JP2013126623A - Catalyst body holding positive hole in light irradiation non-receiving state, method for producing the same, and antiviral/antibacterial cloth - Google Patents

Abstract

PROBLEM TO BE SOLVED: To establish a means for measuring characteristics of a catalyst to be used in a light irradiation non-receiving state and to provide a non-photocatalyst body having a new structure.SOLUTION: A catalyst body holding a positive hole in the light irradiation non-receiving state is obtained by supporting a solid composition containing the positive hole, which is produced by drying one or more kinds selected from carboxylates of transition metals and/or transition metal oxides such as titanium oxalate, titanium lactate, zirconium acetate, zirconium oxalate, manganese oxalate, iron oxalate, cobalt oxalate, nickel oxalate, copper oxalate, zinc oxalate, ammonium titanyl oxalate, oxy-vanadium oxalate and oxy-zirconium acetate, on the surface of a base material in the presence of silicon dioxide as a catalyst layer.

Description

  The present invention relates to a catalyst body formed on the surface of a substrate, and relates to a catalyst body that retains holes in an environment that is not exposed to light such as ultraviolet rays, a method for producing the same, and an antiviral effect that utilizes the characteristics of the catalyst body Concerning sex and antibacterial cloth.

  The photocatalyst is said to decompose, sterilize, and inactivate viruses existing in the atmosphere and water, pathogenic bacteria such as Escherichia coli, and harmful organic substances by active oxygen generated by irradiation with light such as ultraviolet rays. Active oxygen refers to superoxide anion, hydrogen peroxide solution, OH radical (hydroxy radical) and singlet oxygen. Among them, a semiconductor known as a photocatalyst is irradiated with light such as ultraviolet rays, and electrons in the valence band are generated. The OH radicals generated by holes generated after moving to the conductive band take electrons from the water oxidize and decompose and sterilize various substances, and are particularly highly evaluated.

  A method of using titanium dioxide as a photocatalyst for generating such holes is widely known, and many proposals have been made on specific methods of using it. Also, a method of using an organic titanium compound such as titanium oxalate as a titanium dioxide precursor or intermediate (Patent Documents 1 and 2), or a method of improving the adhesion of titanium dioxide particles (Patent Document 3). In addition, methods (Patent Documents 4, 5, and 6) used for the purpose of improving catalytic activity and wear resistance are also known. In addition, methods using methylene blue are known as means for measuring the organic matter decomposition performance of these photocatalysts (Non-Patent Documents 1 and 2). In Non-Patent Document 1, OH radicals have high reactivity and short lifetime, so direct observation at room temperature is difficult. However, OH radicals are reacted at room temperature to be converted into stable radical DMPO-OH to be ESR (electron The method of detecting by spin resonance spectroscopy is introduced.

  However, the photocatalyst requires a high energy light source such as ultraviolet rays to generate holes. In a room that is not exposed to sunlight, there is a problem such as the installation cost and power consumption cost for installing a separate light source, and it has not yet become widespread. In order to avoid this harmful effect, research on visible light responsive photocatalysts has been carried out, but it is said that electron-hole pairs separated by photoexcitation are restored by recombination and often do not exhibit the expected performance. Therefore, there has been a demand for a catalyst that functions in the absence of light as a material used in an environment where light does not reach, such as a sanitary mask core and antibacterial cloth.

  Patent Document 7 proposes a titanium phosphate compound composed of titanium hydroxide, phosphoric acid, and alcohol having a specific blending ratio as an antibacterial, deodorant, and fungicidal method without ultraviolet light irradiation. Further, Patent Document 8 discloses that a functional structure having a metal-deficient non-stoichiometric oxide on which a non-stoichiometric oxide of a transition metal such as titanium forms a p-type semiconductor has an OH radical without ultraviolet irradiation. It is disclosed that it produces the same function as a photocatalyst. In addition, in order to obtain such a functional structure, a means is described in which the metal-deficient non-stoichiometric oxide powder is caused to collide and be fixed to a substrate via a carrier gas having a flow rate of 100 m / s or more. Further, Patent Document 9 proposes a catalyst having an environmental purification function such as inactivating a virus when irradiated with ultraviolet rays in advance in the absence of light by the present inventor.

JP S54-98716 A JP 2000-290533 A JP 2000-271489 A JP 2003-321778 A JP 2005-132944 A JP 2000-109343 A JP 2002-308712 A JP 2006-43574 A JP 2008-296121 A

Yoshio Nosaka and Atsuko Nosaka “Introductory Photocatalyst” 2004 Tokyo Book Satoshi Horikiri et al. BUNSEKIKAGAKU vol. 52. No.10, pp881-885 (2003) Decomposition of methylene blue with porous photocatalyst and high-performance liquid chromatography and mass spectrometry of the decomposition products

  The catalysts described in Patent Documents 7 to 9 can be expected to have the same action as the photocatalytic function in the absence of light, that is, in the absence of light. However, the composition produced by the means described in Patent Document 7 also has an antibacterial effect of residual chlorine, and can be expected to have an antibacterial effect, deodorization, antifungal effect, and a reduction effect of volatile organic compounds without light irradiation. However, the virus inactivation function cannot be expected.

  Patent Document 8 is significant in that it clarifies the basic principle that a “p-type semiconductor having a hole” exhibits a catalytic function equivalent to that of a conventional photocatalyst without being irradiated with light. However, there are various methods for forming a metal-deficient non-stoichiometric oxide or metal-deficient non-stoichiometric nitride. However, as a specific method for producing a non-stoichiometric oxide, Insert the target metal powder or bulk product (sample) into the active state under temperature rising and reducing atmosphere, heat the sample to the target temperature, oxygen or oxygen at a predetermined partial pressure Nitrogen is introduced, and the partial pressure of oxygen or nitrogen decreases with time, so it is adjusted and maintained at a predetermined partial pressure, and the process ends when the decrease in the oxygen partial pressure is no longer observed. Only an example of “cooling as quickly as possible” is described. Specific temperature conditions and pressure adjustment conditions for producing the non-stoichiometric oxide are not shown. In addition, the means for fixing the obtained non-stoichiometric oxide on the substrate also involves large-scale equipment and has not yet been actually manufactured or sold.

  In addition to the above, for the so-called photocatalysts described in Patent Documents 1 to 5, means for measuring the organic matter decomposition performance has been established as described in Non-Patent Documents 1 and 2, but in the absence of light, that is, irradiation of light Currently, no means for evaluating the characteristics of catalysts used in a state where they are not subjected to the above has been established.

  The present invention establishes a means for evaluating the characteristics of a catalyst used in a state where it is not irradiated with light, and proposes a non-photocatalyst having a new configuration, which enables mass production at low cost. The present invention makes it possible to provide a catalyst body that retains holes in a state that is not irradiated with light, a manufacturing method thereof, and an antiviral / antibacterial cloth.

  In the present invention, the solid composition produced when the carboxylic acid of the transition metal or transition metal oxide is dried in the presence of silicon dioxide retains holes without being irradiated with light. The present invention was completed by confirming and establishing a specific means for utilizing this.

The catalyst body that retains holes without being irradiated with light according to the present invention has a catalyst layer of any one of the following (A), (B), and (C) on the surface of the substrate. It is what.
(A) After forming a silicon dioxide layer on the surface of the substrate, an aqueous coating agent containing one or more salts selected from metal carboxylates and metal oxide carboxylates as an active ingredient is applied. -The catalyst layer (B) formed by drying contains, as active ingredients, one or more salts selected from metal carboxylates and metal oxide carboxylates and silicon dioxide on the surface of the substrate. After forming a silicon dioxide layer on the surface of the catalyst layer (C) substrate formed by applying and drying an aqueous coating agent, 1 selected from metal carboxylate and metal oxide carboxylate Catalyst layer formed by applying and drying an aqueous coating agent containing two or more kinds of salts and silicon dioxide as active ingredients. Here, the metal carboxylate is a transition metal carboxylate. What are metal oxide carboxylates? It refers to carboxylate of the transition metal oxide.

  In the above invention, the metal carboxylate is composed of titanium oxalate, titanium lactate, zirconium acetate, zirconium oxalate, manganese oxalate, iron oxalate, cobalt oxalate, nickel oxalate, copper oxalate and zinc oxalate. It is preferable that the selected one type or two or more types. The metal oxide carboxylate is preferably one or more selected from titanyl ammonium oxalate, vanadium oxalate oxide, and zirconium oxide acetate.

  When the metal carboxylate is titanium oxalate or titanium lactate, the local structure of titanium atoms in the catalyst layer formed by applying and drying an aqueous coating agent containing the carboxylate is oxygen A 4-coordinate structure of atoms is preferable. The carboxylate of the metal oxide is titanyl ammonium oxalate, and the local structure of titanium atoms in the catalyst layer formed by applying and drying an aqueous coating agent containing the carboxylate, A 4-coordinate structure of oxygen atoms is preferable.

  It is preferable that the catalyst body that retains holes without being irradiated with light according to the above inventions has a methylene blue rapid decomposition test value of 60% or more in the absence of light.

  In each of the above inventions, the aqueous coating agent preferably contains one or more selected from phosphoric acid and water-soluble phosphate.

  In each of the above inventions, the substrate is preferably a metal plate, a metal plate having an organic coating film, ceramics, a woven fabric, or a nonwoven fabric.

The catalyst body that retains holes in a state that is not irradiated with light according to each of the above aspects of the invention,
A base material preparation step of preparing a base material having a base layer containing silicon dioxide;
An application step of applying an aqueous coating agent containing, as an active ingredient, one or more salts selected from metal carboxylates and metal oxide carboxylates on a substrate having the underlayer;
The aqueous coating agent applied by the above process can be formed by sequentially performing a catalyst layer generating step of drying a catalyst layer having holes by drying at a temperature of 500 ° C. or lower.
Here, the metal carboxylate refers to a transition metal carboxylate, and the metal oxide carboxylate refers to a transition metal oxide carboxylate.

In the above invention, the base material preparing step for preparing the base material having the base layer containing silicon dioxide is prepared by preparing the base material having the base layer containing silicon dioxide on the surface or the base material not having the base layer. As a base material preparation process,
Aqueous coating in which an aqueous coating agent containing one or more salts selected from metal carboxylates and metal oxide carboxylates and silicon dioxide as active ingredients is applied to the prepared substrate. Agent coating process;
It is possible to sequentially perform a catalyst layer generation step of drying the applied aqueous coating agent at a temperature of 500 ° C. or less to generate a catalyst layer having holes.
Here, the metal carboxylate refers to a transition metal carboxylate, and the metal oxide carboxylate refers to a transition metal oxide carboxylate.

  Since conventional antibacterial agents such as silver existed only for cells that are effective against bacteria, there was no antibacterial cloth that could inactivate viruses without cells, whereas the catalyst layer was made of woven or non-woven fabric. It can be carried to make an antiviral / antibacterial cloth.

  According to the present invention, it is possible to provide a catalyst body that retains holes without being irradiated with light that can be mass-produced at low cost, a manufacturing method thereof, and an antiviral / antibacterial cloth.

FIG. 5 is an ESR spectrum demonstrating DMPO-OH generated by trapping OH radicals generated by removing electrons from water molecules in a catalyst body that retains holes without receiving light according to the present invention. .

  The catalyst body according to the present invention is formed by forming a catalyst layer on the surface of a base material, and retains holes without being irradiated with light. This is because the DMPO aqueous solution in contact with the catalyst body is subjected to ESR (electron spin resonance spectroscopy) without irradiating the catalyst body according to the present invention with light such as ultraviolet rays at any stage in advance or in use. ) Can detect and verify OH radicals.

FIG. 1 shows a case where an amorphous silica sol (20% (mass ratio, the same applies hereinafter), Snowtex O manufactured by Nissan Chemical Industries, Ltd., trademark, the same applies hereinafter) is applied to an A5052P aluminum alloy plate having a thickness of 0.4 mm. After 90 seconds, put it in a muffle furnace at a temperature of 10 ° C., and 10 g of titanyl ammonium oxalate (5% TiO ₂ conversion, TKC-305 manufactured by Teika Co., Ltd.) and 14 g of amorphous silica sol (20%, Snowtex O) on the surface. And phosphoric acid (applying an aqueous coating composition containing 0.7 g of 85% and drying in an oven at 200 ° C. for 2 minutes to obtain a catalyst body. The obtained catalyst body was 40 × 40 mm. After preparing a test piece, 300 μl of 20-fold diluted ultrapure water of radical trapping agent DMPO (5,5-dimethyl-1-pyrroline-N-oxide) was dropped on the surface, and then covered with a polypropylene film for 2 minutes. After that, the film was peeled off, and the radical trapping agent aqueous solution was collected in a flat cell and subjected to ESR measurement, and the ESR spectrum shown in FIG. : 4 peaks were observed, and it was confirmed that most of the trapped radicals were OH radicals.

  The catalyst layer constituting the catalyst body according to the present invention is formed in the process of drying the transition metal carboxylate or its oxide carboxylate on the substrate under the condition where silicon dioxide is present. Although details will be described later, it is characterized by the presence of silicon dioxide in the catalyst layer in light of the formation process.

  It is estimated that the catalyst layer contains a metal-deficient non-stoichiometric oxide of a transition metal therein. As described above, this means that the catalyst layer is in contact with water and releases OH radicals, and the following experiment shows that titanium, which is a typical metal element constituting the catalyst body of the present invention, is used. This is based on the fact that the local structure of oxygen around the atom is tetracoordinated.

The experiment conducted to investigate the local structure around the titanium atom is as follows.
(1) Preparation of sample: 20% silica sol (Snowtex O) was applied to an Al-2.5% Mg plate and dried at 200 ° C. to prepare a base material having a base layer containing silicon dioxide on the surface. No. 1 shown in Table 1 for the obtained base material. An aqueous treatment liquid containing components 1 to 3 as active ingredients was applied, and charged and dried in a furnace maintained at a predetermined temperature shown in Table 1 for 90 seconds to form a catalyst body according to the present invention. As a comparative material, No. Samples described in 4 to 6 were prepared.

(2) Measurement: The obtained sample was subjected to local state analysis by micro XAFS method using synchrotron radiation. From the obtained spectrum, a strong peak is observed in the vicinity of 4966 to 4967 eV. The appearance of this peak is identified as the spectrum in the case where four oxygens are coordinated to the titanium atom, and the local structure around the Ti atom. No. All of 1-3 are determined to be tetracoordinate. Furthermore, the spectrum obtained from this sample is significantly different in shape and energy from that of metallic titanium, so it can be said that titanium in the catalyst layer is not metallic. The measurement results are shown in Table 1.

(3) Evaluation results: Experiment No. using a coating agent having a composition according to the present invention. 1 to 3, that is, a silicon dioxide (SiO ₂ , silica) layer formed on the substrate, and further, titanium oxalate as an active ingredient in the presence of silicon dioxide blended in the coating agent When the coating agent to be used was used, it became clear that the local structure of oxygen around the Ti atom is all four-coordinated under the applied drying conditions. In contrast, when the coating agent does not contain titanium oxalate and silicon dioxide and anatase type titanium dioxide are blended as active ingredients (No. 4) and anatase type titanium dioxide powder (No. 6), All the local structures of oxygen around the Ti atom were 6-coordinated. The coordinate oxygen number of titanium metal was determined to be 0.

  In addition to the above, the catalyst body according to the present invention has been found to be in an amorphous state according to X-ray diffraction. However, the finer crystal structure is unknown and may be extremely fine nanocrystal particles.

The catalyst body that retains holes without being irradiated with light according to the present invention has a catalyst layer formed by any of the following means (A), (B), or (C) on the substrate. .
(A) After forming a silicon dioxide layer on the surface of the substrate, an aqueous coating agent containing one or more salts selected from metal carboxylates and metal oxide carboxylates as an active ingredient is applied. -The catalyst layer (B) formed by drying contains, as active ingredients, one or more salts selected from metal carboxylates and metal oxide carboxylates and silicon dioxide on the surface of the substrate. After forming a silicon dioxide layer on the surface of the catalyst layer (C) substrate formed by applying and drying an aqueous coating agent, 1 selected from metal carboxylate and metal oxide carboxylate Catalyst layer formed by applying and drying an aqueous coating agent containing seeds or two or more salts and silicon dioxide

  As the substrate, a metal plate, a metal plate having an organic coating film, a glass plate, a plastic, a natural fiber, a synthetic fiber, a mineral fiber, and a woven or non-woven fabric thereof can be used.

  When a silicon dioxide layer is present on the surface of a substrate such as glass, an aqueous coating agent containing a carboxylate is dried at a temperature of 400 ° C. or more and 500 ° C. or less and is equivalent to an underlayer having a silicon dioxide layer on the substrate. Performance can be obtained. Moreover, when using the glass cloth which performed the silane process, if the heat processing of 500 degreeC or more is performed, a silicon dioxide layer can be obtained on the surface of a base material by the oxidation of a silane.

  As the metal elements constituting the carboxylate, transition metals, especially titanium, zirconium, manganese, iron, cobalt, nickel, copper, zinc, lanthanum and cerium are commercially available oxalates and are easily available. Since there are, it is preferable to adopt these. In particular, titanium metal carboxylic acid has an advantage that it can be easily produced simply by adding tetraisopropoxide to an aqueous oxalic acid solution. Further, titanium oxide oxalate is particularly suitable because it can be obtained as commercial products from a plurality of manufacturers. Furthermore, since titanium does not correspond to a heavy metal, there is an advantage that it can be used for applications such as sanitary masks and antibacterial cloths.

  The transition metal is a component of an aqueous coating agent in the form of a metal or its oxide carboxylate, and in the process of drying, an undercoat layer or aqueous coating containing silicon dioxide formed on the substrate. When coexisting with silicon dioxide blended in the agent, a catalyst coating layer having holes is formed.

  As the metal carboxylate, one selected from titanium oxalate, titanium lactate, zirconium acetate, zirconium oxalate, manganese oxalate, iron oxalate, cobalt oxalate, nickel oxalate, copper oxalate, and zinc oxalate Or 2 or more types can be used. As the carboxylate of the metal oxide, one or more selected from titanyl ammonium oxalate, vanadium oxalate oxide, and zirconium acetate oxide can be used. Titanium lactate ammonium can also be used.

  In particular, when titanium oxalate or titanium lactate is selected as the metal carboxylate, as described above, the locality of titanium atoms in the catalyst layer formed by applying and drying an aqueous coating agent containing this is used. It has been confirmed that the structure is a four-coordinate structure of oxygen atoms, and unlike a rutile-type or anatase-type titanium dioxide having a six-coordinate structure, a metal-deficient non-stoichiometric oxide containing holes is formed. It means that

  As described above, the catalyst body according to the present invention forms a catalyst layer that retains holes in a state where the transition metal or its carboxylate salt is dried in the presence of silicon dioxide and is not irradiated with light. Manufactured by. As a silicon dioxide source coexisting with such a carboxylate, for example, fine silica powder may be used, but it is advantageous to use silica sol dispersed in water or an organic solvent because it can be used without being precipitated in the coating agent. Typically, various types of snowtex from Nissan Chemical Industries, Ltd. can be used. Silicon dioxide may be present in the form of being primed to the substrate or in the form of being blended with a carboxylate in an aqueous coating agent. In addition, it is good for the amount ratio of the said carboxylate salt and a silica sol to be 0.1-40 parts by conversion of a silica sol into a silica part with respect to 1 part of carboxylate by mass ratio.

  The aqueous coating agent can contain 1 type, or 2 or more types selected from phosphoric acid. Inclusion of this phosphoric acid or water-soluble phosphate makes it possible to improve product characteristics such as improved adhesion and to take a wide range of heat treatment temperatures, which will be described later, and to stabilize the treatment process. As the phosphoric acid source, water-soluble phosphates such as aluminum phosphate, magnesium phosphate, calcium phosphate, zinc phosphate, and manganese phosphate can be used in addition to phosphoric acid.

  In addition to the addition of phosphoric acid and water-soluble phosphate, a coloring pigment or photocatalytic titanium dioxide powder can also be added to the aqueous coating agent.

In the case of a plate-like material such as a metal plate, the basis weight on the substrate of the catalyst layer constituting the catalyst body according to the present invention is that the basis weight as a dry film thickness is 0.1 to 12 g / m ^2. Good. If it is 0.1 g / m ² or less, the performance is insufficient, and if it exceeds 12 g / m ² , the formed catalyst layer is easily peeled off in powder form, which is not preferable. On the other hand, in the case of a woven fabric or a non-woven fabric, the surface area is much larger than that of a plate-like product, so that the basis weight is preferably 0.5 to 30 g / m ² . The application method is not particularly limited, and in the case of a small scale, brush coating is easy to work, and the amount of adhesion can be controlled by changing the liquid concentration. For mass production, a method of dipping the belt-shaped substrate in the treatment liquid and controlling the amount of adhesion by adjusting the squeezing of the roll, spray coating, or spray coating may be used.

  The catalyst body according to the present invention is produced by coating and drying the transition metal or its carboxylate salt in the presence of silicon dioxide to form a catalyst layer. In this step, it does not matter whether or not light is received. In the above step, the catalyst layer thus formed can retain a wide range of drying conditions after application of the aqueous coating agent, in which holes are retained without being irradiated with light. However, when the drying temperature is higher than 500 ° C., for example, when a titanium carboxylate is used, crystalline titanium dioxide is produced when the holding time for drying is longer than 2 hours. There is a possibility that the object of the present invention cannot be achieved. In general, an upper limit temperature of 300 ° C. or less of a commercial dryer is sufficient. Although the drying temperature may be room temperature, it takes time, so it is preferable to set the drying time to 150 ° C. or higher and adjust the drying time according to the thickness of the substrate. A drying time of 5 minutes or less is usually sufficient. As in general drying, it is preferable to use a natural convection dryer or a forced convection dryer so that air moves.

  The catalyst body according to the present invention can be manufactured as described above, and the product retains holes without being irradiated with light, as described above, using DMPO. This can be confirmed by an OH radical detection test. However, the OH radical detection test requires a large amount of equipment for ESR (electron spin resonance spectroscopy measurement) to obtain the result. Instead of this OH radical detection test, the following methylene blue rapid decomposition test in the absence of light is performed. It is possible to determine that a measured value of 60% or more holds holes in a state where it is not irradiated with light.

Rapid methylene blue decomposition test method in the absence of light (when the catalyst is a plate)
(1) Preparation of sample: A flat test piece having a side of 30 mm square on which a catalyst is formed is prepared.
(2) Preparation of methylene blue aqueous solution: Prepare a methylene blue aqueous solution with a concentration of 100 mg / l.
(3) Place the flat sample prepared in (1) in a petri dish, drop 0.1 ml of the methylene blue aqueous solution prepared in (2) on the surface, and cover with a 30 mm square plastic film.
(4) After being left for 2 minutes in this state, the plastic film is peeled off from the sample surface, washed with 3 mL of purified water, and used as a solution for measuring absorbance in a spectrophotometer together with the washing solution.
(5) Measurement: Measurement of absorbance: The absorbance at a wavelength of 664 nm of the absorbance measurement solution obtained in (3) above is measured, and the measured value is a. At the same time, the absorbance of the methylene blue aqueous solution diluted by adding 3 ml of purified water to 0.1 ml of a 100 mg / l methylene blue aqueous solution is measured and set as the reference value b.
(6) Calculation of methylene blue rapid degradation test value in the absence of light: [(b−a) / b] × 100% is calculated as the methylene blue rapid degradation test value.

(When the catalyst body is a cloth body)
(1) Preparation of sample: A flat test piece having a side of 30 mm square on which a catalyst is formed is prepared.
(2) Preparation of methylene blue aqueous solution: Prepare a methylene blue aqueous solution with a concentration of 20 mg / l.
(3) A 30 × 30 mm plastic film is spread on a petri dish, and 0.5 ml of a 20 mg / l methylene blue aqueous solution is dropped. Another 30 × 30 mm plastic film is placed on the test piece prepared in (1) and placed on the dropped methylene blue aqueous solution. However, when this aqueous solution does not spill over the entire surface of the test piece and the plastic film, purified water is added dropwise in units of 0.1 ml in addition to 0.5 ml.
(4) After being allowed to stand for 6 minutes, the plastic film is peeled off from the sample surface, washed with (2.6-added amount of added water) ml of purified water, and used as a solution for measuring absorbance in a spectrophotometer together with the washing solution.
(5) Measurement: Measurement of absorbance: The absorbance at a wavelength of 664 nm of the absorbance measurement solution obtained in (3) above is measured, and the measured value is a. In addition, the absorbance of a methylene blue aqueous solution diluted by adding 3 ml of purified water to 0.1 ml of a 100 mg / L methylene blue aqueous solution is measured and set as a reference value b.
(6) Calculation of methylene blue rapid degradation test value in the absence of light: [(b−a) / b] × 100% is calculated as the methylene blue rapid degradation test value in the absence of light.

The mechanism by which viruses in water are inactivated in the absence of light is presumed to be due to the fact that this catalyst retains holes in the absence of light and has the function of cleaving the H ₃ C—N bond of methylene blue. It was thought that it was because the amino acids constituting the protein were decomposed. Therefore, an aqueous solution of arginine and histidine each having a CN bond in the side chain as an amino acid was brought into contact with a glass cloth carrying a catalyst, and FT-IR infrared spectroscopic analysis was performed before and after that. As a result, no change was observed in the case of histidine, whereas in the case of arginine, new strong absorption was generated by the catalytic treatment in the region of 1000 to 1500 cm ⁻¹ , and the C—NH ₂ bond was cleaved. The possibility is strong, and it can be said that this coating has retained holes under no light.

Example 1
A 55% aluminum-43% zinc alloy hot-dip steel sheet having a thickness of 0.2 mm was prepared as a base material. A 20% silica sol (Snowtex C) containing silicon dioxide was brush-coated (hereinafter the same) on this substrate and then dried to form a silicon dioxide layer. Titanyl ammonium oxalate was selected as the carboxylate of the titanium oxide, and 10 g of its 5% aqueous solution (in terms of TiO ₂ ) was mixed with 14 g of 20% Snowtex O as silicon dioxide and 1 g of a 50% aqueous solution of aluminum phosphate. After applying the aqueous coating agent, it was dried in an oven at 160 ° C. for 2 minutes to obtain a catalyst body. The obtained catalyst body showed a methylene blue decomposition rapid test value of 79% in the absence of light, and was confirmed to be a catalyst body that retains holes without being irradiated with light.

(Example 2)
As a base material, a glass cloth (Nittobo WAR420BH) having a thickness of 0.42 mm, a mass of 378 g / m ₂ , a density of 33/33 (lines / 25 mm) and a heat cleaning treatment was prepared. A 20% silica sol (Snowtex O) was diluted to 2 times with purified water and applied to this glass cloth, then placed in a 300 ° C. muffle furnace and taken out after 60 seconds to form a silicon dioxide underlayer. Zirconium oxide oxide (ZrO (C ₂ H ₃ O ₂ ) ₂ , Zircozole ZA-20, a first rare element chemical industry), as a metal oxide carboxylate, was obtained on a base material with an underlayer of silicon dioxide. An aqueous solution containing 20%) was diluted 2 times with purified water, applied, placed in a furnace maintained at 300 ° C., held for 90 seconds, and then removed to obtain a catalyst body. The obtained catalyst body showed a methylene blue decomposition rapid test value of 83% in the absence of light.

(Example 3)
A 55% aluminum-43% zinc alloy-plated steel sheet with a thickness of 0.2mm coated with a polyester-based colored organic coating film is used as a base material, and the surface is coated with Snowtex O or C as a silica sol. There wasn't. Therefore, an amorphous silica sol composed of 30% amorphous silica and 70% IPA (Nissan Chemical Industry Co., Ltd. IPA-ST) was diluted twice with purified water and applied, so it could be applied without flipping. The substrate was dried for 90 seconds to obtain a substrate with a silicon dioxide underlayer. An aqueous coating solution having the following composition was applied thereon, followed by drying in a furnace at 200 ° C. for 90 seconds. Titanium lactate: 44%, IPA: 43%, 10 g of a titanium lactate-IPA solution (Matsumoto Pharmaceutical Co., Ltd. OlgaTicks TC-310) consisting of the remaining water was prepared, and 0.7 g of 85% phosphoric acid was purified. 10 g of water was added to make an aqueous coating solution. The obtained aqueous coating solution was applied to the substrate with the silicon dioxide underlayer and dried in a furnace at 200 ° C. for 90 seconds to obtain a catalyst body. The methylene blue decomposition rapid test value in the absence of light was calculated to be 85%.
When this organic catalyst coated steel sheet carrying this catalyst and an organic coated alloy plated steel sheet not carrying this catalyst were attached to the wall of a bathroom in the home and observed after 3 months, the surface of the steel sheet not carrying this catalyst was covered with cocoons. On the other hand, no wrinkles were observed on the steel sheet carrying the catalyst.

Example 4
Thickness 0.21 mm, plain weave glass cloth M200X (manufactured by Unitika Ltd., mass 200 g / m ² , density 19/18 (lines / 25 mm), heat cleaning (lubricating oil decomposed by heat treatment), and then treated with acrylic lysine agent Was heated in a muffle furnace at 500 ° C. for 5 minutes and used as a base material. Aqueous treatment by adding 20% silica sol (Snowtex O) to 15 g of zirconium oxalate 10% aqueous solution (Daiichi Elemental Chemical Co., Ltd.) and 1.1 g of 85% phosphoric acid and 30 g of purified water to 10 g. A liquid was used. The obtained aqueous treatment liquid was applied to the heat-treated glass cloth and heated in a furnace at 300 ° C. for 90 seconds to obtain a catalyst body. The methylene blue decomposition rapid test value in the absence of light was measured and found to be 90%.

(Example 5)
A nylon non-woven fabric having a thickness of 0.26 mm (mass: 40 g / m ² , Niace P0403 WTO manufactured by Unitika Co., Ltd.) is used as a base material, and 20% silica sol (Snowtex) is added to 10 g of an aqueous solution of titanyl ammonium oxalate (TKC-305). 20 g of O) and 0.5 g of 50% aluminum phosphate were added, and an aqueous treatment solution diluted 3-fold with purified water was applied, and dried in a 120 ° C. oven for 3 minutes to obtain a catalyst body. The methylene blue decomposition rapid test value in the absence of light was calculated to be 82%.

(Example 6)
After applying 20% silica sol (Snowtex O) to a steel plate hot-plated with 55% aluminum-43% zinc alloy with a thickness of 0.2 mm, 0.2 mm thick, it was placed in a 200 ° C. muffle furnace and heated for 30 seconds. A substrate with a base was used. After applying an aqueous coating agent containing 14 g of 20% silica sol (Snowtex O) and 1 g of 50% aluminum phosphate to 10 g of an aqueous solution of titanyl ammonium oxalate (TKC-305), it was placed in a furnace at 300 ° C. after 90 seconds. A catalyst body was taken out to obtain a catalyst body. The methylene blue decomposition rapid test value in the absence of light was calculated and found to be 92%.

(Example 7)
A 2.5% Mg-Al aluminum alloy plate with a thickness of 0.4 mm is used as a base material. Amorphous silica 20% silica sol (Snowtex C) is applied to the base plate, placed in a 200 ° C. muffle furnace, and taken out after 90 seconds. A substrate with an underlayer of silicon dioxide was obtained. Titanium tetraisopropoxide (Ti (C ₃ H ₇ O) ₄ ): 100 g of an aqueous solution containing 9% oxalic acid (COOH) ₂ , a concentration of 10.4% isopropyl alcohol and a concentration of 9.8% titanium oxalate It was created. An aqueous treatment liquid was prepared by blending 20 g of silica sol (Snowtex O) with a concentration of 20% to 10 g of this aqueous titanium oxalate solution. This aqueous treatment liquid was applied to the substrate with the silicon dioxide underlayer, and then charged in a muffle furnace at 400 ° C. and held for 90 seconds to obtain a catalyst body. The methylene blue decomposition rapid test value in the absence of light was calculated and found to be 96%.

(Example 8)
The antiviral properties of the catalyst body obtained in Example 7 were tested as follows.
The catalyst support plate was cut to 30 × 30 mm, sterilized at 180 ° C. for 30 minutes, then added with 50 μl of Sindbis virus solution (1.0 × 104 pfu / ml), covered with a polypropylene membrane, 30 seconds, 5 minutes, 15 minutes, After treatment at room temperature for 45 minutes, the virus was recovered with 2 ml of PBS, and the virus titer was measured. As a result, it was found that about 80% in 30 seconds, but almost all became inactivated after 45 minutes.
After the test piece used for the antiviral test was naturally dried indoors, the same antiviral test was performed again, and almost the same result was obtained. This indicates that even if the holes possessed by the catalyst are lost in the virus solution, they are recovered by natural drying, and it has been proved that the substrate carrying the catalyst can be used repeatedly.

Example 9
A glass cloth of wet nonwoven fabric of ultra fine glass fiber with a thickness of 1 μm or less (AGM paper with a thickness of 0.65 mm and a mass of 90 g / m ² , manufactured by Nippon Sheet Glass Co., Ltd.), and a silica sol with a concentration of 20% ( Snowtex O) was diluted 3 times with purified water and applied, and then placed in a 200 ° C. muffle furnace and held for 90 seconds to form a glass cloth having a silicon dioxide underlayer. Titanium lactate 44%, IPA 43%, balance water 10g (OrgaTix TC-310) 10 times diluted with purified water, 85% phosphoric acid 0.7g, 20% silica sol (Snowtex O) 30g The treatment liquid was applied and treated in a furnace at 200 ° C. for 90 seconds. The methylene blue decomposition rapid test value in the absence of light was measured and found to be 89%.

(Example 10)
Cotton non-woven fabric with a thickness of 0.38 mm (based on a mass of 60 g / m ² (trade name: Cotto Ace C60S / A01, manufactured by Unitika Co., Ltd.). 10 g of titanyl ammonium oxalate (5% TKC-305 in terms of TiO ₂ ) 10 g of amorphous silica sol (Snowtex O) and 0.5 g of 50% aluminum phosphate were added and diluted with purified water three times to obtain an aqueous treatment coating solution, which was applied to the cotton nonwoven fabric, and then 120 The catalyst body was obtained by drying in an oven at 0 ° C. for 3 minutes, and the methylene blue decomposition rapid test value in the absence of light was calculated to be 87%.
When the same catalyst-supported cotton nonwoven fabric was immersed in tap water for 5 days and subjected to a methylene blue decomposition rapid test in the absence of light after natural drying, a value almost equal to 86% was obtained, demonstrating water resistance.

As described above, the catalyst body according to the present invention exhibits an action as a catalyst that functions in the absence of light, as understood from the results of the rapid measurement test for methylene blue in the absence of light. This contributes to the dissociation reaction of the -N bond, thereby causing the action of decomposing water pollutants, as well as bactericidal action and antiviral inactivation action. In addition, it acts as an oxidation catalyst for NO _X and SO _X , thereby making environmental pollutants harmless.

The present invention is highly likely to produce many new products such as antiviral sanitary masks, antibacterial cloths, and air filters using such effects. In addition, it has become possible to apply to air conditioner (air conditioner) fins and filters, where the use of photocatalysts has been postponed due to the inability to install a light source. These are applications using a woven or non-woven fabric of fiber as a base material. However, since they are naturally dried at room temperature in the atmosphere, they can be applied to bathroom walls and ceilings to prevent wrinkles. Repeated immersion and drying in water while rotating the metal plate carrying this catalyst can inactivate viruses in the water and sterilize bacteria without using chemicals, thus contributing to fishing and agriculture.

Claims (11)

The catalyst body which has a hole in the state which does not receive light irradiation characterized by having the catalyst layer in any one of following (A), (B) and (C) on the surface of a base material.
(A) After forming a silicon dioxide layer on the surface of the substrate, an aqueous coating agent containing one or more salts selected from metal carboxylates and metal oxide carboxylates as an active ingredient is applied. -The catalyst layer (B) formed by drying contains, as active ingredients, one or more salts selected from metal carboxylates and metal oxide carboxylates and silicon dioxide on the surface of the substrate. After forming a silicon dioxide layer on the surface of the catalyst layer (C) substrate formed by applying and drying an aqueous coating agent, 1 selected from metal carboxylate and metal oxide carboxylate Catalyst layer formed by applying and drying an aqueous coating agent containing two or more kinds of salts and silicon dioxide as active ingredients. Here, the metal carboxylate is a transition metal carboxylate. What are metal oxide carboxylates? It refers to carboxylate of the transition metal oxide.   The metal carboxylate is selected from titanium oxalate, titanium lactate, zirconium acetate, zirconium oxalate, manganese oxalate, iron oxalate, cobalt oxalate, nickel oxalate, copper oxalate and zinc oxalate The catalyst body that retains holes without being irradiated with light according to claim 1, wherein the catalyst body is two or more kinds.   The metal oxide carboxylate is one or more selected from titanyl ammonium oxalate, vanadium oxalate oxide, and zirconium oxide acetate. Catalytic body holding holes.   The metal carboxylate is titanium oxalate or titanium lactate, and the local structure of titanium atoms in the catalyst layer formed by applying and drying an aqueous coating agent containing the carboxylate is oxygen atom The catalyst body having holes in a state where it is not irradiated with light according to claim 2, wherein the catalyst body has a four-coordinate structure.   The carboxylate of the metal oxide is titanyl ammonium oxalate, and the local structure of titanium atoms in the catalyst layer formed by applying and drying an aqueous coating agent containing the carboxylate is oxygen atom 4. The catalyst body having holes in a state of not being irradiated with light according to claim 3, wherein the catalyst body has a four-coordinate structure.   6. The catalyst body that retains holes without being irradiated with light according to any one of claims 1 to 5, wherein the methylene blue rapid decomposition test value in the absence of light is 60% or more. The aqueous coating agent contains one or more selected from phosphoric acid and a water-soluble phosphate, and does not receive light irradiation according to any one of claims 1 to 6 A catalyst body that retains holes in a state.
Catalyst body.   The base material is any one of a metal plate, a metal plate having an organic coating film, a glass plate, a plastic, a natural fiber, a synthetic fiber, a mineral fiber, and a woven or non-woven fabric of these. The catalyst body which retains a hole in the state which does not receive irradiation of the light in any one of. A base material preparation step for preparing a base material having a base layer containing silicon dioxide on the surface;
An aqueous coating agent coating step of coating an aqueous coating agent containing one or more salts selected from a metal carboxylate and a metal oxide carboxylate as an active ingredient on the substrate having the base layer. When,
A catalyst layer generating step of drying the applied aqueous coating agent at a temperature of 500 ° C. or less to generate a catalyst layer having holes, and sequentially performing holes without receiving light. The manufacturing method of the catalyst body which holds.
Here, the metal carboxylate refers to a transition metal carboxylate, and the metal oxide carboxylate refers to a transition metal oxide carboxylate. A base material preparation step for preparing a base material having a base layer containing silicon dioxide on the surface or a base material not having the base layer;
Aqueous coating for applying an aqueous coating agent containing one or more salts selected from metal carboxylates and metal oxide carboxylates and silicon dioxide as active ingredients on any of the above-mentioned substrates. A coating agent coating process;
A catalyst layer generating step of drying the applied aqueous coating agent at a temperature of 500 ° C. or less to generate a catalyst layer having holes, and sequentially performing holes without receiving light. The manufacturing method of the catalyst body which holds.
Here, the metal carboxylate refers to a transition metal carboxylate, and the metal oxide carboxylate refers to a transition metal oxide carboxylate. An antiviral / antibacterial cloth characterized in that the catalyst layer according to any one of claims 1 to 8 is supported on a woven fabric or a nonwoven fabric.

Images