located in the resin, and even if the photocatalytic film is irradiated with visible light or the like, electrons will jump out to the vicinity. Cannot be obtained and sufficient photocatalytic activity cannot be obtained.
  • the negatively charged substance according to this embodiment may have a pH lower limit of about 7. This is because below this value, the photocatalyst coating solution will gel.
  • the upper limit of the pH of the negatively charged substance is preferably 9 or less. If it exceeds this, the photocatalyst coating solution becomes white turbid, and a photocatalytic film having translucency cannot be obtained. In other words, when the photocatalytic film of the present embodiment does not have to be translucent, the pH of the negatively charged substance may be higher than 9.
  • the lower limit of the particle size with an average primary particle size is 1 nm, preferably 5 nm. This is because the storage stability of the photocatalyst coating solution tends to decrease as the particle size decreases, and if it is less than 1 nm, it is difficult to ensure the storage stability of the photocatalyst coating solution of this embodiment. In other words, when the photocatalyst coating solution is used without being stored for a long period of time after production, a negatively charged substance having a particle size smaller than the above can be employed.
  • the measurement of the primary particle size of negatively charged substances is described in G. W. Sears, Jr. By using the Sears method described in “Analytical Chemistry ⁇ 28, 1981-1983 (1956)”.
  • the upper limit of the particle size of the negatively charged substance is 400 nm, preferably 100 nm, and more preferably 50 nm. This is because the transparency of the photocatalytic film decreases as the particle size increases. In other words, when the photocatalytic film of the present embodiment does not have to be translucent, the particle size of the negatively charged substance may exceed 400 nm, specifically, the average secondary particle size.
  • the upper limit can be about 4000 nm.
  • a negatively charged substance that satisfies the above requirements can be used in the form of an aqueous dispersion, whether it is acidic or basic. What type of negatively charged substance is used may be appropriately selected according to the photocatalyst-containing body to be mixed and the stable region of the resin.
  • each of the photocatalyst-containing bodies produced, the resin, and the negatively charged substance are mixed. Specifically, first, a negatively charged substance is introduced into the photocatalyst-containing body while stirring the photocatalyst-containing body at a rotational speed of, for example, about 100 rpm to 700 rpm.
  • a rotational speed for example, about 100 rpm to 700 rpm.
  • the ratio is 15 wt%: 55 wt% when the photocatalyst film is manufactured.
  • the stirring time depends on the charging speed of the negatively charged substance with respect to the photocatalyst-containing body, the total amount of the photocatalyst-containing body and the negatively charged substance, the size of the stirring blade, and the like. If the total amount with the negatively charged substance is about 40 kL, it may be about 30 minutes.
  • the resin is charged therein.
  • the photocatalyst-containing body containing a negatively charged substance resin is charged so that the ratio is, for example, 70 wt%: 30 wt%.
  • the stirring time depends on the charging rate of the resin with respect to the photocatalyst-containing body containing the negatively charged substance, but at room temperature, for example, about 20 kL with respect to the photocatalyst-containing body containing about 40 kL of the negatively charged substance.
  • the resin When the resin is added, it may be about 20 minutes.
  • metals such as Ag, Cu, and Zn can be added to the photocatalyst coating liquid of the present embodiment.
  • the surface layer to which such a metal is added can kill bacteria, sputum and algae attached to the surface even in the dark, and thus can further improve antibacterial properties.
  • the amount added may be about 1 wt% to 5 wt%.
  • platinum group metals such as Pt, Pd, Ru, Rh, Ir, and Os can be added to the coating liquid of this embodiment.
  • the surface layer to which such a metal is added can enhance the redox activity of the photocatalyst, and can improve the degradability of organic contaminants and the decomposability of harmful gases and odors.
  • the amount added may be about 1 wt% to 5 wt%.
  • the photocatalyst coating liquid of this embodiment can form a photocatalyst coating film having high hydrophilicity by coating on the surface of various substrates and curing.
  • the substrate is not particularly limited as long as a photocatalytic coating film can be formed.
  • the base material include various materials such as wood, organic materials including paper, inorganic materials including metal, and mixtures or compounds thereof.
  • organic materials include vinyl chloride resin, polyethylene, polypropylene, polycarbonate, acrylic resin, polyacetal, fluorine resin, silicone resin, ethylene-vinyl acetate copolymer (EVA), acrylonitrile-butadiene rubber (NBR), polyethylene terephthalate ( PET), ethylene-vinyl alcohol copolymer (EVOH), polyimide resin, polyphenylene sulfide (PPS), acrylonitrile-butadiene-styrene (ABS) resin, synthetic resin materials such as melamine resin, natural, synthetic or semi-synthetic fiber materials
  • polyethylene terephthalate having a good balance in terms of transparency, strength, and price is generally preferable. These may be commercialized into a required shape and configuration such as a photocatalyst film, other molded products, and laminates.
  • the base material is made of an organic material
  • This treatment improves the wettability and coatability of the photocatalyst coating liquid of the present embodiment to the substrate.
  • the surface activation treatment for example, corona treatment, normal pressure (or atmospheric pressure) plasma treatment, low-pressure low-temperature plasma treatment, easy adhesion treatment, or the like can be used.
  • inorganic materials include glass and ceramic materials. These can be commercialized in various forms such as tiles, insulators, mirrors and the like.
  • a metal is mentioned as an inorganic material. This includes cast iron, steel, iron, iron alloy, aluminum, aluminum alloy, nickel, nickel alloy, zinc die cast, etc., which may be plated and coated with organic paint. Further, it may be a metal plating coating applied to the surface of an inorganic or organic material.
  • FIG. 1 is a cross-sectional photograph of a substrate on which a photocatalytic film is formed by applying a photocatalyst coating solution.
  • the base material is a place plotted with “003”
  • the surface thereof is a place plotted with “003”
  • the photocatalytic film on the base material surface is a place plotted with “002” It is.
  • FIG. 2 is a diagram showing the results of component analysis of the surface of the photocatalytic film plotted by “002” in FIG. 1 using SEM-EDX (JSM-6390A manufactured by JEOL Ltd.). . As shown in FIG. 2, it can be seen that titanium as a photocatalyst was detected as indicated by “TiK ⁇ ” near the center.
  • the photocatalyst film of the present embodiment is first subjected to a photocatalyst coating solution under the condition that the thickness is, for example, in the range of 0.1 ⁇ m to 100 ⁇ m, preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 0.1 ⁇ m to 5.0 ⁇ m. Is applied to the film production equipment table.
  • This coating method may be a known one, specifically, dip coating method, spin coating method, spray coating method, brush coating method, impregnation method, roll method, wire bar method, die coating method, micro gravure coating method.
  • An ink jet method or the like may be used.
  • the film production apparatus base coated with the photocatalyst coating liquid is transported into a drying furnace, and the photocatalyst coating liquid is cured by heating and drying with hot air drying, a far infrared heater or a panel heater.
  • the drying temperature may be 70 ° C. to 160 ° C., preferably 90 ° C. to 120 ° C.
  • the reason for applying the photocatalyst coating solution under the condition that the thickness of the photocatalyst film falls within the above range is that the photocatalytic activity as a photocatalyst film cannot be sufficiently obtained when the coating thickness is lower than the lower limit.
  • the photocatalyst film or the precursor during production thereof may be peeled off from the film production equipment table, cracked, or warped, resulting in a decrease in durability of the thin film. This is to do.
  • a photocatalyst film having a thickness of 0.1 ⁇ m to 100 ⁇ m was produced using a photocatalyst coating solution suitable for the photocatalyst film.
  • the photocatalyst film had a haze value of about 5
  • the total light transmittance was 80% or more and the self-cleaning property was 5 or more.
  • the base material used here had a Haze value of 1.3. For this reason, the Haze value of the photocatalytic film itself is approximately 3.7 or less.
  • Example 1 As a composition of the photocatalyst coating liquid, Photocatalyst-containing body: Sagan Coat TPX-HL manufactured by Sakai Corporation Resin: WBR made by Taisei Fine Chemical Co., Ltd. as an aqueous urethane resin Silica particles: Hyper Glass N manufactured by Toso Sangyo Co., Ltd. Prepared. And these photocatalyst containing body: resin: silica particle was mixed in the ratio used as about 15 wt%: 30 wt%: 55 wt%, and the photocatalyst coating liquid was manufactured through the above-mentioned stirring process. In addition, the ratio shown by this specification shall include the ratio to about +/- 10% of the explicit numerical value.
  • Table 1 is a table showing the test results of the antibacterial test of the photocatalyst film of this example.
  • the antibacterial property test here was implemented 3 times for staphylococcus aureus and Escherichia coli according to JIS R1702.
  • an unprocessed test piece (glass plate) was also prepared as a comparison target for this antibacterial test.
  • the numerical values in Table 1 are average values of test results performed three times.
  • the photocatalytic film and the unprocessed test piece of this example were inoculated with Staphylococcus aureus and Escherichia coli, respectively, and then irradiated with ultraviolet light for about 8 hours. It shows the number of viable bacteria, the number of viable bacteria in the photocatalyst film and unprocessed test piece after being stored in the dark for about 8 hours, and the “antibacterial activity value” and “effect by light irradiation” that can be calculated from these. .
  • the antibacterial activity value is 4.0, and the effect of light irradiation is 2.2.
  • the antibacterial activity value is 2.0 or more, and if the effect of light irradiation is 0.3 or more, it is determined that there is antibacterial property, Each of these numerical values greatly exceeds the reference value such that the antibacterial activity value is 4.0 and the effect of light irradiation is 2.2.
  • the photocatalyst film of a present Example has the very outstanding antimicrobial property also with respect to Staphylococcus aureus.
  • the photocatalytic film of this example has very excellent antibacterial properties against E. coli.
  • the decomposition activity index which is a measure of the self-cleaning performance of the photocatalytic material utilizing wet decomposition performance, was “11.5 ⁇ mol / L / min”.
  • the decomposition activity index is usually “5 ⁇ mol / L / min” or more, it is considered that the self-cleaning performance is excellent, and in the case of the photocatalytic film of this example, this value is well exceeded. It can be seen that it has a very good self-cleaning performance.
  • Table 2 is a table
  • the photocatalytic film of this example is placed under a black light having an illuminance of about 12 lx and an ultraviolet intensity of about 1,200 ⁇ W / cm 2 in a measurement region of 310 nm to 400 nm. The contact angle and the contact angle after UV irradiation were measured.
  • Table 2 shows contact angles “before UV irradiation”, “1 day after UV irradiation”, and “2 days after UV irradiation”, respectively. According to the test results of the hydrophilicity test shown in Table 2, the contact angles are 40.3 °, 19.9 ° and 10.8 °, respectively. Therefore, it can be seen that the photocatalytic film of this example has a contact angle that is reduced by irradiating with ultraviolet rays, and the photocatalytic film exhibits hydrophilicity.
  • the weather resistance test of the photocatalyst film of this example was performed.
  • This test was performed by the QUV method, and “Accelerated Weathering Tester” manufactured by Q-Lab was used as a weathering tester for ultraviolet fluorescent lamps.
  • the test conditions are ASTM G154 CYACLE2, that is, in Step 1, ultraviolet rays are irradiated for 4 hours at a dose of 0.71 w / m 2 and a temperature of 60 ° C.
  • Step 2 a test was performed in which the total light transmittance was measured in 48 cycles, assuming that the condition of condensation for 4 hours at a temperature of 50 ° C. was one cycle.
  • the total light transmittance% was 91.99% before the start of the weather resistance test, 90.89% at 10 cycles, that is, 80 hours after the start of the test, and 20 cycles. 90.44%, 91.17% at the stage of 30 cycles, 91.10% at the stage of 40 cycles, and 91.00% at the stage of 48 cycles.
  • Example 2 As the composition of the photocatalyst coating solution, the same composition as in Example 1 was prepared, and these photocatalyst-containing bodies: resin: silica particles were mixed at a ratio of approximately 10 wt%: 50 wt%: 40 wt%. A photocatalyst coating solution was produced through the stirring step described above.
  • Example 3 As the composition of the photocatalyst coating solution, the same composition as in Example 1 was prepared, and these photocatalyst-containing bodies: resin: silica particles were mixed in a ratio of approximately 35 wt%: 5 wt%: 60 wt%. A photocatalyst coating solution was produced through the stirring step described above.
  • Example 4 As the composition of the photocatalyst coating solution, the same composition as in Example 1 was prepared, and these photocatalyst-containing bodies: resin: silica particles were mixed at a ratio of approximately 15 wt%: 20 wt%: 65 wt%. A photocatalyst coating solution was produced through the stirring step described above.
  • Example 1 As the composition of the photocatalyst coating solution, the same resin and silica particles as in Example 1 were prepared, and as the photocatalyst-containing body, Titania Sol STS-01 (product name) manufactured by Ishihara Sangyo Co., Ltd. was prepared. These photocatalyst-containing materials: resin: silica particles were mixed at a ratio of approximately 15 wt%: 30 wt%: 55 wt% in the same manner as in Example 1, and a photocatalyst coating solution was produced through the stirring step described above.
  • the Sagancoat TPX-HL used in each example has a TEM photograph of 10 nm (average particle size of 40 nm to 45 nm for Malvern's Zetasizer Nano S), and titania sol STS-01 is the average particle size of Zetasizer Nano S Is 60 nm to 65 nm.
  • Comparative Example 2 As the composition of the photocatalyst coating solution, the same photocatalyst-containing body and resin as in Example 1 were prepared, and as silica particles, Snowtex XS made by Nissan Chemical Co., Ltd. was prepared. These photocatalyst-containing bodies: Resin: Silica particles were mixed at a ratio of approximately 15 wt%: 30 wt%: 55 wt% in the same manner as in Example 1, and a photocatalyst coating solution was produced through the aforementioned stirring step. Snowtex XS has a pH of about 9.5 to 10 and a zeta potential of about ⁇ 23 mV to ⁇ 35 mV.
  • Table 4 summarizes the relationship between the components and mixing ratios of the above-described examples and comparative examples.
  • photocatalyst is an abbreviation for “photocatalyst-containing body”
  • sica is an abbreviation for “silica particles”.
  • a photocatalyst film having a thickness of 1 ⁇ m was formed by the method described in the embodiment using the photocatalyst coating liquid of each example and each comparative example. About these photocatalyst films, the following items were measured or evaluated, respectively.
  • the titanium oxide used for this coating liquid had visible light responsiveness, it replaced with irradiating with ultraviolet light, and irradiated with visible light.
  • Table 5 summarizes various measurements or evaluation results of the respective examples and comparative examples described above.
  • Example 1 and 2 “visual appearance observation”, “appearance appearance evaluation”, and “transparency%” were all highly evaluated.
  • Comparative Examples 1 and 2 uniform dispersion of the photocatalyst-containing body could not be realized, and a mottled pattern could be confirmed.
  • Example 3 although the thing of Example 3 is not transparent, either because the photocatalyst-containing body is uniformly dispersed, or as "appearance of appearance", no mottled pattern is seen. In comparison, it was not so bad.
  • Comparative Examples 1 and 2 had a mottled pattern as described above, and could not be evaluated. On the other hand, in Examples 1 to 3, the degradation activity exceeding 3.5 was confirmed at least.
  • the total light transmittance was relatively high in all of Examples 1 to 3, and those of Comparative Examples 1 and 2 were relatively low.
  • the above measurement or evaluation result is scored based on the following indices.
  • “visual appearance observation”, “appearance appearance evaluation”, and “transparency” all indicate transparency, and there is also a correlation with “decomposition activity”. Focusing on “appearance of appearance”, “ ⁇ ” is 5 points, “ ⁇ ” is 3 points, and “ ⁇ ” is 1 point. This index is intended to increase the score because the use is not limited if the photocatalytic film is “transparent” as described above.
  • total light transmittance 89% or more is 5 points, 86% to 88% is 4 points, 83% to 85% is 3 points, 80% to 82% is 2 points, less than 80% 1 point. This index is such that the higher the transmittance, the higher the score.
  • Example 1 According to the above index, the one of Example 1 is the most excellent, and since it is transparent, its use is not limited, so it can be said that it is the most convenient.
  • Example 3 is limited in terms of application and is transparent. However, it is not suitable for a touch panel or the like that requires translucency, but can be suitably used when the ground color such as a handrail of stairs can be white. In addition, since the decomposition activity of Example 2 is not high, it is not suitable for a touch panel or the like that is frequently touched by hands. It can be used suitably.
  • the photocatalyst-containing body used in Example 1 is smaller in particle size than the photocatalyst-containing body used in Comparative Example 1. This is a feature of No. 1, specifically, a nano-order size.
  • the particle size is small, the film forming property of the photocatalyst film is stabilized, and as a result, the adhesion is improved. Further, the small particle size contributes to the improvement of transparency.
  • the silica used in Example 1 is that the pH of the Comparative Example 2 is alkaline while the pH is neutral. Since the photocatalyst-containing material used in Example 1 is neutral, the photocatalyst coating solution is also neutral, so that the photocatalyst coating solution and thus the photocatalyst film does not become cloudy. . Moreover, the silica used in Example 1 has a high zeta potential, and acts so that a large amount of the photocatalyst-containing body is located on the surface of the photocatalyst film.
  • the photocatalyst particles are 3 wt% to 70 wt% with respect to the photocatalyst film manufactured using the photocatalyst coating liquid, and the negatively charged substance is used using the photocatalyst coating liquid. It was found that the resin can be selected from 19 wt% to 80 wt% with respect to the manufactured photocatalyst film, and the resin can be selected from 3 wt% to 60 wt% with respect to the photocatalyst film manufactured using the photocatalyst coating solution.
  • Example 1 was applied to a substrate in which the applied photocatalyst coating solution is generally difficult to adhere, such as a product made of vinyl chloride resin, aluminum, cycloolefin polymer (COP) film, or fluororesin.
  • the photocatalyst coating solution was diluted with isopropyl alcohol (IPA) and then applied, and performance was evaluated for appearance, hardness, adhesion, and decomposition activity.
  • IPA isopropyl alcohol
  • Table 6 is a table showing the performance evaluation results of the photocatalyst film in which the photocatalyst coating liquid of Example 1 was applied to each substrate made of vinyl chloride resin, aluminum, COP film, and fluororesin.
  • the photocatalyst coating liquid applied to the vinyl chloride resin base material is not diluted, but the photocatalyst coating liquid applied to the aluminum base material is diluted twice with IPA, and the COP film base material and the fluororesin The photocatalyst coating liquid applied to the substrate is diluted 1.25 times with IPA.

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Abstract

L'invention vise à fournir un liquide de revêtement photocatalytique permettant d'obtenir une activité photocatalytique suffisante et qui peut, dans certaines conditions, et au moyen d'un seul liquide, appliquer un film photocatalyseur sans faire l'objet d'étapes compliquées. Le liquide de revêtement photocatalytique contient : des particules de photocatalyseur ayant une taille de l'ordre du nanomètre ; une substance chargée négativement ayant un potentiel zêta de -30 mV à -70 mV et qui rebondit par rapport aux particules de photocatalyseur dans une solution contenant les particules de photocatalyseur ; et une résine dans un état non durci. Le liquide de revêtement photocatalytique amène le photocatalyseur à être positionné au niveau d'une surface revêtue.
PCT/JP2015/055085 2014-03-03 2015-02-23 Liquide de revêtement photocatalytique et film photocatalyseur l'utilisant WO2015133316A1 (fr)

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CN116694217A (zh) * 2023-07-03 2023-09-05 天津市职业大学 一种太阳光催化自清洁涂料及其制备和应用方法
JP7424867B2 (ja) 2019-03-12 2024-01-30 東曹産業株式会社 珪酸塩系水溶液

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JP6939025B2 (ja) * 2017-03-31 2021-09-22 東洋インキＳｃホールディングス株式会社 光輝性呈色樹脂組成物、光輝性呈色物品およびその製造方法
JP6606239B1 (ja) * 2018-08-22 2019-11-13 株式会社オリジン 塗布物質塗布済対象物の製造方法
CN111187530B (zh) * 2020-01-06 2021-11-26 浙江大学衢州研究院 一种氟硅复合可见光催化抑菌防污涂料及其制备方法

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