WO2018225629A1 - Matériau de base et son procédé de fabrication - Google Patents

Matériau de base et son procédé de fabrication Download PDF

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Publication number
WO2018225629A1
WO2018225629A1 PCT/JP2018/021076 JP2018021076W WO2018225629A1 WO 2018225629 A1 WO2018225629 A1 WO 2018225629A1 JP 2018021076 W JP2018021076 W JP 2018021076W WO 2018225629 A1 WO2018225629 A1 WO 2018225629A1
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oxide
base material
water
coating agent
photocatalyst
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PCT/JP2018/021076
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English (en)
Japanese (ja)
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垰田　博史
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Ｈｏｔｔａｐａｌａｄ Ｍａｒｂｌｅ Ｊａｐａｎ株式会社
垰田　博史
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Publication of WO2018225629A1 publication Critical patent/WO2018225629A1/fr

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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
    • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
    • 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
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18—Arsenic, antimony or bismuth
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • 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
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/65—Coating or impregnation with inorganic materials

Definitions

  • the present invention relates to an antifouling technique for base materials such as stone, glass, metal, paper, cloth, and wood used as walls and floors of buildings, garden stones, tombstones, stone statues, monuments, objects, roads, paving stones, and the like.
  • the surface is water-absorbing, soaks rainwater and moisture, and when used outdoors for a long period of time, mold, moss, algae, germs, and other dirt may erode and adhere to the surface. is there. As a result, even after washing, the stains cannot be removed because they are soaked. In addition, even when used indoors, even if there is no nutrient, only moisture or moisture adheres to the surface, and mold, moss, algae, germs, etc. grow and become dirty.
  • the surface of the base material grows mold, moss, and algae due to these causes, and the aesthetics are impaired.
  • the surface of the base material is cleaned using a scrubbing brush, sponge, mop, high-pressure washing, etc. It was implemented, and it took a lot of time and money.
  • the photocatalyst is usually superhydrophilic
  • the surface of the substrate on which the photocatalyst is processed becomes hydrophilic, and moisture and moisture adhere to the surface, so when there is no light such as at night, mold, moss, Algae and other germs grow and become contaminated.
  • light is blocked by the dirt so that the photocatalyst on the substrate surface does not hit the light and the effect of the photocatalyst cannot be exhibited, so mold, moss, algae, germs, etc. Dirt due to breeding could not be prevented.
  • An object of the present invention is to provide a revolutionary base material with an excellent antifouling function by eliminating the weak points of this photocatalyst that has been a problem for a long time.
  • a substrate characterized in that a coating agent containing a photocatalytic material and an organic binder is coated on the surface of the substrate, and the coated surface is water-repellent.
  • a coating agent containing a photocatalytic material and an organic binder is coated on the surface, and the coated surface is water repellent.
  • the photocatalytic material may be particles having a particle diameter of 80 nm or less.
  • the photocatalyst material is one in which an inorganic substance is partially supported on a metal oxide or metal oxide particle surface.
  • the metal oxide is any one or more of titanium oxide, tungsten oxide, zinc oxide, lead oxide, tin oxide, antimony oxide, indium oxide, indium tin oxide, and tin oxide-antimony oxide. (That is, a single substance or a mixture of two or more).
  • the inorganic substance is one or more of apatite, silica, and alumina.
  • the organic binder is composed of one or more of organic silicate, alkali metal organic silicate, silicon resin, and fluororesin (that is, composed of a single substance or a mixture of two or more).
  • the coating agent further contains a solvent, and the content of the photocatalytic material is 0.01 wt% to 10 wt%.
  • the content of the organic binder with respect to the photocatalytic material in the coating agent is 0.1 or more and 100 or less in terms of weight.
  • the base material similar to the thing in said each aspect will be manufactured. can do.
  • each of the above-described manufacturing methods includes a step of allowing a coating agent containing a photocatalytic material and an organic binder to penetrate into the surface of the base material, and a step of heat drying. Substrates similar to those in the aspect can be produced.
  • the eleventh aspect of the present invention comprises at least one of titanium oxide, tungsten oxide, zinc oxide, lead oxide, tin oxide, antimony oxide, indium oxide, indium tin oxide, and tin oxide-antimony oxide.
  • a coating agent comprising a photocatalytic material in which an inorganic substance is partially supported on a metal oxide, and an organic binder composed of at least one of organic silicate, alkali metal organic silicate, silicon resin, and fluororesin.
  • a water-repellent photocatalyst film particularly a transparent water-repellent photocatalyst film is formed on the substrate surface.
  • the surface of the base material repels water and water does not permeate, preventing rain water from seeping into the base material and changing it into a wet color, and preventing mold, moss, algae, germs, etc. from growing.
  • Various effects such as prevention of corrosion by acid rain, prevention of corrosion by acid rain, prevention of freezing of water that has soaked in winter, and prevention of salt damage.
  • effects such as prevention of icing and icicles can be obtained.
  • this water-repellent film has small holes and does not allow water to pass through but allows moisture to pass through.
  • the photocatalytic decomposition action cleans the dirt adhering to the substrate surface by oxidizing and decomposing it into water and carbon dioxide, thus providing a synergistic effect of self-cleaning.
  • bacteria, viruses, bad odors, etc. coming into contact with the substrate surface can be decomposed by the photocatalyst, so antibacterial and deodorizing effects can be obtained at the same time.
  • the substrate is paper or cloth, water resistance and heat resistance, Effects such as flameproofing can also be obtained.
  • the base material is a tombstone made of natural granite or marble with a mirror-polished surface, for example, granite or marble paving stone cut to about 40 cm square, lantern, garden stone, monument, object, building, ruins, etc.
  • Various materials such as bricks, tiles, roof tiles, glass, metal, paper, cloth, wood, etc. can be used in addition to stone materials such as various natural stones and artificial stones, materials made of concrete, materials made of mortar . And it is possible to process not only a substrate that has been newly cut or manufactured, but also a substrate that has been installed for several decades.
  • the water repellency of the substrate surface coated with the coating agent containing the photocatalyst material according to the present invention and the organic binder is measured by measuring the contact angle between the substrate surface and the water droplet by dropping water droplets onto the substrate surface.
  • the contact angle with water is preferably 90 ° or more and 180 ° or less, and particularly preferably 110 to 180 °. If the water contact angle of the wall of the substrate is 90 degrees or more, water hardly adheres, and if it is 110 degrees or more, even if water is applied to the surface of the substrate, the water droplets roll and do not get wet.
  • the organic binder used in the coating agent containing the photocatalytic material according to the present invention is desirably water-repellent when dried, and desirably has durability against the decomposition action by the photocatalyst.
  • examples thereof include organic silicates, alkali metal organic silicates, silicon resins, fluororesins, and the like.
  • the organic silicate is typically an alkyl silicate such as methyl silicate or ethyl silicate, and becomes a water-repellent organic silica film when dried. Since it is quick-drying, it can be formed even at room temperature and a glass film excellent in transparency can be produced.
  • Alkali metal organic silicates are typically alkyl silicates such as sodium methyl silicate, methyl potassium silicate, lithium ethyl silicate, and potassium propyl silicate. When dried, a water-repellent organic silica-silicate film is formed. Since the membrane surface is alkaline, a membrane resistant to acid rain and mold can be obtained. In the case of silicon resin or fluorine resin, a soft and flexible film can be obtained. These films are water repellent and durable against the degradation action by the photocatalyst.
  • the photocatalyst material used for the coating agent containing the photocatalyst material according to the present invention is a metal such as titanium oxide, tungsten oxide, zinc oxide, lead oxide, tin oxide, antimony oxide, indium oxide, indium tin oxide, tin oxide-antimony oxide. It is an oxide. Titanium oxide works by irradiation of ultraviolet rays, and has the advantages of being inexpensive, excellent in durability, and abundant in resources. Tungsten oxide, zinc oxide, and lead oxide have the advantage that they have a longer light absorption wavelength than titanium oxide and can use not only ultraviolet rays but also visible light.
  • the heat blocking function can be used simultaneously with the photocatalytic function.
  • a base material coated with a coating agent containing these photocatalyst materials and an organic binder is used for a long period of time, the organic content in the water-repellent film formed on the base material surface is gradually reduced by the photocatalyst. Since the water repellency is gradually degraded due to decomposition into carbon dioxide, it is desirable to use those in which an inorganic substance such as apatite, silica, alumina or the like is partially supported on the surface of the metal oxide particles.
  • the photocatalyst material used in the coating agent containing the photocatalyst material according to the present invention is preferably ultrafine particles. If the particle diameter is ultrafine particles of 80 nm or less, light scattering can be suppressed when dispersed in the coating agent, so that a transparent coating agent or coating film can be obtained. If the particle size of the photocatalyst exceeds 80 nm, the coating material containing it will scatter light and become white, and when processed to the surface of black granite or marble, the color of the stone itself becomes white and turbid, This is not preferable because the color and texture are impaired.
  • the concentration of the photocatalytic material added to the coating agent it is desirable that the solid content of the photocatalytic material is 0.01% to 10%, particularly 0.1% to 5%. If the concentration of the photocatalyst material is too high, the photocatalyst particles aggregate to increase the particle size and the photocatalyst particles can be easily removed and become white. Conversely, if the concentration is too low, the oxidative decomposition power of the photocatalyst film decreases.
  • the coating agent containing the photocatalytic material according to the present invention preferably has a photocatalytic material: organic binder ratio of 1: 0.1 to 100, particularly 1: 0.5 to 50, as the concentration ratio of the photocatalytic material to the organic binder. If the concentration ratio of the organic binder is less than 0.1, the photocatalyst material can be easily removed, and adhesion and durability are remarkably lowered. If the concentration ratio is higher than 100, the photocatalyst material is buried in the organic binder and light is difficult to hit. It becomes difficult to demonstrate performance.
  • the coating agent containing the photocatalyst material according to the present invention further comprises a solvent in the photocatalyst material and the organic binder.
  • a solvent for example, water or alcohol can be used, and water is most preferable as the solvent.
  • the substrate surface is porous, hydrophilic and water-absorbing. Therefore, if the solvent is water, the coating agent containing the photocatalytic material has an affinity for the base material, so that it can easily be coated by being immersed in the surface of the base material.
  • organic solvents such as hydrocarbons are flammable and have dangers and hazards such as explosion, and are expensive, whereas water is safe and non-toxic and easy to handle at low cost.
  • the processing to the substrate it is better not only to apply the coating agent solution containing the photocatalyst material only to the surface of the substrate but also to penetrate the inside of the surface.
  • the water-repellent film is coated with a sword-like structure of organic base on the porous and uneven surface of the stone material.
  • a water-repellent film having a larger size and excellent durability can be obtained.
  • it penetrate it becomes water-repellent to the inside of the base material, preventing water from entering, preventing cracking due to freezing in winter, and preventing invasion of mold, moss, algae, germs, etc., and lasting for a long time An antifouling layer is formed.
  • the coating agent solution containing the photocatalytic material is infiltrated into the surface and the inside of the surface due to the porous property of the base material, and then dried by heating at a temperature of 200 ° C. or less.
  • a temperature of 200 ° C. or less By heating after coating, an antifouling water-repellent layer having excellent durability is formed in a short time.
  • the heating temperature is preferably 200 ° C. or lower. At that time, if the temperature is increased by heating from room temperature, a water-repellent film having excellent adhesion to the substrate can be formed.
  • a solution of a coating agent containing a photocatalytic material may be applied to the surface of the base material heated to a temperature of 30 ° C. or higher and 200 ° C. or lower in advance.
  • a highly durable antifouling layer can be formed in a short time.
  • a solution of a coating agent containing a photocatalytic material is applied to the surface of the base material that has been heated to a temperature of 30 ° C. or higher and 200 ° C. or lower in advance, and is further heated and dried at a temperature of 200 ° C. or lower. It is particularly desirable. By doing so, a highly durable antifouling layer can be formed.
  • the water contact angle of the surface after applying or impregnating the coating agent it is preferable to adjust the water contact angle of the surface after applying or impregnating the coating agent to 100 degrees or more and 170 degrees or less, more preferably 130 degrees or more and 160 degrees or less. If the water contact angle is less than 100 degrees, it is not preferable because sufficient water repellency cannot be exhibited. On the other hand, if the water contact angle exceeds 170 degrees, handling of the coating agent becomes difficult and productivity is deteriorated. Absent.
  • the substrate and the coating agent according to the present invention will be described in more detail based on examples, but the present invention is not limited to the embodiments of the examples and does not depart from the spirit of the present invention. Thus, it can be changed as appropriate.
  • a coating liquid was prepared by dispersing 1% of titanium oxide sol (Jupiter F4APS, manufactured by Showa Denko KK), 10% of ethyl silicate, and 0.1% of indium oxide in water partially supporting apatite on the particle surface. Soak this coating solution in a rag, wipe the surface of the concrete outer wall covered with green mold on one side of the university building in Bangkok, Thailand, wipe the mold cleanly and coat the coating liquid inside the concrete outer wall Infiltrated. Since the outside air temperature was 40 ° C., the coating liquid was dried in one day to form a water repellent film.
  • Example 2 Disperse the coating liquid by dispersing 0.1% titanium oxide powder (Jupiter S manufactured by Showa Denko KK) with silica partially supported on the particle surface, 5% silicon resin emulsion and 0.05% indium tin oxide in water. Prepared. Soak this coating solution into the sponge, wipe the black granite tombstone that has been installed for 5 years to clean the surface and infiltrate the coating solution into the surface of the tombstone, so that the surface temperature becomes 50 ° C. Then, the surface of the tombstone was dried using an electric heater to form a water repellent film. The water contact angle of this surface was measured in an atmosphere of 23 ° C.
  • Example 3 Prepare a coating solution by dispersing 5% titanium oxide powder (Jupiter F4AP manufactured by Showa Denko KK), 20% ethyl silicate, and 0.1% tin oxide-antimony oxide in water. did. Next, the coating liquid was infiltrated into the surface of a new marble plate having a size of 40 cm square and a thickness of 2 cm while being coated with a roll coater. Then, it was heated and dried using an electric heater so that the surface temperature of the marble was 60 ° C. As a result, the surface of the marble became water-repellent and could not be soaked even with water.
  • the water contact angle of this surface was measured in the same manner using a contact angle meter DM-301 manufactured by Kyowa Interface Science Co., Ltd. and found to be 138 degrees.
  • This marble plate was subjected to an accelerated deterioration test for 1500 hours using a sunshine weather meter. As a result, it was found that even after 1500 hours, the water contact angle was 135 degrees, the same water repellency could be maintained, and the durability was excellent. And when it was left outdoors and exposed to wind and rain for one year, there was no adhesion of mold, moss, etc. on the surface, and a clean state was maintained.
  • Table 1 shows the evaluation results of the antifouling function of the base material (marble) together with the properties of the base material.
  • a coating solution was prepared by dispersing 5% of titanium oxide powder (Jupiter F4AP manufactured by Showa Denko KK) with apatite partially supported on the particle surface and 0.1% of tin oxide-antimony oxide in water. This was coated on the surface of marble in the same manner as in Example 3, heated and dried. When the water contact angle of this surface was measured in the same manner, it was 49 degrees. After performing an accelerated deterioration test in the same manner as in Example 3, the water contact angle on the surface was measured and found to be hydrophilic at 8.5 degrees. And when it was left outdoors and exposed to wind and rain for 1 year, adhesion of mold, moss, etc. was seen on the surface. Table 1 shows the evaluation results of the antifouling function of the base material (marble) together with the properties of the base material.
  • a coating solution was prepared by dispersing 3% of titanium oxide powder (Jupiter S manufactured by Showa Denko KK) having silica partially supported on the particle surface, 30% of a fluororesin emulsion, and 0.05% of antimony oxide in water.
  • the garden stone was dried using an electric furnace so that the surface temperature of the garden stone (chart rock) became 70 ° C.
  • the half of the surface of the garden stone was soaked by applying the prepared coating solution with a brush. The temperature was raised again in the electric furnace until the surface reached about 60 ° C. This was cooled to room temperature, and then the lower half was immersed in an outdoor pond and actually used as a garden stone.
  • Table 1 shows the evaluation results of the antifouling function of the base material (chart rock) together with the properties of the base material.
  • a coating solution was prepared by dispersing 1% of titanium oxide powder (Jupiter S manufactured by Showa Denko KK) with silica partially supported on the particle surface, 15% of lithium methyl silicate, and 0.1% of indium oxide in water.
  • the paving stone of a new concrete block was heated using an electric heater so that the surface temperature became 50 ° C., and after the moisture of the paving stone was evaporated, it was prepared to about half of the surface of the paving stone which became 50 ° C.
  • the coating solution was applied by spray and soaked into the surface. Then, it was dried again with an electric heater until the surface reached about 100 ° C. This was cooled to room temperature and then used as a paving stone outdoors.
  • the coated part was free of mold and moss, and the paving stones remained clean, while the uncoated part turned black. It is considered that a durable antifouling treatment has been achieved against wear that occurs when a person walks on the person.
  • a base material mentioned above what consists of a material which can couple
  • Example 6 The same amount of methyl alcohol is added to methyl silicate, and the resulting mixture is added dropwise to 9 times the amount of water with stirring.
  • the resulting liquid is partially supported by titanium oxide sol (four for which apatite is supported on the particle surface and iron is doped).
  • 2% of F4T-30AF manufactured by Tea Science Laboratory Co., Ltd. was added and dispersed to prepare a coating solution. This was applied while immersing the liquid in the paper with a brush, then placed in a drier and heated from room temperature to 80 ° C. to dry. The resulting paper did not fall apart when immersed in water, and even burned with a lighter, it burned a little and did not burn (see FIG. 2). A stain resistance test was performed on the paper.
  • Example 3 A coating solution was prepared by adding 2% of titanium oxide sol (F4T-30AF, manufactured by Forty Kaken Co., Ltd.), which is partially supported by apatite on the particle surface and doped with iron, and dispersed in water. This was applied to the paper in the same manner as in Example 6 to prepare a test piece. When the obtained test piece was immersed in water, it was broken apart. Also, when the lighter was lit, it burned and became ash. Using this test piece, a stain resistance test was conducted in the same manner as in Example 6. As a result, the decomposition rate of the black ink was 30%. It seems that the photocatalyst particles were detached from the paper. Table 1 shows the evaluation results of the antifouling function of the base material (paper paper) together with the properties of the base material.
  • stone walls, floors, garden stones, tombstones, stone walls, stone statues, objects, stone monuments, roads, paving stones, etc. used as stone, glass, metal, paper, cloth, wood, etc. It is possible to provide a product with an excellent soiling function, and it can be used for various purposes.

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

Abstract

Le problème selon l'invention concerne des matériaux de base tels que le métal, le verre et les matériaux en pierre qui sont utilisés pour construire des murs, des sols, des roches de jardin, des graviers, des murs en pierre, des statues en pierre, des objets d'art, des monuments en pierre, des routes et des pavés, qui ont des propriétés d'absorption d'eau et hydrophiles, dont les surfaces sont soumises à l'érosion et à l'adhérence par les moisissures, mousse, algues, divers germes et d'autres taches pendant l'utilisation et peuvent ainsi subir une perméation de taches difficiles à éliminer même avec un lavage. En conséquence, une grande quantité de temps et d'argent était nécessaire pour le nettoyage. Par conséquent, l'invention concerne un matériau de base ayant un aspect externe qui peut rester propre sans nécessiter un nettoyage fréquent. La solution selon l'invention porte sur un matériau de base qui est obtenu par revêtement de la surface avec un agent de revêtement qui contient un matériau photocatalyseur et un liant organique, qui a une surface hydrofuge repoussant l'eau et qui a une excellente fonction d'auto-nettoyage par décomposition des taches par l'action de décomposition du photocatalyseur.
PCT/JP2018/021076 2017-06-09 2018-05-31 Matériau de base et son procédé de fabrication WO2018225629A1 (fr)

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