WO2023032686A1 - Milieu de culture hydroponique, procédé de production de milieu de culture hydroponique, procédé hydroponique utilisant un milieu de culture hydroponique, et liquide de dispersion pour supprimer l'apparition d'algues - Google Patents

Milieu de culture hydroponique, procédé de production de milieu de culture hydroponique, procédé hydroponique utilisant un milieu de culture hydroponique, et liquide de dispersion pour supprimer l'apparition d'algues Download PDF

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WO2023032686A1
WO2023032686A1 PCT/JP2022/031156 JP2022031156W WO2023032686A1 WO 2023032686 A1 WO2023032686 A1 WO 2023032686A1 JP 2022031156 W JP2022031156 W JP 2022031156W WO 2023032686 A1 WO2023032686 A1 WO 2023032686A1
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culture medium
dispersion
titanium oxide
algae
growth
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PCT/JP2022/031156
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English (en)
Japanese (ja)
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厚 中村
幸介 藤田
美代 坂井
俊介 河中
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Dic株式会社
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Priority to CN202280053463.7A priority Critical patent/CN117794645A/zh
Priority to JP2023545436A priority patent/JP7477053B2/ja
Publication of WO2023032686A1 publication Critical patent/WO2023032686A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/10—Growth substrates; Culture media; Apparatus or methods therefor based on or containing inorganic material
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/30—Growth substrates; Culture media; Apparatus or methods therefor based on or containing synthetic organic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/40—Growth substrates; Culture media; Apparatus or methods therefor characterised by their structure
    • A01G24/44—Growth substrates; Culture media; Apparatus or methods therefor characterised by their structure in block, mat or sheet form
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/40—Growth substrates; Culture media; Apparatus or methods therefor characterised by their structure
    • A01G24/48—Growth substrates; Culture media; Apparatus or methods therefor characterised by their structure containing foam or presenting a foam structure
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G31/00—Soilless cultivation, e.g. hydroponics
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
    • 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—
    • B01J35/56—
    • 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
    • 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
    • B01J37/04—Mixing

Definitions

  • the present invention relates to a hydroponic culture medium, a method for producing a hydroponic culture medium, a hydroponic culture method using the hydroponic culture medium, and a dispersion liquid for suppressing the growth of algae.
  • Hydroponics is a cultivation method in which crops are grown in a "culture solution” using raw water and liquid fertilizer. Hydroponics is a cultivation method that does not require work such as soiling and fertilization, is less affected by the geographical environment, and has high utility value.
  • a problem unique to cultivation that uses water is the occurrence of algae. Since algae grow as long as they have light and nutrients, the occurrence of algae is inevitable in hydroponics. When a large amount of algae grows, it changes the balance of components in the culture solution. If the culture solution becomes alkaline, the roots of crops will be damaged.
  • Non-Patent Documents 1 and 2 It has been reported that the use of silver that exhibits bactericidal activity can suppress the growth of algae in hydroponics (see, for example, Non-Patent Documents 1 and 2).
  • Non-Patent Documents 1 and 2 above, algae control measures using silver can suppress the growth of algae, but if a certain amount of silver is used to achieve the effect, the growth of plants is also inhibited. I know it will be suppressed. Therefore, it has been desired to provide a hydroponic cultivation method that suppresses the growth of algae and does not inhibit the growth of plants.
  • the purpose of the present invention is to provide a hydroponic culture medium for use in a hydroponic culture method that suppresses the growth of algae and does not inhibit the growth of plants.
  • the inventors have made intensive studies to solve the above problems, and as a result, a hydroponic culture medium in which a photocatalyst composition in which a metal is supported on a titanium oxide composition is supported on a porous material is provided. can be solved, and the present invention has been completed.
  • the present invention includes the following aspects.
  • the photocatalyst composition (B) is a hydroponic culture medium, which is a photocatalyst composition in which a metal is supported on a titanium oxide composition.
  • the hydroponic culture medium according to [6] wherein the porous material (A) is urethane foam with a density of 10 to 30 g/m 3 .
  • the dispersion (E) further contains a wetting and dispersing agent (F), Production of a hydroponic culture medium according to [10] or [11], wherein the wetting and dispersing agent (F) is a copolymer having an ammonium base or a copolymer having an acid value of 10 mg KOH/g or more having a free fatty acid group.
  • Method. [13] A hydroponic cultivation method using the hydroponic cultivation medium according to any one of [1] to [9] and light irradiation means.
  • a dispersion for suppressing the growth of algae used in hydroponics contains at least a medium (D) and a photocatalyst composition (B),
  • the photocatalyst composition (B) is a dispersion liquid for suppressing the growth of algae, which is a photocatalyst composition in which a metal is supported on a titanium oxide composition.
  • the binder resin (C) is a urethane resin or an acrylic resin.
  • the dispersion (E) further contains a wetting and dispersing agent (F),
  • the wetting and dispersing agent (F) is a copolymer having an ammonium base or a copolymer having an acid value of 10 mg KOH/g or more having a free fatty acid group, suppressing algae growth according to any one of [14] to [20].
  • a hydroponic cultivation medium for use in a hydroponic cultivation method that suppresses the growth of algae and does not inhibit the growth of plants.
  • FIG. 1 shows the results of the follow-up observation of the growth of algae in the bat and the growth of lettuce with or without sowing lettuce seeds in Example 1, Comparative Example 1, and Comparative Example 2, and the observation results on the 7th day.
  • FIG. 2 shows the results of the follow-up observation of the state of algal growth and the state of lettuce growth in the bat with and without sowing lettuce seeds in Example 1, Comparative Example 1, and Comparative Example 2, and the observation results on the 14th day.
  • FIG. 3 shows the results of the follow-up observation of the growth of algae in the bat and the growth of lettuce with or without sowing lettuce seeds in Example 1, Comparative Example 1, and Comparative Example 2, and the observation results on the 21st day.
  • FIG. 4 is a schematic diagram showing an example of a hydroponic cultivation apparatus for carrying out the hydroponic cultivation method.
  • FIG. 5 is a schematic diagram showing an example of a hydroponic cultivation apparatus for carrying out the hydroponic cultivation method.
  • the photocatalyst composition (B) is supported on the porous material (A).
  • the porous material (A) is not particularly limited as long as it is a substrate having a large number of pores and can support the photocatalyst composition (B), and can be appropriately selected according to the purpose.
  • Examples include rockwool, vermiculite, and foams containing cellular structures.
  • foams include synthetic resin foams such as polyurethane, polystyrene, polyethylene, and polypropylene, as well as pulp- and cotton-derived cellulose sponges, sponge-derived natural sponges, and plant-derived fiber porous bodies such as luffa.
  • a biodegradable porous material is preferable because it is discarded after being used for a short period of about one month.
  • a foam having an open-cell structure is suitable as a sponge for hydroponic cultivation because the cells are connected, so that moisture and air can easily pass through the foam.
  • a preferred embodiment of the porous material (A) is a urethane foam porous material.
  • urethane foam is obtained by, for example, using polyol and polyisocyanate as raw materials, stirring and mixing a foaming agent, a foam stabilizer, a catalyst, etc., and simultaneously performing a foaming reaction and a resinification reaction. , refers to plastic foam.
  • urethane foam porous materials a urethane foam porous body having a density of 10 to 30 g/m 3 is more preferable.
  • the density here means the mass per unit volume of a sample containing both air-permeable and air-impermeable cells (here, a porous urethane foam material), ie, the so-called apparent density.
  • This apparent density can be determined according to JIS K 7222:2005 (Foamed plastics and rubber-Determination of apparent density).
  • the photocatalyst composition (B) is a composition exhibiting visible light responsiveness due to the metal being supported on the titanium oxide composition.
  • the titanium oxide composition of the present invention must contain at least titanium oxide, but may contain metal elements other than titanium oxide.
  • a preferred embodiment of the titanium oxide composition of the present invention includes, for example, a titanium oxide composition substantially containing at least one metal element selected from the group consisting of zirconium and niobium.
  • the titanium oxide in the titanium oxide composition preferably contains rutile-type titanium oxide.
  • titanium oxide may also contain anatase-type titanium oxide, brookite-type titanium oxide, and the like.
  • the content of rutile-type titanium oxide in titanium oxide (rutilization rate) is preferably 15 mol% or more from the viewpoint of satisfying excellent anti-algae properties, plant growth, and visible light responsiveness.
  • Titanium oxide produced by either a vapor phase method or a liquid phase method can be used, but it is preferable to use one produced by a liquid phase method.
  • a liquid phase method and a gas phase method are generally known as methods for producing a titanium oxide composition.
  • the liquid phase method is a method of obtaining titanium oxide by hydrolyzing or neutralizing titanyl sulfate obtained from a liquid in which raw ore such as ilmenite ore is dissolved.
  • the vapor phase method is a method of obtaining titanium oxide through a vapor phase reaction between oxygen and titanium tetrachloride obtained by chlorinating raw material ore such as rutile ore.
  • ilmenite ore may be used as the raw material ore for titanium oxide, or titanium slag obtained by metallurgically treating ilmenite ore to increase the purity of titanium may be used.
  • the BET specific surface area of titanium oxide in the titanium oxide composition is preferably in the range of 1 to 200 m 2 /g, preferably 3 to 100 m, from the viewpoint of satisfying excellent anti-algae properties, plant growth, and visible light responsiveness. 2 /g, more preferably 4 to 70 m 2 /g, even more preferably 4 to 50 m 2 /g. A range of 2 /g is particularly preferred.
  • the method for measuring the BET specific surface area of titanium oxide will be described later in Examples.
  • the primary particle size of titanium oxide in the titanium oxide composition is preferably in the range of 0.01 to 0.5 ⁇ m from the viewpoint of satisfying excellent anti-algae properties, plant growth, and visible light responsiveness. A range of 0.03 to 0.35 ⁇ m is more preferable, and a range of 0.06 to 0.35 ⁇ m is even more preferable.
  • the method for measuring the primary particle size of titanium oxide indicates a value measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM).
  • each primary particle of titanium oxide is measured, the average is taken as the particle diameter of the primary particles, and then for 100 or more titanium oxide particles, each particle The volume (weight) of is approximated to a cube of the determined particle size, and the volume average particle size can be taken as the average primary particle size.
  • the titanium oxide composition of the present invention is preferably a titanium oxide composition substantially containing at least one metal element selected from the group consisting of zirconium and niobium.
  • the content ratio of zirconium to titanium 100 (Zr/Ti ratio) in the titanium oxide composition is preferably 0.03 or more, more preferably 0.04 or more, still more preferably 0.05 or more, and preferably 0. 0.8 or less, more preferably 0.5 or less, and still more preferably 0.3 or less. Any combination of these upper and lower limits may be used.
  • the content ratio of zirconium to titanium 100 (Zr/Ti ratio) in the titanium oxide composition is preferably 0.03 to 0.8, more preferably 0.04 to 0.5, still more preferably 0.05 to 0.5. 3.
  • the content ratio of niobium to titanium 100 (Nb/Ti ratio) in the titanium oxide composition is preferably 0.05 or more, more preferably 0.08 or more, still more preferably 0.1 or more, and preferably 0. 0.8 or less, more preferably 0.5 or less, and still more preferably 0.3 or less. Any combination of these upper and lower limits may be used.
  • the content ratio of niobium to titanium 100 (Nb/Ti ratio) in the titanium oxide composition is preferably 0.05 to 0.8, more preferably 0.08 to 0.5, still more preferably 0.10 to 0.5. 3.
  • titanium oxide substantially contains a metal element means that the content ratio of the metal element in titanium oxide is 0.02 or more to 100 of titanium.
  • Titanium oxide substantially containing a metal element is a titanium oxide composition substantially containing a metal element (zirconium and/or niobium).
  • Titanium oxide which substantially contains a metal element (zirconium and/or niobium), has a small cohesive force with respect to the specific surface area (BET value) due to the primary particles, and can suppress the viscosity of the mixed liquid. , and is presumed to contribute to the improvement of the concentration of titanium oxide.
  • a method for producing the titanium oxide composition it can be produced by the general sulfuric acid method based on the liquid phase method described above, or the general chlorine method based on the vapor phase method described above.
  • a titanium oxide composition can be produced as follows. a) According to a general sulfuric acid method, sulfuric acid, water, and iron are added to and dissolved in ilmenite ore to obtain a solution containing titanium sulfate and iron sulfate as main components. Next, impurities such as iron sulfate are removed, followed by thermal hydrolysis to obtain a hydrous titanium hydroxide composition. Next, the titanium hydroxide composition is washed, sintered at a temperature in the range of 400° C. to 1,600° C., and the obtained solids are pulverized. Thereby, a titanium oxide composition can be obtained.
  • a titanium oxide composition can be produced as follows. b) According to a general chlorine method, rutile ore, coke and chlorine are reacted to obtain titanium tetrachloride. Titanium tetrachloride is distilled to remove impurities, subjected to combustion treatment under oxygen at a temperature range of 700° C. to 1,600° C., and after cooling, the resulting solid is pulverized. Thereby, a titanium oxide composition can be obtained.
  • the titanium oxide composition when producing a titanium oxide composition substantially containing at least one metal element selected from the group consisting of zirconium and niobium, for example, the titanium oxide composition is prepared as follows. can be manufactured. c) According to a general sulfuric acid method, sulfuric acid, water, and iron are added to and dissolved in a mixture of ilmenite ore, niobium pentoxide, and zirconium oxide to obtain a solution containing titanium sulfate and iron sulfate as main components. . Next, impurities such as iron sulfate are removed, followed by thermal hydrolysis to obtain a hydrous titanium hydroxide composition.
  • the titanium hydroxide composition is washed, sintered at a temperature in the range of 400° C. to 1,600° C., and the obtained solids are pulverized. Thereby, a titanium oxide composition substantially containing at least one metal element selected from the group consisting of zirconium and niobium can be obtained.
  • the above-mentioned Surface treatments such as inorganic substance treatment and organic substance treatment may be arbitrarily combined with respect to the titanium oxide composition.
  • inorganic treatment include surface treatment with inorganic metal hydrous oxides such as alumina, silica, zinc oxide, zirconia, titania, tin oxide and antimony oxide.
  • Surface treatment with compounds such as polyols, alkanolamines, and silicones can be used as the organic treatment.
  • a surface treatment method a known method used for titanium oxide, such as surface treatment of alumina of titanium oxide pigment, surface treatment of silane coupling agent, and the like can be used.
  • a metal is supported on the titanium oxide composition to form a photocatalyst composition (B).
  • the metal may be in the form of a metal element, an alloy, or a compound containing metal ions or metal elements.
  • Compounds containing metal elements include, for example, metal chlorides, bromides, iodides, oxides, suboxides, sulfides, cyanides, hydroxides, fluorides, sulfate compounds, sulfite compounds, nitrate compounds, Nitrate compounds, phosphate compounds, phosphite compounds, carbonate compounds, etc. are included, and organometallic compounds are not included.
  • the metal supported on titanium oxide works as an active site, promotes multi-electron reactions by accumulating charges, and functions as a co-catalyst such as promoting charge separation, thereby improving the visible light range of the photocatalyst composition.
  • Photocatalytic activity can be improved.
  • various functions can be imparted to the photocatalyst composition by supporting the metal, and in particular, the photocatalyst composition of the present invention can satisfy both the effects of suppressing the growth of algae and promoting the growth of plants.
  • the supported metal is preferably insoluble or sparingly soluble in water, and in the hydroponic culture medium of the present invention, the metal is eluted as metal ions from the porous material (A). Therefore, plants can be cultivated safely.
  • the photocatalyst composition of the present invention is also excellent in antibacterial effect.
  • the metal element of the metal supported on the photocatalyst composition (B) may be a typical metal or a transition metal. Not included. Specifically, for example, transition metals such as copper, iron, tungsten, zirconium, molybdenum, cobalt, manganese, neodymium, nickel, palladium, platinum and gold, and typical metals such as zinc, aluminum, antimony, tin and bismuth. It can be used preferably.
  • copper is preferred, and divalent copper is more preferred, from the viewpoint of satisfying excellent anti-algae properties, plant growth, visible light responsiveness, and the like.
  • divalent copper compounds examples include copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate, copper ammonium chloride, copper pyrophosphate, and carbonate.
  • Inorganic acid salts of divalent copper such as copper; halides of divalent copper such as copper chloride, copper fluoride and copper bromide; copper oxide, copper sulfide, azurite, malachite, copper azide and the like can be used. These compounds may be used alone or in combination of two or more.
  • CuX2 (In formula (1), X represents a halogen atom, CH 3 COO, NO 3 , or (SO 4 ) 1/2 .)
  • X in the above formula (1) is more preferably a halogen atom, more preferably a chlorine atom.
  • a processing method for supporting the support (the metal) on the photocatalyst composition (B) a known method can be used as long as it is a wet method. Examples thereof include a method of adsorbing with a mixed solution of a titanium oxide composition suspended in an aqueous solution of a support and a solvent, and a method of reacting a titanium oxide composition with a mixed solution of a support, a solvent and an alkaline substance. Make a mixture for processing. The mixture contains at least a titanium oxide composition and a solvent.
  • the concentration of the titanium oxide composition in the mixed solution is preferably in the range of 3 to 40% by mass.
  • the amount of the support raw material used in the mixed solution is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.1 to 15 parts by mass, with respect to 100 parts by mass of titanium oxide. 0.3 to 10 parts by mass is more preferable.
  • the solvent only water may be used, or a mixed solvent of water and an organic solvent may be used.
  • a mixed solvent an aqueous solvent containing water as a main component is preferred.
  • the aqueous solvent containing water as a main component refers to a solvent having the highest water content in the total amount of the solvent, preferably 50% by mass or more of water.
  • the composition of the organic solvent is determined according to the properties of the desired mixed liquid. From the viewpoint of reducing environmental load and improving safety, the mixed solvent preferably contains an organic solvent in an amount of 30% by mass or less, preferably 5% by mass or less in the total amount of the solvent.
  • organic solvent that can be used as the solvent is not particularly limited, but for example, an organic solvent that is miscible with water is preferably used.
  • Organic solvents that can be used as solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, and 3-methyl-3-pentane.
  • monofunctional alcohols such as tanol, Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, 1,12-dodecanediol, propylene glycol, 1,2-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-methyl-1,3-propanediol, 1,2 -
  • diols such as hexanediol, dipropylene glycol and diethylene glycol
  • polyhydric alcohols such as glycerin
  • ketones such as methyl ethyl ketone and methyl isobutyl ketone
  • dimethylformamide tetrahydrofuran
  • 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propyl alcohol (NPA), isopropyl alcohol (IPA ), propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol) (PGM), and ethylene glycol are preferred.
  • alkaline substance examples include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, basic surfactants, and the like. It is preferable to use
  • the alkaline substance is preferably added in the form of a solution, since the reaction can be easily controlled.
  • a range of L is more preferred, and a range of 0.5 to 3 mol/L is even more preferred.
  • a more preferred embodiment of the method for producing the photocatalyst composition (B) includes a production method for obtaining the photocatalyst composition (B) by supporting a divalent copper compound on a titanium oxide composition.
  • a method for supporting a divalent copper compound on a titanium oxide composition will be described in detail below.
  • the mixed solution may be obtained by mixing the titanium oxide composition, the divalent copper compound raw material, the solvent, and the alkaline substance.
  • a method of mixing raw materials of a valent copper compound, stirring, and then adding an alkaline substance and stirring may be used.
  • the divalent copper compound derived from the divalent copper compound raw material is supported on the titanium oxide composition.
  • the total stirring time for the mixed solution is, for example, 5 to 120 minutes, preferably 10 to 60 minutes.
  • the reaction temperature of the mixed solution is, for example, in the range of room temperature to 70°C.
  • the titanium oxide composition, the divalent copper compound raw material, and water are mixed and stirred, and then the alkaline substance is mixed and stirred.
  • the pH of the mixed solution is preferably in the range of 8 to 11, more preferably in the range of 9.0 to 10.5.
  • the solid content can be separated.
  • the method for separation include filtration, sedimentation, centrifugation, and evaporation drying, with filtration being preferred.
  • the separated solid content may then be washed with water, pulverized, classified, etc., if necessary.
  • the solid content is heat-treated from the viewpoint that the divalent copper compound derived from the divalent copper compound raw material and supported on the titanium oxide composition can be more strongly bonded.
  • the heat treatment temperature is preferably in the range of 150 to 600°C, more preferably in the range of 250 to 450°C.
  • the heat treatment time is preferably 1 to 10 hours, more preferably 2 to 5 hours.
  • a photocatalyst composition (B) in which a divalent copper compound is supported on a titanium oxide composition can be obtained.
  • the amount of the bivalent copper compound supported by the titanium oxide composition is in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of titanium oxide. It is preferable from the viewpoint of satisfying plant growth and visible light responsiveness.
  • the amount of the divalent copper compound supported can be adjusted by adjusting the amount of the divalent copper compound raw material used in the mixed solution. A method for measuring the supported amount of the divalent copper compound will be described later in Examples.
  • the mixed solution may contain other ingredients as long as the effects of the present invention can be obtained.
  • Other components include pigments, leveling agents, antifoaming agents, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants and the like.
  • the content of the photocatalyst composition (B) in the porous material (A) is is preferably 0.1 kg/m 3 to 2 kg/m 3 .
  • a preferable embodiment of the hydroponic culture medium includes a hydroponic culture medium in which the photocatalyst composition (B) is supported on the porous material (A) via the binder resin (C).
  • the binder resin (C) include urethane-based resins and acrylic-based resins.
  • the urethane-based resin include polyester-polyurethane resin, polyether-polyurethane resin, polycarbonate-polyurethane resin, and the like.
  • a water-dispersible polyurethane resin having an alkylene oxide chain in the molecule can be used.
  • the molecule may contain a hydrophilic group such as a carboxylic acid or a sulfonic acid.
  • a hydrophilic group such as a carboxylic acid or a sulfonic acid.
  • examples of commercially available water-dispersible polyurethane resins containing an alkylene oxide chain in the molecule include "Hydran” (trade name) manufactured by DIC Corporation and “Impranil” (trade name) manufactured by Covestro. , "Permaline” (trade name) manufactured by Sanyo Chemical Industries, Ltd., and the like.
  • a water-dispersible resin of polycarbonate-polyurethane resin for example, Hydlan WLS-210, a commercially available product, can also be used.
  • the acrylic resin is obtained by polymerizing a polymerizable monomer containing an acrylic monomer as an essential component. Moreover, in order to improve solubility or dispersion in an aqueous medium, it is preferable to use a polymerizable monomer having a carboxyl group.
  • acrylic monomers include polyethylene glycol mono (meth) acrylate, stearoxy polypropylene glycol mono (meth) acrylate, allyloxy polyethylene glycol mono (meth) acrylate, allyloxy polypropylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate.
  • Alkyl group-terminated polyalkylene glycol mono(meth)acrylates such as (meth)acrylates and nonylphenoxypolypropylene glycol mono(meth)acrylate; silane-based (meth)acrylates such as trimethylsiloxyethyl (meth)acrylate; 3-(meth)acryloyl (Meth)acryloyloxyalkyls such as oxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, etc.
  • Silane compounds fluorine-based (meth)acrylates such as perfluoroalkylethyl (meth)acrylate; glycidyl (meth)acrylate, epoxy (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylene glycol tetra(meth)acrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis[4-(acryloxymethoxy)phenyl]propane, 2,2-bis [4-(Acryloxyethoxy)phenyl]propane, dicyclopentenyl (meth)acrylate tricyclodecanyl (meth)acrylate, tris (acryloxyethyl) isocyanurate, urethane (meth)acrylate and other (meth)acrylate compounds; Examples thereof include (meth)acrylates having an alkylamino group such as dimethyla
  • (meth)acrylate refers to one or both of methacrylate and acrylate
  • (meth)acryloyl refers to one or both of methacryloyl and acryloyl
  • (meth)acrylic acid refers to one or both of methacrylic acid and acrylic acid.
  • the raw materials include, for example, (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, polymerization having a carboxyl group such as citraconic acid can be used.
  • These polymerizable monomers can be used alone or in combination of two or more.
  • part or all of the carboxyl group is replaced with a metal hydroxide such as potassium hydroxide or sodium hydroxide. ; it may be neutralized with a base such as ammonia, an organic substance such as triethylamine.
  • polymerizable monomers examples include styrene, styrene derivatives ( ⁇ -methylstyrene, p-dimethylsilylstyrene, (p-vinylphenyl)methylsulfide, p-hexynylstyrene, p-methoxystyrene, p-tert-butyl dimethylsiloxystyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, etc.), aromatic vinyl compounds such as vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene; acrylamide, N,N-dimethylacrylamide, isopropylacrylamide, diacetoneacrylamide and other polymerizable monomers.
  • the polymerizable monomer examples include styrene, styrene derivatives ( ⁇ -methyls
  • a known emulsion polymerization method can be used as a method for producing the acrylic resin.
  • the dispersion liquid used for manufacturing the hydroponic culture medium will be described in detail below.
  • the binder resin (C) will also be described in detail.
  • the photocatalyst composition (B) By supporting the photocatalyst composition (B) on the porous material (A) via the binder resin (C), the photocatalyst composition (B) is more firmly supported on the porous material (A). , detachment of the photocatalyst composition (B) from the porous material (A) can be prevented. Therefore, even if water is circulated, the photocatalyst composition (B) can be prevented from falling off, and a medium suitable for hydroponics can be provided. A method for producing a hydroponic culture medium in which the photocatalyst composition (B) is supported on the porous material (A) via the binder resin (C) will be described later.
  • the method for producing a hydroponic culture medium of the present invention comprises: (I) step: a step of dispersing the photocatalyst composition (B) in the medium (D) to obtain a dispersion (E); (II) step: a step of impregnating the porous material (A) with the dispersion (E); (III) step: a step of drying and removing the medium (D) from the porous material (A); have
  • the photocatalyst composition (B) when the photocatalyst composition (B) is supported on the porous material (A) via the binder resin (C), the photocatalyst composition (B) is more likely to be absorbed by the porous material (A).
  • the following production method can be mentioned, since a firmly supported hydroponic culture medium can be obtained.
  • step a step of dispersing the photocatalyst composition (B) and the binder resin (C) in the medium (D) to obtain a dispersion (E);
  • step a step of impregnating the porous material (A) with the dispersion (E);
  • step a step of drying and removing the medium (D) from the porous material (A);
  • the photocatalyst composition (B) is dispersed in the medium (D) to obtain a dispersion (E).
  • the medium (D) is provided with the photocatalyst composition (B) and the binder resin (C). Disperse to obtain a dispersion (E).
  • the photocatalyst composition (B) is as described in the section ⁇ Photocatalyst composition (B)> above.
  • the binder resin (C) is as described in the section ⁇ preferred embodiment of hydroponic culture medium>>.
  • Medium (D) contains water.
  • the medium (D) is an aqueous medium containing water as a main component and may contain an organic solvent.
  • an organic solvent In the present invention, only water may be used, or a mixture of water and an organic solvent may be used, but from the viewpoint of reducing environmental load and improving safety, the amount of organic solvent used is preferably as small as possible.
  • the medium (D) preferably contains the organic solvent in an amount of 30% by mass or less, preferably 5% by mass or less.
  • the organic solvent that can be used is not particularly limited. - monofunctional alcohols such as pentanol, methyl ethyl ketone, methanol, ethanol, n-propyl alcohol (hereinafter also referred to as NPA) and isopropyl alcohol (hereinafter also referred to as IPA), various diols, polyhydric alcohols such as glycerin, ethylene Glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol , 1,12-dodecanediol, propylene glycol, 1,2-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-methyl-1,3-propanedio
  • Bisphenol A aromatic diols which are adducts of alkylene oxides having 2 or 3 carbon atoms (average addition mole number of 1 to 16) of bisphenol A, alicyclic diols such as hydrogenated bisphenol A, polyoxypropylene-2,2- Bis(4-hydroxyphenyl)propane, polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane, cyclohexanediol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether , diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol
  • the dispersion (E) may further contain a wetting and dispersing agent (F).
  • a wetting and dispersing agent (F) any dispersing agent can be used as long as it is effective in improving the wettability and dispersibility of the metal oxide.
  • Copolymers having free fatty acid groups and having an acid value of 10 mg KOH/g or more are included.
  • the wetting and dispersing agents (F) dispersing agents having an acid value are preferably used.
  • the above copolymer preferably has a relatively high molecular weight.
  • the molecular weight of the copolymer is preferably 500 to 200,000, more preferably 1,000 to 150,000.
  • copolymers having an ammonium base for example, polyfunctional polymers and acrylic copolymers are preferred. If the molecular weight of the copolymer is within the above range, the dispersibility is improved.
  • polyfunctional polymers include polymers having, as structural units, plural types of polymerizable monomers having functional groups such as amine groups, carboxyl groups, ether groups, and silyl groups.
  • acrylic copolymers include copolymers having acrylic polymerizable monomers, such as methacrylic acid and acrylic acid, as constitutional units.
  • Ammonium bases include, for example, alkylolamine salts.
  • the free fatty acid group can be obtained by using a polymerizable monomer having a carboxyl group such as (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, or citraconic acid as a structural unit. be.
  • the acid value of the copolymer having a free fatty acid group is 10 mg KOH/g or more, preferably 20 mg KOH/g or more, and usually 150 mg KOH/g or less, preferably 100 mg KOH/g or less.
  • the acid value of the copolymer having free fatty acid groups may be 10 mg KOH/g or more and 150 mg KOH/g or less, may be 10 mg KOH/g or more and 100 mg KOH/g or less, may be 20 mg KOH/g or more and 150 mg KOH/g or less, and may be 20 mg. KOH/g or more and 100 mg KOH/g or less may be sufficient.
  • Acid number is defined as milligrams of potassium hydroxide required to neutralize free fatty acids contained in 1 g.
  • wetting and dispersing agent (A) falling within the above range include BYK-154, DISPERBYK180, DISPERBYK181, DISPERBYK190, DISPERBYK191, and DISPERBYK194N manufactured by BYK-Chemie Japan.
  • the dispersion liquid (E) contains the above-described components
  • the mixing method can be appropriately selected in consideration of the type of each component to be used.
  • the method for producing the dispersion (E) described below can be mentioned.
  • An example in which the dispersion (E) also contains the wetting and dispersing agent (F) will be described below.
  • the photocatalyst composition (B), the wetting and dispersing agent (F) and the medium (D) are mixed and stirred.
  • the mixing ratio of the photocatalyst dispersing element (G) and the binder resin (C) in the dispersion (E) is preferably 10:90 to 90:10 in solid content ratio.
  • the porous material (A) is impregnated with the dispersion (E).
  • the porous material (A) can be impregnated with the dispersion (E) by placing the dispersion (E) in an impregnation tank and supplying the porous material (A) into this bath.
  • the medium (D) is removed by drying from the porous material (A).
  • the medium (D) is dried and removed from the porous material (A) using squeeze rolls or a drying oven. More specifically, for example, after the impregnation in the step (II), the porous material (A) is squeezed with a squeeze roll to adjust the adhesion amount of the dispersion (E) in the porous material (A).
  • the squeezing roll interval is adjusted so that the dispersion liquid (E) in an amount such that the dry weight of the dispersion liquid (E) is 0.1 kg/m 3 to 3 kg/m 3 adheres to the porous material (A). do.
  • the porous material (A) is passed through the squeezing rolls. After passing through the squeezing rolls, the porous material (A) is passed through a drying furnace set at 60°C to 160°C and dried with hot air. Thereby, the hydroponic culture medium of the present invention can be obtained.
  • dispersion liquid As described above, the dispersion liquid (E) is prepared in order to support the photocatalyst composition (B) on the porous material (A) when producing the hydroponic culture medium.
  • Dispersion (E) contains medium (D) and photocatalyst composition (B).
  • a preferred embodiment of the dispersion (E) further contains a binder resin (C).
  • the dispersion liquid (E) can be used for medium processing to produce a hydroponic culture medium.
  • the dispersion liquid (E) according to the present invention is applicable not only to the production of culture media, but also to hydroponics in general where suppression of algae growth is desired.
  • it can be applied to a water tank for hydroponics (also called a cultivation container (bat)), a hydroponic panel (also called a cultivation board), etc., as a dispersion for suppressing the growth of algae used in hydroponics.
  • a water tank for hydroponics also called a cultivation container (bat)
  • a hydroponic panel also called a cultivation board
  • a dispersion for suppressing the growth of algae used in hydroponics .
  • More specifically, for example, application to cultivation vessels (bats), growth boards, culture solution circulation tanks, filtering devices, filters, piping, and the like can be mentioned.
  • hydroponic cultivation devices it is preferably applied to a portion in contact with the culture medium, near the site where algae are generated, and more preferably applied to the site irradiated with light. Therefore, it is particularly preferable to apply the dispersion (E) according to the present invention to hydroponic culture media, cultivation containers (bats), growth boards, and the like.
  • the binder resin (C) contained in the dispersion (E) is desirably selected from resin solutions, resin dispersions, and curable liquid resins that can impart adhesiveness to the application member.
  • the binder resin (C) include acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, biodegradable resins such as cellulose, which are used as resins for coating agents and adhesives, UV curable ( A meth)acrylate resin or the like can be used. These resins may be used in combination as appropriate. Water, an organic solvent, or the like can be appropriately used as a diluent for the dispersion (E).
  • the dispersion (E) may be a solventless type such as a UV curable or thermosetting resin. An aqueous dispersion is preferred from the viewpoint of environmental friendliness and safety of coating workers.
  • the hydroponic culture medium of the present invention plants are grown using the hydroponic culture medium of the present invention. More specifically, the hydroponic culture medium of the present invention, a light irradiation means for irradiating the hydroponic culture medium with visible light, and more preferably a vessel for holding the culture solution and a circulation means for circulating the culture solution. and are used to grow plants.
  • the culture solution a culture solution generally used in hydroponics can be used, and examples thereof include an aqueous solution containing plant nutrients.
  • Nutrients for plants include nutrients containing nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, boron, iron, manganese, zinc, molybdenum, and the like.
  • Nutrients for plants include inorganic nutrients and organic nutrients containing these elements.
  • the nutrient composition of the plant in the culture solution is selected according to the growing plant and the growth state of the plant.
  • the light irradiating means is, for example, means for irradiating the growing plant and the hydroponic culture medium with visible light (for example, a device arranged at a position where the portion irradiated with light is above the container).
  • the light irradiating means may be a device that irradiates at least the hydroponic culture medium with visible light.
  • the light irradiation means is preferably a device that irradiates the plants and the hydroponic culture medium with visible light. .
  • the light irradiation means has a light source that emits visible light.
  • the light source include an LED (Light Emitting Diode) unit, a laser unit, a fluorescent lamp, etc. Among them, an LED lighting means is preferable.
  • the irradiation time of the light irradiation means in hydroponics can be appropriately selected according to the type of growing plant, but for example, the irradiation time per day is 16 hours (8 hours in a dark place). be able to.
  • the photocatalyst composition (B) according to the present invention when a copper compound is used as the metal, the photocatalyst composition (B) supporting the copper compound is also excellent in dark place activity. is effective in suppressing
  • a hydroponic cultivation apparatus (10) shown in FIGS. 4 and 5 is an apparatus for growing a plant (11) supported on a culture medium (14) using a culture solution (12).
  • the hydroponic cultivation apparatus has a cultivation container (13), a culture solution circulation filtration pump (16), light irradiation means (20), and a light source (21).
  • the cultivation medium (14) includes a plant support portion (14a) for supporting the plant (11) and the plant support portion (14a). and a holding portion (14b) for holding. In the holding part (14b), if the opening for inserting the plant support part (14a) is narrow and the plant is held by the holding part even if the plant is directly inserted into the opening, The plant support portion (14a) may not be provided.
  • the dispersion liquid (E) according to the present invention to hydroponic culture media, cultivation containers (bats), cultivation boards, and the like in which algae easily grow by light irradiation.
  • Porous material A1 A soft urethane foam (open cell type) with a thickness of 28 mm is cut so that one block can be separated into 23 mm squares, and a cross cut is made in the center of each block for seed planting. Used as material A1. The apparent density of the porous material A1 was 13 kg/m 3 .
  • Titanium oxide composition b According to a general sulfuric acid method, sulfuric acid, water, and iron were added and dissolved in a mixture of ilmenite ore, niobium pentoxide, and zirconium oxide to obtain a solution containing titanium sulfate and iron sulfate as main components. Impurities such as iron sulfate were removed, followed by thermal hydrolysis to obtain a hydrous titanium hydroxide composition. The titanium hydroxide composition was washed, calcined at 900° C., and the obtained solid was pulverized to obtain a titanium oxide composition b having the following characteristics.
  • Photocatalyst dispersion G1 25 parts of photocatalyst composition B1, 75 parts of water, and 8 parts of wetting and dispersing agent F1 (acid value 75 mgKOH/g, BYK-Chemie Co., Ltd. "DISPERBYK-194N") are mixed and stirred, and 100 parts of 1.0 mm ⁇ ceramic beads are mixed. was added and ground in a sand grinder for 4 hours. After grinding, the beads were separated from the dispersion liquid to obtain a photocatalyst dispersion G1.
  • Dispersion E1 Water 561 parts by mass, photocatalyst dispersion G1 (solid content 25% by mass) 20 parts by mass, polycarbonate-polyurethane resin water dispersion C1 ("Hydran WLS-210" manufactured by DIC Corporation) 19 parts by mass (total 600 parts by mass) were uniformly mixed using a dispersion stirrer (TK Homodisper manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a dispersion E1 for processing the medium.
  • the solid content of this dispersion was 19.2% by mass, and the solid content ratio of the photocatalyst composition B1 and the binder resin C1 was 44:56.
  • Example 1 Preparation of hydroponic culture medium>
  • a hydroponic culture medium in which the photocatalyst composition was supported on the porous material was produced. That is, the above dispersion E1 was placed in an impregnation tank, 28 mm thick flexible urethane foam A1 was supplied into the bath, and the squeezing roll interval was adjusted so that the dry weight of the dispersion was 0.6 kg/m 3 .
  • the soft urethane foam A1 was passed through a squeezing roll and dried with hot air in a drying furnace set at 120° C. to obtain the target hydroponic culture medium.
  • the hydroponic culture medium the growth of algae and the growth of lettuce were evaluated by the methods described below.
  • the porous material As the porous material, the flexible polyurethane foam described in Japanese Patent No. 2813693 was used as a reference.
  • the hydroponic culture medium is a commercially available antibacterial sponge that is a soft urethane foam containing a silver-based antibacterial agent (Crypika Sponge Ag antibacterial product manufactured by Kikuron Co., Ltd.; apparent density 30 kg/m 3 ) processed to the same dimensions as the porous material A1.
  • a silver-based antibacterial agent Cosmetic Sponge Ag antibacterial product manufactured by Kikuron Co., Ltd.; apparent density 30 kg/m 3
  • algae generation and lettuce growth conditions were evaluated, except that the conditions were as follows.
  • Titanium oxide was completely dissolved in a hydrofluoric acid solution, and the extract was analyzed by an ICP emission spectrometer to quantify the supported amount (parts by mass) of the divalent copper compound with respect to 100 parts by mass of titanium oxide.
  • FIG. 1 is a photograph showing the observation results on the 7th day
  • FIG. 2 is a photograph showing the observation results on the 14th day
  • FIG. 3 is a photograph showing the observation results on the 21st day.
  • Example 1, Comparative Example 1, and Comparative Example 2 the observation results of the state of algae generation in the bat with and without seeding of lettuce seeds and the state of lettuce growth were evaluated according to the above evaluation criteria, and the results are shown in the table below. 1.
  • Example 1 suppresses the generation of algae as compared with Comparative Example 1.
  • Comparative Example 2 algae growth was greatly suppressed, but the growth of lettuce was significantly inhibited. It was confirmed that hydroponics using a medium supporting the photocatalyst composition of the present invention can achieve both the contradictory effects of less inhibition of crop growth and suppression of algae growth.

Abstract

La présente invention concerne un milieu de culture hydroponique, dans lequel une composition de photocatalyseur (B) est supporté sur un matériau poreux (A). Ladite composition de photocatalyseur (B) est une composition de photocatalyseur dans laquelle un métal est supporté sur une composition d'oxyde de titane. Ce milieu de culture hydroponique est destiné à être utilisé dans un procédé hydroponique qui supprime l'apparition d'algues et n'inhibe pas la croissance de plantes.
PCT/JP2022/031156 2021-09-01 2022-08-18 Milieu de culture hydroponique, procédé de production de milieu de culture hydroponique, procédé hydroponique utilisant un milieu de culture hydroponique, et liquide de dispersion pour supprimer l'apparition d'algues WO2023032686A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10108564A (ja) * 1996-10-04 1998-04-28 Takagi Ind Co Ltd 栽培基材及び栽培装置
JP2005313055A (ja) * 2004-04-28 2005-11-10 Toagosei Co Ltd 機能性分散液
JP2005329360A (ja) * 2004-05-21 2005-12-02 Noritake Co Ltd 浄化材及びその製造方法
JP2011518094A (ja) * 2007-12-19 2011-06-23 ザ ボード オブ トラスティーズ オブ ザ ユニヴァーシティー オブ イリノイ 共ドープ酸化チタン発泡体および水殺菌装置
JP2011172539A (ja) * 2010-02-25 2011-09-08 Chugoku Electric Power Co Inc:The 栽培装置
JP2015019653A (ja) * 2013-07-23 2015-02-02 東洋ゴム工業株式会社 人工土壌粒子
JP2017039784A (ja) * 2015-08-17 2017-02-23 Toto株式会社 塗料組成物および塗装体
JP2017155368A (ja) * 2016-03-03 2017-09-07 Dic株式会社 繊維加工用樹脂組成物、それを用いた布帛
JP2017184622A (ja) * 2016-03-31 2017-10-12 前澤化成工業株式会社 水耕栽培用マット
JP2020146013A (ja) * 2019-03-15 2020-09-17 富士ゼロックス株式会社 水耕栽培用培地、および水耕栽培装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015097989A (ja) 2013-11-19 2015-05-28 昭和電工株式会社 ウイルス除去剤及びウイルス除去方法
JP2018149503A (ja) 2017-03-14 2018-09-27 日本曹達株式会社 防藻方法及び防藻材

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10108564A (ja) * 1996-10-04 1998-04-28 Takagi Ind Co Ltd 栽培基材及び栽培装置
JP2005313055A (ja) * 2004-04-28 2005-11-10 Toagosei Co Ltd 機能性分散液
JP2005329360A (ja) * 2004-05-21 2005-12-02 Noritake Co Ltd 浄化材及びその製造方法
JP2011518094A (ja) * 2007-12-19 2011-06-23 ザ ボード オブ トラスティーズ オブ ザ ユニヴァーシティー オブ イリノイ 共ドープ酸化チタン発泡体および水殺菌装置
JP2011172539A (ja) * 2010-02-25 2011-09-08 Chugoku Electric Power Co Inc:The 栽培装置
JP2015019653A (ja) * 2013-07-23 2015-02-02 東洋ゴム工業株式会社 人工土壌粒子
JP2017039784A (ja) * 2015-08-17 2017-02-23 Toto株式会社 塗料組成物および塗装体
JP2017155368A (ja) * 2016-03-03 2017-09-07 Dic株式会社 繊維加工用樹脂組成物、それを用いた布帛
JP2017184622A (ja) * 2016-03-31 2017-10-12 前澤化成工業株式会社 水耕栽培用マット
JP2020146013A (ja) * 2019-03-15 2020-09-17 富士ゼロックス株式会社 水耕栽培用培地、および水耕栽培装置

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