Odor removal catalyst and use therefor

Abstract

The present invention addresses the problem of providing: an odor removal catalyst which is capable of efficiently and safely reducing various odor components, in particular, odor components such as aldehydes, for a long period of time, is less likely to cause recurrence of odor, and is capable of continuously reducing and removing odor even under relatively low-temperature conditions such as 40 °C or lower; and a use thereof.　The odor removal catalyst is obtained by supporting a Pt-containing metal component on zeolite, wherein the zeolite has a silica / alumina ratio (SiO2 / Al2O3 (mol / mol) of 50 to 3,000.

Description

Odor removal catalyst and its uses

[0001] The present invention relates to an odor removal catalyst and its use. More specifically, the present invention relates to an odor removal catalyst in which a metal component including Pt is supported on a zeolite, and its use.

[0002] Various odors generated in the environment (exhaust gas, garbage and food odors, odors emitted from newly constructed homes and buildings, etc.) are major social issues, and effective countermeasures are needed for each environment. Odors are particularly problematic in enclosed spaces such as homes, public facilities such as hotels and restaurants, and transportation facilities such as trains and automobiles. However, since people coexist in these spaces, installing specialized equipment (e.g., ozone deodorizers, hypochlorous acid deodorizers) that pose safety concerns is difficult, and easy-to-use adsorbents are therefore preferred. However, continued use of adsorbents can exceed their adsorption capacity and cause breakthrough, requiring frequent replacement. Furthermore, particularly on hot days, desorption of adsorbed odorous components can cause unpleasant odors.

[0003] Among the many different substances that cause odors, acetaldehyde has a unique odor and is irritating. It is an air pollutant derived from automobile exhaust, cigarette smoke, plywood adhesives, etc., and is known to be one of the causes of sick building syndrome, so there is a need to reduce or eliminate this odor. Furthermore, as mentioned above, since adsorbents need to be replaced frequently, there has been a need for an odor removal catalyst that can decompose and reduce or eliminate odorous components, including acetaldehyde, over the long term.

[0004] Patent Document 1 teaches that a catalyst comprising a platinum and ruthenium composite supported on porous silica can oxidatively decompose ethylene or mercaptan compounds. Patent Document 2 discloses palladium-doped ZSM-5 as an adsorbent for volatile organic compounds (VOCs) derived from organic substances, and indicates that it can adsorb ethylene.

[0005] Patent Document 3 describes a deodorizer in which a chemically impregnated layer of aniline or the like is provided on the surface of a porous carrier, and a catalytic component such as ruthenium, platinum, or palladium is supported thereon, and Patent Document 4 describes a deodorizer in which a metal oxidation catalyst is supported on activated carbon. However, according to the studies of the present inventors, each of the above-mentioned technologies has problems such as insufficient deodorizing effect, inability to be used for a long period of time without regeneration, or inability to obtain sufficient deodorizing effect over time.

[0006] International Publication No. 2019 / 027057, Japanese Patent Publication No. 2015-213908, Japanese Patent Publication No. 2002-200150, Japanese Patent Publication No. 2000-312710, International Publication No. 2022 / 071379

[0007] In light of this situation, the present applicant has discovered and proposed an odor removal catalyst in which a metal component including Pt is supported on a composite oxide, which has excellent odor removal effects and also has antibacterial properties (see Patent Document 5). Although this odor removal catalyst has excellent odor removal performance, the present inventors' investigations have shown that when used to decompose and deodorize aldehydes such as propionaldehyde, it has better decomposition performance at high temperatures, such as 80°C, than at room temperature.

[0008] An object of the present invention is to provide an odor removal catalyst that can efficiently and safely reduce various odorous components, particularly odorous components such as aldehydes, for a long period of time, is less likely to cause odor recurrence, and can continuously reduce and remove odorous components such as aldehydes even under relatively low temperature conditions such as 40°C or lower, as well as uses thereof.

[0009] In view of the above circumstances, the inventors conducted diligent research and found that a catalyst in which a metal component containing Pt is supported on a specific zeolite can solve the above problems, and thus completed the present invention. The present invention relates, for example, to the following matters [1] to

[13] .

[0010] [1] An odor removal catalyst in which a metal component containing Pt is supported on a zeolite, wherein the silica / alumina ratio of the zeolite (SiO ２ / Al ２ O３ (mol / mol)) is 50 or more and 3000 or less. [2] The odor removal catalyst according to [1], wherein the metal component contains Pt and at least one metal element selected from Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Cu, Ag, and Au.

[0011] [3] The odor removal catalyst according to [1] or [2], wherein the zeolite is an MFI-type zeolite. [4] The odor removal catalyst according to any one of [1] to [3], wherein the zeolite is an alkali metal-free zeolite. [5] The odor removal catalyst according to any one of [1] to [4], wherein the average particle size is 0.5 μm or more and 20 μm or less.

[0012] [6] The odor removal catalyst according to any one of [1] to [5], wherein the amount of the metal component supported is 0.01 to 10 mass% in terms of the metal content of the entire metal components. [7] The odor removal catalyst according to any one of [1] to [6], and a silica / alumina ratio (SiO ２ / Al ２ O ３ [8] A deodorant composition comprising an MFI zeolite having a silica / alumina ratio (SiO 2 (mol / mol)) of 20 or more and 45 or less. ２ / Al ２ O ３ and an MFI zeolite having a molecular weight (mol / mol) of 50 or more and 3,000 or less.

[0013] [9] A method for producing an odor removing catalyst according to any one of [1] to [6], and a silica / alumina ratio (SiO ２ / Al ２ O ３

[10] A deodorant composition according to [7], wherein the mass ratio of the odor removal catalyst according to any one of [1] to [6] and an MFI zeolite having a silica / alumina ratio (SiO ２ / Al ２ O ３[8] The deodorant composition according to [8], wherein the mass ratio of the MFI zeolite having a molecular weight (mole / mol) of 50 or more and 3,000 or less to the MFI zeolite is 99 / 1 or more and 1 / 99 or less.

[0014]

[11] A deodorizing product comprising the odor removing catalyst according to any one of [1] to [6] or the deodorizing composition according to any one of [7] to

[10] .

[12] The deodorizing product according to

[11] , which is a deodorizing fiber, a deodorizing paint, or a deodorizing sheet.

[13] The deodorizing product according to

[11] , which is clothing, a wig, shoes, gloves, rubber gloves, upholstery, curtains, carpets, tiles, wallpaper, a deodorizing air filter, or an interior material for a vehicle.

[0015] According to the present invention, it is possible to provide an odor removal catalyst and uses thereof that can efficiently and safely reduce various odorous components, particularly odorous components such as acetic acid and aldehydes, that is less likely to cause odor recurrence, and that can continuously reduce and remove odorous components such as aldehydes even under relatively low temperature conditions such as below 40° C. The odor removal catalyst of the present invention and the deodorant composition and deodorizing product containing it can continuously reduce odors over a long period of time by being installed in a space containing an odorous component, can be suitably used at both high and low temperatures, and can effectively deodorize odors in the installation space, such as the interior of a vehicle or other room.

[0016] Fig. 1 is a graph showing the change over time in the propionaldehyde deodorizing properties of odor removal catalyst A obtained in Example 1 at 80°C. Fig. 2 is a graph showing the change over time in the propionaldehyde deodorizing properties of odor removal catalyst A obtained in Example 1 at 40°C. Fig. 3 is a graph showing the change over time in the propionaldehyde deodorizing properties of odor removal catalyst B obtained in Example 2 at 80°C. Fig. 4 is a graph showing the change over time in the propionaldehyde deodorizing properties of odor removal catalyst B obtained in Example 2 at 40°C. Fig. 5 is a graph showing the change over time in the propionaldehyde deodorizing properties of odor removal catalyst C obtained in Comparative Example 1 at 80°C. Fig. 6 is a graph showing the change over time in the propionaldehyde deodorizing properties of odor removal catalyst C obtained in Comparative Example 1 at 40°C.

[0017] The present invention will be described in detail below. <Odor Removal Catalyst> The odor removal catalyst of the present invention is provided with a metal component containing Pt supported on a specific zeolite.

[0018] Zeolite The zeolite used in the production of the odor removal catalyst in this invention is a porous crystalline aluminosilicate capable of supporting metal components, with a silica / alumina ratio (SiO ２ / Al ２ O ３ There are no particular restrictions on the zeolite used in the present invention, and it may be a natural zeolite or a synthetic zeolite, and its skeletal structure is not particularly limited. However, synthetic zeolite is preferred because it has excellent homogeneity, and MFI zeolite (ZSM-5 zeolite) is more preferred because it provides high deodorizing properties.

[0019] The silica / alumina ratio (SiO₂) of the zeolite used in this invention ２ / Al ２ O ３ The silica / alumina ratio (mol / mol) is 50 or more and 3000 or less, preferably 100 or more and 2500 or less, more preferably 500 or more and 2000 or less, even more preferably 1000 or more and 1800 or less, and particularly preferably 1400 or more and 1600 or less. A silica / alumina ratio in this range is preferred because it provides an excellent adsorption effect for odorous substances and the like. The average particle size of the zeolite used in the present invention is usually in the range of 10 nm to 20 μm, preferably 100 nm to 15 μm, more preferably 1 μm to 10 μm, and even more preferably 2 μm to 5 μm. In one preferred embodiment, the average particle size of the zeolite used in the present invention is 0.5 μm to 20 μm.

[0020] The zeolite used in the present invention is not particularly limited as long as it contains an aluminosilicate as the main component, but it is preferable that it does not contain alkali metals. The zeolite used in the present invention may be a synthesized product or a commercially available product. An example of a commercially available zeolite that can be suitably used in the present invention is HSZ 891HOA (MFI type zeolite, H-ZSM-5, silica / alumina ratio (SiO ２ / Al ２ O ３ ratio (mol / mol): 1500, average particle size: 4 μm), Clariant CZP 90 (MFI type zeolite, H-ZSM-5, silica / alumina ratio (SiO ２ / Al ２ O ３ Ratio (mol / mol): 80-100), CZP 200 (MFI type zeolite, H-ZSM-5, silica / alumina ratio (SiO ２ / Al ２ O ３ Examples include the ratio (mol / mol): >200.

[0021] The odor removal catalyst of the present invention supports one or more metal components, including Pt (platinum). Metals other than Pt included in the metal component are not particularly limited, but include, for example, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Cu, Ag, and Au. The supported metal species may be Pt alone or a combination of Pt and other metals, preferably Pt alone or a combination of Pt and at least one selected from Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Cu, Ag, and Au. The proportion of Pt in the total supported metals (the sum of Pt and other metals) is usually 1 mol% or more, preferably 10 mol% or more.

[0022] The metal component may be supported on the zeolite in any form, but is preferably supported on the zeolite in the form of a simple metal or an alloy. When the metal component contains Pt and another metal, Pt and the other metal may exist as simple metals or as an alloy, but it is preferable that at least a portion of them form an alloy, and it is more preferable that the alloy form a solid solution. When Pt and the other metal form a solid solution, the alloy state is preferable because the deodorizing performance per amount of Pt used is improved.

[0023] The amount of metal components in the odor removal catalyst, calculated as the metal amount of all metal components, is usually in the range of 0.01 to 10 mass%, preferably 0.01 to 5 mass%, more preferably 0.05 to 3 mass%, and even more preferably 0.08 to 1.5 mass%. When the amount of supported metal components is in this range, a sufficient odor removal effect can be achieved, which is preferable.

[0024] Odor Removal Catalyst The average particle size of the odor removal catalyst of the present invention is preferably in the range of 10 nm to 20 μm. The lower limit of the average particle size of the odor removal catalyst is more preferably 100 nm, even more preferably 0.5 μm, even more preferably 1 μm, and particularly preferably 2 μm. The upper limit of the average particle size of the odor removal catalyst is more preferably 15 μm, even more preferably 10 μm, and particularly preferably 5 μm. In a preferred embodiment, the average particle size of the odor removal catalyst of the present invention is 0.5 μm or more and 20 μm or less. The average particle size of the odor removal catalyst can be measured by known methods, but specifically, it can be measured, for example, under the following conditions. Furthermore, if no particular aggregation or pulverization is involved in the production of the odor removal catalyst, the average particle size of the odor removal catalyst is equivalent to the average particle size of the zeolite used in the production of the odor removal catalyst. Measurement conditions for average particle size: Equipment: Laser diffraction particle size distribution analyzer Mastersizer 3000 (Malvern Panalytic Corporation) Dispersion unit: Hydro MV Dispersion medium: Water particle refractive index: 1.473 Dispersion medium refractive index: 1.330

[0025] The odor removal catalyst of the present invention has an excellent deodorizing effect and can suitably reduce and remove odorous substances such as aldehydes, carboxylic acids, and esters, and is particularly suitable for deodorizing odorous substances including aldehydes such as acetaldehyde and propionaldehyde. Specifically, the odor removal catalyst of the present invention rapidly reduces odorous substances in the surrounding gas by adsorbing them into the pores of the zeolite, and decomposes at least a portion of the adsorbed odorous substances with a metal component containing Pt supported on the zeolite. For this reason, even when the odor removal catalyst of the present invention is exposed to high temperatures after adsorbing odorous substances, it is less likely to release odorous substances and diffuse the odor, and the adsorption capacity does not decrease significantly as the adsorbed odorous substances are decomposed and diffused, so it can be used for deodorization for a long period of time.

[0026] <Method for producing odor removal catalyst> As a method for producing the odor removal catalyst of the present invention, any method of supporting one or more metal components including Pt (platinum) on the above-mentioned zeolite can be used without any particular limitation.

[0027] Methods for producing odor removal catalysts include, for example, supporting a metal containing Pt, a metal compound, or a mixture thereof on a zeolite by impregnation, physical mixing, ion exchange, pore filling, etc., and then drying, calcining, and reduction, or any or all of these, as needed. Preferably, a method is used in which a solution or dispersion of a metal compound containing Pt is impregnated into the zeolite, dried as needed, and then calcined and reduced.

[0028] Examples of Pt compounds used for impregnation include platinum chloride, platinum oxide, platinum nitrate, dinitrodiamine platinum, platinum acetate, and platinum oxalate. Other metal compounds include metal salts and metal oxides. Furthermore, the metal compound used for impregnation may be a double salt containing Pt and other metals.

[0029] The reduction of metal compounds supported by impregnation can be carried out, for example, by thermal decomposition reduction, reduction using a gaseous reducing agent such as hydrogen or carbon monoxide, or reduction using a liquid reducing agent such as ethanol, methanol, hydrazine, or sodium borohydride. Furthermore, by using a liquid-phase reduction method, the support and reduction of a Pt-containing metal compound on a zeolite support can be carried out simultaneously, thereby obtaining an odor removal catalyst supported with a Pt-containing metal. Specifically, the liquid-phase reduction method can be carried out by adding a dinitrodiammine Pt ethanol solution, citric acid, and ethanol to a zeolite support and heating under reflux. The support and reduction of a Pt-containing metal compound can be carried out in a single operation, or by repeating the process multiple times.

[0030] <Deodorant composition> The odor removing catalyst according to the present invention may be used alone or in combination with other components. For example, it can be used as a deodorant composition containing the odor removing catalyst according to the present invention and other odor removing components that remove, neutralize, or decompose odorous components.

[0031] As other odor-removing components, known compounds can be used without limitation, but it is preferable to use physical adsorbents or chemical adsorbents. Examples of physical adsorbents include porous composite oxides and activated carbon. Preferred commercially available physical adsorbents include zeolite (H-ZSM-5, HSZ 822HOA manufactured by Tosoh Corporation), silica / alumina ratio (SiO ２ / Al ２ O ３Examples of suitable chemical adsorbents include Mizusawa Chemical Industries' Mizuka Sieves EX122, Silton MT-100, MT-400, and MT-8000. Other preferred commercially available chemical adsorbents include Toagosei's Kesmon NS-750 (organic amine-supported silica; for aldehydes), NS-70 (Ca, Mg compounds; for acids), NS-10 (zirconia phosphate; for ammonia), NS-20C (Cu compound-supported silica; for sulfur compounds), Otsuka Chemical's ChemCatch (adipate dihydrazide; for aldehydes), and Sinasen Zeomic's Dashlight S (amine compound-supported silica; for aldehydes).

[0032] The deodorant composition of the present invention can be any combination of the odor removal catalyst of the present invention and other odor removal components as described above, but it is preferable to include the odor removal catalyst of the present invention and a physical adsorbent or chemical adsorbent, more preferably the odor removal catalyst of the present invention and a physical adsorbent, and even more preferably the odor removal catalyst of the present invention and a zeolite.

[0033] In a preferred embodiment, the deodorant composition of the present invention contains, together with the odor removing catalyst of the present invention, a silica / alumina ratio (SiO ２ / Al ２ O ３ The composition includes a zeolite with a silica / alumina ratio (SiO₂) of 20 to 45 or 50 to 3000, and the zeolite is more preferably an MFI type zeolite. Such a combination of deodorant compositions is preferred in terms of adsorption effect of odor substances, etc. A commercially available zeolite that can be suitably used as another odor removal component in such a deodorant composition is HSZ 822HOA (H-ZSM-5, manufactured by Tosoh Corporation, silica / alumina ratio (SiO₂)). ２ / Al ２ O ３ Ratio (mol / mol): 24, average particle size: 5 μm), HSZ 891HOA (H-ZSM-5, manufactured by Tosoh Corporation, silica / alumina ratio (SiO ２ / Al ２ O ３ ratio (mol / mol): 1500, average particle size: 4 μm).

[0034] In the deodorant composition of the present invention, the ratio of the odor removal catalyst of the present invention to other odor removal components such as physical adsorbents is not particularly limited as long as it exhibits a deodorizing effect. For example, the ratio of odor removal catalyst to odor removal component may be in the range of 99 / 1 to 1 / 99 (mass ratio), 90 / 10 to 1 / 99 (mass ratio), 50 / 50 to 3 / 97 (mass ratio), 30 / 70 to 5 / 90 (mass ratio), or 15 / 85 to 10 / 90 (mass ratio). Such a range is preferable because it provides excellent adsorption effect for odor substances.

[0035] The deodorant composition of the present invention may further comprise the odor removing catalyst of the present invention and a silica / alumina ratio (SiO ２ / Al ２ O ３ When a zeolite with a mol / mol ratio of 20 to 45 or 50 to 3000 is included, the mass ratio of the odor removal catalyst to the zeolite (odor removal catalyst / zeolite) is preferably 99 / 1 to 1 / 99, more preferably 90 / 10 to 1 / 99 (mass ratio), more preferably 50 / 50 to 3 / 97 (mass ratio), even more preferably 30 / 70 to 5 / 90 (mass ratio), and particularly preferably 15 / 85 to 10 / 90 (mass ratio), from the viewpoint of adsorption effect of odor substances, etc. Here, the zeolite as the odor removal component is preferably MFI type zeolite.

[0036] <Deodorizing Products (Deodorizers)> The odor removal catalyst and deodorizing agent composition of the present invention have a deodorizing effect, and therefore, for example, a deodorizing product can be provided in the form of powder or granules in a container such as a cartridge. By leaving this deodorizing product undisturbed in the vicinity of odor sources indoors or outdoors, the concentration of unpleasant odors or odor components can be reduced.

[0037] The odor removal catalyst and deodorizer composition of the present invention can be prepared as a liquid, solid, or gel-like solid by known methods and used for various industrial and household deodorizer applications. Examples of deodorizing liquids include those dissolved in an appropriate organic solvent such as water or ethanol, or emulsified with an appropriate surfactant, or aerosol deodorizers prepared by filling these liquids with a propellant into a spray container. Examples of solid deodorizers include powders mixed with powdered inorganic substances such as silica or perlite, those adsorbed on paper or porous materials, or those kneaded into any synthetic resin such as polyethylene or elastomer resin. Examples of gel-like solid deodorizers include those added to a natural or synthetic polymer gel base such as agar, carrageenan, or polyethylene glycol. If necessary, surfactants, disinfectants, fragrances, colorants, etc. may be added to these formulations. Such solid deodorizers or gel-like solid deodorizers may contain the odor removal catalyst of the present invention in any amount taking into consideration the usage form and deodorizing performance, and are not particularly limited. However, one preferred embodiment includes those containing the odor removal catalyst of the present invention in an amount of typically 0.01 to 50% by mass, preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass.

[0038] For home use, the deodorizing product of the present invention can be used to deodorize rooms, refrigerators, toilets, trash cans, etc., and to remove and prevent body odor. Furthermore, for industrial use, it can be used appropriately to remove odors in sewage treatment plants, fish processing plants, fish meal manufacturing plants, livestock barns, livestock or poultry manure drying plants, pulp factories, etc., and is particularly suitable for reducing and removing odorous substances such as acetaldehyde.

[0039] One useful deodorizing product using the odor removal catalyst and deodorizing composition of the present invention is a deodorizing fiber. In this case, the odor removal catalyst and deodorizing composition may be attached or bonded to the surface of raw fiber (1), or the odor removal catalyst and deodorizing composition may be embedded in the raw fiber so that they are exposed to the surface (2). The raw fiber may be either a natural fiber or a synthetic fiber, and may be any of short fiber, long fiber, and composite fiber with a core-sheath structure. The deodorizing fiber (1) can be obtained by applying a deodorizing agent-containing liquid composition (coating liquid) consisting of an aqueous or organic solvent-based suspension containing the deodorizing agent composition to the surface of the raw fiber by gravure coating, dipping, spray coating, or other methods, and then removing the medium such as the solvent.

[0040] This deodorant-containing liquid composition (coating liquid) may contain a binder to improve the adhesion of the deodorant composition to the surface of the raw fiber. Examples of binders include acrylic binders, acrylic silicone binders, styrene binders, and acrylic styrene binders. The ratio of deodorant to binder (demodorant / binder, mass ratio) is usually 95 / 5 to 10 / 90, preferably 80 / 20 to 20 / 80, and more preferably 60 / 40 to 25 / 75, and an appropriate ratio can be selected depending on the application. The lower the binder ratio, the more easily the deodorant's performance is exhibited, but it also tends to be more easily removed from the fiber.

[0041] If the viscosity of the deodorant-containing liquid composition is low and the deodorant settles, a thickening agent can be added. Examples of thickening agents include polysaccharides such as sodium alginate, methylcellulose, hydroxypropylcellulose, and xanthan gum, polyvinyl alcohol, and polymethacrylic acid-based thickening agents. The amount added to the coating solution is 0.01 to 10% by mass, preferably 0.1 to 5% by mass, and more preferably 0.2 to 2% by mass. If the wettability of the coating solution to the fibers is insufficient, a surfactant may be added. Examples of surfactants include alkyl sulfates such as sodium alkylbenzenesulfonate, sodium alkyloxybenzenesulfonate, and sodium lauryl sulfate, and acetylene glycol-based surfactants. The amount added to the coating solution is 0.01 to 10% by mass, preferably 0.1 to 5% by mass, and more preferably 0.2 to 2% by mass. There are no particular restrictions on the pH of the aqueous coating solution containing the deodorant composition, but in order to fully exhibit the performance of the deodorant composition, the pH is preferably around 6 to 8.

[0042] Furthermore, the deodorizing fiber (2) can be obtained by blending the deodorizing agent composition of the present invention with a molten liquid fiber resin or a dissolved fiber resin solution, and then fiberizing the resulting deodorizing agent-containing resin composition. The fiber resin that can be used in this method is not particularly limited, and known chemical fibers can be used. Preferred resins include polyester, polyamide, acrylic, polyethylene, polypropylene, polyvinyl, polyvinylidene, polyurethane, and polystyrene. These resins may be homopolymers or copolymers. In the case of copolymers, the polymerization ratio of monomers is not particularly limited.

[0043] The proportion of odor removal catalyst and deodorant composition contained in the deodorant-containing resin composition is not particularly limited. Generally, increasing the content of odor removal catalyst and deodorant composition can strongly enhance deodorizing properties and extend their duration. However, even if the content exceeds a certain level, there may not be a significant difference in the deodorizing effect, or the strength of the deodorizing fibers may decrease. Therefore, the content is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the fiber resin.

[0044] Another major deodorizing product of the odor removal catalyst and deodorant composition of the present invention is a deodorant-containing paint composition. The oils or resins that form the main component of the paint vehicle used in the production of the deodorant-containing paint composition are not particularly limited and may be natural vegetable oils, natural resins, semi-synthetic resins, or synthetic resins. Examples of oils and resins that can be used include drying oils or semi-drying oils such as linseed oil, linseed oil, and soybean oil, rosin, nitrocellulose, ethylcellulose, cellulose butyrate, benzylcellulose, novolac-type or resol-type phenolic resins, alkyd resins, aminoalkyd resins, acrylic resins, vinyl chloride resins, silicone resins, fluororesins, epoxy resins, urethane resins, saturated polyester resins, melamine resins, and polyvinylidene chloride resins. The deodorant-containing paint composition may be thermoplastic or curable.

[0045] The proportion of the odor-removing catalyst and deodorant composition of the present invention contained in the deodorant-containing paint composition is not particularly limited. Generally, increasing the content of the odor-removing catalyst and deodorant composition can strongly enhance the deodorizing effect and make it last longer, but even if the content exceeds a certain amount, there is no significant difference in the deodorizing effect, or the gloss of the painted surface may be lost or cracks may occur. Therefore, the content ratio of the odor-removing catalyst and deodorant composition is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass, based on 100% by mass of the composition.

[0046] The odor removal catalyst and deodorizer composition of the present invention can be used in both liquid and powder paints. The deodorizer-containing paint composition may be a type that forms a film by any mechanism, and when the coating is cured, it may be an oxidative polymerization type, moisture polymerization type, heat curing type, catalyst curing type, ultraviolet curing type, polyol curing type, or the like. It may also be applied to sintered coating, which is cured by baking. The pigments, dispersants, and other additives incorporated into the composition are not particularly limited, except for those that may chemically react with the odor removal catalyst and deodorizer composition of the present invention. The deodorizer-containing paint composition can be easily prepared by thoroughly dispersing and mixing the raw material components using a common mixing device such as a ball mill, roll mill, disperser, or mixer.

[0047] Furthermore, another deodorizing product using the odor removal catalyst and deodorant composition of the present invention is a deodorizing sheet (including a deodorizing film). The raw material sheet before processing is not particularly limited, and its material, microstructure, etc., can be made according to the application. Preferred materials for the raw material sheet are organic materials such as resin and paper, inorganic materials, or composites thereof. The raw material sheet preferably has breathability from one side to the other. Other preferred specific examples of the raw material sheet include Japanese paper, synthetic paper, nonwoven fabric, resin film, etc., and a particularly preferred raw material sheet is paper made from natural pulp and / or synthetic pulp. When natural pulp is used, deodorant particles are easily sandwiched between the finely branched fibers, and it can become a practical carrier without the use of a binder. On the other hand, synthetic pulp has the advantage of excellent chemical resistance. When using synthetic pulp, it can be difficult to support deodorant particles by sandwiching the powder between the fibers. To suppress this, some of the fibers may be melted during the drying process after papermaking to increase the adhesion between the powder and the fibers, or other thermosetting resin fibers may be mixed in with some of the fibers. By mixing natural pulp and synthetic pulp in appropriate proportions, it is possible to obtain paper with various properties adjusted. Generally, increasing the proportion of synthetic pulp yields paper with excellent strength, water resistance, chemical resistance, and oil resistance, while increasing the proportion of natural pulp yields paper with excellent water absorption, gas permeability, hydrophilicity, moldability, and texture.

[0048] In the deodorizing sheet, the deodorizing composition may be contained throughout the entire raw material sheet from one side to the other side, or may be disposed in a surface layer on one side or the other side, or may be disposed inside the raw material sheet excluding the surface layer.

[0049] The amount of the odor removal catalyst and deodorant composition of the present invention supported in the deodorizing sheet is not particularly limited. Generally, increasing the amount of the odor removal catalyst and deodorant composition supported will make the deodorizing effect more powerful and last for a longer period of time, but even if more than a certain amount is supported, there will be no significant difference in the deodorizing effect. Therefore, the amount of the odor removal catalyst and deodorant composition supported is preferably 0.1 to 10 parts by mass per 100 parts by mass of the raw material sheet.

[0050] The method for producing the deodorizing sheet is not particularly limited. The odor removal catalyst and deodorizer composition of the present invention may be supported either simultaneously with or after the production of the raw material sheet. For example, when supporting them on paper, a method of introducing the odor removal catalyst and deodorizer composition in any step of the papermaking process, or a method of applying, immersing, or spraying a deodorizer-containing liquid composition (coating liquid) containing a binder onto pre-produced paper can be applied. The type of binder, and the thickener and surfactant that can be added to the coating liquid are the same as those explained in the section on deodorizing fibers. When a deodorizer-containing liquid composition is used, the amount of the odor removal catalyst and deodorizer composition supported is 0.05 to 10 g / m 2 It is preferable to coat the film so that the thickness is approximately equal to the thickness of the film.

[0051] <Uses> The odor removal catalyst of the present invention and the deodorizing composition and deodorizing product containing the same adsorb and decompose surrounding odorous substances, thereby reducing and eliminating odors caused by odorous substances selected from, for example, aldehydes, carboxylic acids, esters, amines, thiols, and hydrocarbons for a long period of time.

[0052] The odor removing catalyst of the present invention and the deodorizing composition and deodorizing product containing the same may be used as is or may be used in combination with other materials such as resins. For example, even when the odor removing catalyst of the present invention is mixed with other materials such as resins to obtain a molded product, it can maintain its deodorizing performance and reduce and remove odors over a long period of time.

[0053] The odor removal catalyst of the present invention and the deodorizer composition containing the same can be suitably used to reduce and remove odors caused by odorous substances in the atmosphere, and can be particularly suitably used for deodorizing indoor spaces such as the inside of a building or an automobile.

[0054] Furthermore, the odor removal catalyst, deodorizer composition, and deodorizing product of the present invention can be used in a variety of applications without particular limitation, for example, in clothing, wigs, shoes, gloves, rubber gloves, upholstery, curtains, carpets, tiles, wallpaper, deodorizing air filters, or vehicle interior materials, etc. Any of the above forms of the deodorizing product may be used for these applications.

[0055] Vehicle interiors include automobiles, trains, passenger planes, and ships, while vehicle interior materials include ceiling materials, inner panels, door trims, headrests, steering wheels, shift levers, instrument panels, seat covers, floor materials, floor mats, and back door panels.

[0056] Other uses of the deodorizing product of the present invention include, in particular, the use of the deodorizing fiber in textile products and rubber products such as clothing such as underwear, socks, and aprons, nursing clothing, wigs, gloves, rubber gloves, futons, cushions, blankets, carpets, sofas, air filters, futon covers, curtains, and car seats, which are processed with deodorizing sheets.

[0057] As another application of the deodorizing product of the present invention, the deodorizing coating composition can be suitably used, for example, for the interior and exterior walls of buildings, vehicles, railways, etc., waste incineration facilities, food waste containers, deodorizing air filters, etc. It can be used particularly for building materials such as flooring and interior walls of factories with high VOC concentrations and flooring and interior walls of fish markets.

[0058] <Odor Removal Method> The odor removal method of the present invention is a method of reducing and removing odors caused by odor substances using the odor removal catalyst of the present invention or a deodorant composition or deodorant product containing the same (hereinafter also referred to as the odor removal catalyst, etc.), and preferably a method of reducing odors caused by at least one odor substance selected from aldehydes, carboxylic acids, esters, amines, thiols, and hydrocarbons. The odor removal catalyst may be used in its original form or in combination with other materials.

[0059] The odor removal method of the present invention can be achieved by bringing the odor removal catalyst, etc. of the present invention described above into contact with a gas to be odor-removed (a gas containing odorous substances). Specifically, this method includes placing the odor removal catalyst, etc. of the present invention in a space to be odor-removed, or passing a gas containing odorous substances through a space where the odor removal catalyst, etc. of the present invention is present.

[0060] When odor removal is performed using the odor removal catalyst according to the present invention, the zeolite constituting the odor removal catalyst adsorbs surrounding odor substances, resulting in a high initial odor reduction effect. Furthermore, the adsorbed odor substances are decomposed by the supported metal component containing Pt, preventing the release of adsorbed odor substances and restoring the adsorption capacity. As a result, odors caused by odor substances can be reduced and removed over a long period of time. In addition, when a deodorant composition or deodorant product containing a physical adsorbent capable of adsorbing and decomposing odor substances, or a chemical adsorbent that deodorizes through chemical interaction with odor substances, is used together with the odor removal catalyst according to the present invention, the initial odor reduction effect can be further improved.

[0061] Furthermore, when using the odor removal catalyst according to the present invention to remove odors such as aldehydes, in addition to being able to significantly reduce and remove odors under high-temperature conditions of around 80°C where high catalytic activity is expected, an unexpected effect is obtained in that odors can be reduced and removed to the same or better degree than under high-temperature conditions, even under relatively low-temperature conditions such as 40°C or below, where conventional odor removal catalysts sometimes performed worse than under high-temperature conditions.

[0062] Although the detailed factors that produce such effects are not clear, the odor removal catalyst according to the present invention has a silica / alumina ratio (SiO ２ / Al ２ O ３ The inventors surmise that the odor removal catalyst of the present invention uses zeolite with a high silica / alumina ratio of 50 or more and 3000 or less (mol / mol). This high hydrophobicity allows it to preferentially adsorb odors in the air over water, and that the water produced by decomposition of the odors is easily released into the air immediately, even at low temperatures such as 40°C or less. This allows the catalyst to continue to adsorb, decompose, and release odors for a long period of time, resulting in improved deodorizing performance.

[0063] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0064] Example 1 Preparation of Odor Removal Catalyst A 0.292 g of hexachloroplatinic (IV) acid hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was weighed as a platinum-containing compound and dissolved in 80 mL of distilled water to obtain a solution. This solution was placed in a 300 mL eggplant-shaped flask, and then MFI-type zeolite (H-ZSM-5, manufactured by Tosoh Corporation, HSZ 891HOA, silica / alumina ratio (SiO ２ / Al ２ O ３ The platinum compound solution was impregnated into the zeolite, with 11 g of platinum (Pt) (ratio (mol / mol): 1500, average particle size: 4 μm) being added, so that the platinum (Pt) loading was 1 mass %. The eggplant-shaped flask was then attached to a rotary evaporator, and the water was evaporated at 70°C under vacuum, and the remaining powder was recovered. The recovered powder was placed in an electric furnace and calcined in air at 400°C for 12 hours to obtain a powdery calcined body.

[0065] Next, the BELCAT-B catalyst analyzer (manufactured by Microtrac-Bel Co., Ltd.) was used as a heating furnace to hydrogen-reduce the powdered calcined material obtained by the calcination process. This catalyst analyzer includes an electric furnace, a cooling fan for cooling the electric furnace, and gas ports capable of supplying various gases. First, the powdered calcined material was placed in a quartz tube, and the quartz tube was set in the electric furnace section of the catalyst analyzer. Subsequently, the powdered calcined material was heated to 400°C at a rate of 10°C per minute under a helium gas flow, then held at 400°C for 2 hours under a 5% hydrogen / argon gas flow, and then cooled while running the cooling fan attached to the catalyst analyzer under a helium gas flow (it took about 1 hour to cool from 400°C to 40°C) to perform hydrogen reduction and prepare odor removal catalyst A, which is a Pt / zeolite catalyst.

[0066] <Evaluation of Acetic Acid Deodorizing Performance> 10 mg of the odor removal catalyst A prepared above was weighed and wrapped in a nylon mesh (manufactured by AS ONE Corporation, mesh size: 10 μm). The nylon mesh was then placed in a 5 L sampling bag (manufactured by Omi Odor Air Service Co., Ltd., material: vinyl alcohol-based polymer film). A sampling bag without odor removal catalyst A was used as a blank. 3 L of air passed through an activated carbon filter was introduced into the sampling bag, and then an aqueous solution of acetic acid was injected until the acetic acid concentration in the sampling bag reached 30 ppm. After standing for 2 hours and 24 hours at room temperature (25°C), the concentration of acetic acid was measured, and the deodorization rate was calculated using the following formula. Here, the concentration of acetic acid was measured using an acetic acid detection tube "Acetic Acid 81 L" (manufactured by Gastec Co., Ltd.). The results are shown in Table 1. Deodorization rate (%) = (X - Y) / X × 100 X: Concentration of acetic acid in the blank sampling bag Y: Concentration of acetic acid in the sampling bag containing odor removal catalyst A

[0067] <Evaluation of Propionaldehyde Deodorizing Properties (80°C and 40°C)> Using 10 mg of the odor removal catalyst A prepared above, a continuous decomposition test was conducted in a fixed-bed flow system to continuously treat gas containing propionaldehyde as an odorant, as follows. (1) Evaluation of Propionaldehyde Deodorizing Properties (80°C) 10 mg of odor removal catalyst A was evenly spread in a cylindrical glass reaction tube with an inner diameter of 1 cm and a length of 20 cm, and glass wool was packed into both ends of the tube. This was placed horizontally in an oven, and a 10 ppm propionaldehyde mixed gas (air diluted) was passed through at 3 L / h at an oven temperature of 80°C. 1 mL of gas was sampled at the inlet and outlet of the reaction tube, and the propionaldehyde concentration was measured over time by GC (gas chromatography). The GC analysis conditions were as follows. The results are shown in Table 2 and the graph in Figure 1. Apparatus: GC-2014 (Shimadzu Corporation) Column: DB-5 (Agilent Technologies Inc.), 0.53 mm x 60 m, diameter 1.50 μm Detector: FID (Flame Ionization Detector) Carrier gas: Helium Column temperature: 50°C (constant) (2) Evaluation of propionaldehyde deodorizing property (40°C) This was evaluated in the same manner as in (1) Evaluation of propionaldehyde deodorizing property (80°C) above, except that the oven temperature was changed to 40°C. The results are shown in Table 3 and the graph in Figure 2.

[0068] [Example 2] <Preparation of Odor Removal Catalyst B> Odor removal catalyst A prepared in Example 1 and MFI type zeolite (H-ZSM-5, HSZ 822HOA manufactured by Tosoh Corporation, silica / alumina ratio (SiO ２ / Al ２ O ３A Pt / zeolite catalyst (Pt / zeolite catalyst, Pt / zeolite ratio (mol / mol): 24, average particle size: 5 μm) and a Pt / zeolite catalyst (Pt / zeolite catalyst, P ...

[0069] Comparative Example 1 Preparation of Odor Removal Catalyst C MFI type zeolite (H-ZSM-5, manufactured by Tosoh Corporation, HSZ 891HOA, silica / alumina ratio (SiO ２ / Al ２ O ３ Instead of the silica / alumina ratio (mol / mol): 1500, average particle size: 4 μm, MFI type zeolite (H-ZSM-5, manufactured by Tosoh Corporation, HSZ 822HOA, silica / alumina ratio (SiO ２ / Al ２ O ３ Odor removal catalyst C, which was a Pt / zeolite catalyst, was prepared in the same manner as in Example 1, except that a Pt / zeolite catalyst (Pt / zeolite catalyst ratio (mol / mol)): 24, average particle size: 5 μm) was used. <Evaluation of Acetic Acid Deodorizing Property> Except that the odor removal catalyst C prepared above was used instead of odor removal catalyst A, evaluation of acetic acid deodorizing property was performed in the same manner as in Example 1. The results are shown in Table 1.

[0070] <Evaluation of Propionaldehyde Deodorizing Property (80°C and 40°C)> Evaluation of propionaldehyde deodorizing property (80°C and 40°C) was carried out in the same manner as in Example 1, except that the odor elimination catalyst C prepared above was used instead of odor elimination catalyst A. The results of the propionaldehyde deodorizing property (80°C) are shown in Table 2 and the graph in Figure 5, and the results of the propionaldehyde deodorizing property (40°C) are shown in Table 3 and the graph in Figure 6.

[0071]

[0072]

[0073]

[0074] From the results in Table 1, it was found that in Examples 1 and 2, which used a catalyst containing Odor Removal Catalyst A, the odor removal catalyst of the present invention, the deodorization rate of acetic acid was higher than in Comparative Example 1, which used a catalyst without Odor Removal Catalyst A. This indicates that acetic acid (carboxylic acids) can be efficiently deodorized by using Odor Removal Catalyst A.

[0075] 1 to 6, Examples 1 and 2, which used catalysts containing odor removal catalyst A or B, demonstrated propionaldehyde deodorizing properties even after 24 hours or more at both 80°C and 40°C, demonstrating the ability to continuously remove propionaldehyde (aldehydes). On the other hand, Comparative Example 1, which used odor removal catalyst C without the odor removal catalyst of the present invention, demonstrated propionaldehyde deodorizing properties even after continuous treatment at 80°C, but at 40°C, a decrease in propionaldehyde concentration was only observed initially in the test. That is, odor removal catalyst C of Comparative Example 1, which is a conventional zeolite / Pt catalyst, had a lower deodorizing rate at low temperatures of around 40°C than at high temperatures of around 80°C, and did not achieve a sufficient propionaldehyde deodorizing effect, whereas odor removal catalysts A and B of Examples 1 and 2, which are odor removal catalysts of the present invention, showed an unexpected tendency to have a higher propionaldehyde deodorizing rate at low temperatures than at high temperatures, and also showed sufficient deodorizing properties even after a long period of time had passed. This shows that the odor removal catalyst of the present invention can continuously reduce and remove odorous components such as aldehydes even under relatively low temperature conditions, such as below 40°C, and is therefore more suitable for deodorizing under room temperature conditions, etc.

[0076] [Example 3] <Preparation of Elastomer Sheet E> Odor removal catalyst D, with an average particle size of 2 μm, was prepared by crushing odor removal catalyst A prepared in Example 1 with a super jet mill (SJ-500, manufactured by Nisshin Engineering). Subsequently, using an 8-inch roll, each component was kneaded in the mixing ratio (parts by mass) shown in Table 4 to obtain an elastomer composition containing odor removal catalyst D. The kneading conditions were: roll temperature front roll / rear roll = 50°C / 50°C, roll peripheral speed front roll / rear roll = 18 rpm / 15 rpm, roll gap = 3 mm, and kneading time 8 minutes with dispensing.

[0077]

[0078] The components listed in Table 4 are as follows. The polymer composition of the elastomer resin components was determined using the method described in ASTM D3900 for ethylene content and ASTM D6047 for diene (ENB) content. • EPDM1: Ethylene-propylene-5-ethylidene-2-norbornene (ENB) copolymer, Mooney viscosity (ML(1+4)125℃) = 43, ethylene content = 65% by mass, ENB content = 4.5% by mass, oil spread = 20 phr • EPDM2: Ethylene-propylene-ENB copolymer, Mooney viscosity (ML(1+4)125℃) = 57, ethylene content = 61% by mass, ENB content = 5.4% by mass - "Suncellar M" (product name): 2-mercaptobenzothiazole, manufactured by Sanshin Chemical Industry Co., Ltd., vulcanization accelerator - "Suncellar TT" (product name): tetramethylthiuram disulfide, manufactured by Sanshin Chemical Industry Co., Ltd., vulcanization accelerator - "Suncellar BZ" (product name): dibutyldithiocarbamate zinc, manufactured by Sanshin Chemical Industry Co., Ltd., vulcanization accelerator - "Suncellar CM" (product name): N-cyclohexyl-2-benzothiazole sulfenamide, manufactured by Sanshin Chemical Industry Co., Ltd., vulcanization accelerator - "Sunfer R" (product name): morpholine disulfide, manufactured by Sanshin Chemical Industry Co., Ltd., vulcanization accelerator - "Vesta BS" (product name): manufactured by Inoue Lime Industry Co., Ltd., defoaming agent

[0079] Next, the obtained elastomer composition was vulcanized at 170°C for 10 minutes using a press molding machine to prepare an elastomer sheet E with a thickness of 2 mm.

[0080] <Sensory Evaluation of Deodorizing Properties> The sensory evaluation of the elastomer sheet E prepared above was carried out in accordance with ISO 12219-7 as follows. - Method for preparing standard odor bags ISO 12219-7 specifies the relationship between each odor intensity and the degree of odor, divided into six levels from 1 to 6 as criteria for sensory evaluation (see Table 5 below). 50 mL of water / 1-butanol solution for each standard odor corresponding to each odor intensity was prepared according to Table 6 below. 10 L of dry deodorized air was introduced into a 10 L sampling bag (deodorized Tedlar bag, manufactured by GL Sciences Co., Ltd.), 10 mL of water / 1-butanol solution corresponding to each odor intensity was added, the valve at the inlet was closed, and it was left at room temperature for 2 hours to create each standard odor corresponding to odor intensity 1 to 6.

[0081]

[0082]

[0083] • Method for creating evaluation sample bags: Cut a slit in the bottom of a 10L sampling bag (deodorized Tedlar bag, manufactured by GL Sciences Co., Ltd.) to separate each evaluation sample by 100cm. 2 The sample was placed in a sampling bag and heat-sealed. 5 liters of dry, deodorized air was introduced, and the valve at the inlet was closed to create an evaluation sample bag.

[0084] - Sensory evaluation test regarding deodorization: Sample bags were heated to 80°C, and the odor intensity was evaluated in 0.5 increments by comparing it to a reference odor bag after 2 hours, 4 hours, and 24 hours. The evaluation was performed by five panelists, and the average value was used as the odor intensity of the evaluation sample. The results are shown in Table 7.

[0085] [Comparative Example 2] An elastomer sheet F without odor removal catalyst D was prepared in the same manner as in Example 3, except that odor removal catalyst D was not used. A sensory evaluation test regarding deodorization was conducted, and the results are shown in Table 7.

[0086]

[0087] Table 7 shows that, despite containing only a very small amount of the odor removal catalyst, the vulcanized molded article of Example 3, which is made from the elastomer composition of Comparative Example 2, which is made from the elastomer composition of which is not made from the odor removal catalyst, exhibited significantly reduced odor intensity and suppressed the increase in odor over time.

[0088] [Example 4] <Preparation of Binder F> 550 g of deionized water and 1 g of sodium dodecyldiphenyl ether disulfonate were charged into a reaction vessel equipped with a stirrer, reflux condenser, dropper, and thermometer, and the temperature was raised to 72°C while purging with nitrogen under stirring. Maintaining the internal temperature at 72°C, 3 g of potassium persulfate was added as a polymerization initiator. After dissolution, an emulsion prepared by adding 15 g of acrylamide, 590 g of methyl methacrylate, 330 g of n-butyl acrylate, 20 g of 2-hydroxyethyl methacrylate, 20 g of methacrylic acid, 15 g of ethylene glycol dimethacrylate, and 1 g of t-dodecyl mercaptan to 400 g of deionized water and 3 g of sodium dodecyldiphenyl ether disulfonate under stirring was continuously added dropwise to the reaction solution over 4 hours. After the addition was complete, the mixture was allowed to mature for 2 hours. The obtained aqueous solution containing Binder 1 was cooled to room temperature, and then ion-exchanged water and an aqueous ammonium solution were added to adjust the solid content to 50% and the pH to 7.5, thereby obtaining Acrylic Binder F having a glass transition temperature (Tg) of 56°C as measured by DSC.

[0089] <Preparation of coating mixture (coating liquid)> 2 g of odor removal catalyst A prepared in Example 1, 5 g of binder F, 3.9 g of aqueous solution of 5% thickener SN615 (manufactured by Sannobuko Co., Ltd.), 3.6 g of aqueous solution of 10% DOWFAX2A1 (manufactured by Dow Ltd.), and 14 g of water were mixed and stirred to obtain coating liquid G in which particles were uniformly dispersed.

[0090] <Preparation of deodorizing material> The coating solution G obtained above was applied to a PET nonwoven fabric (05TH-80, manufactured by Hirose Paper Co., Ltd., basis weight 80 g / m) using a spray coater (manufactured by Anest Iwata Corporation, product name WIDER1-10E1G). 2 ) at room temperature (23°C), the amount of odor removal catalyst A held on one side was 0.5 g / m 2The material was spray-coated uniformly to achieve the above result. This was dried at 80°C for 10 minutes to obtain a deodorizing material H that retained the odor-removing catalyst component in the aforementioned amount.

[0091] <Evaluation of Deodorizing Materials> (Deodorizing Evaluation) Deodorizing material H obtained above 100cm 2 The bag was placed in a 5L sampling bag (Frec Sampler, manufactured by Omi Odor Air Service Co., Ltd.), 3L of air was introduced, and a silicone cap was placed on the inlet. Next, 5.5mL of 20,000vol. ppm acetic acid / air was injected into the sampling bag using a gas-tight syringe, and the acetic acid concentration in the bag was adjusted to 30ppm. The acetic acid concentration in the bag after standing at room temperature for 4 hours was evaluated using a detector tube (manufactured by Gastec Corporation), and the results are shown in Table 7. In the evaluation, the same evaluation was performed using only the sampling bag without the odor removal catalyst, and the result was used as the blank, and the deodorization rate relative to the blank was recorded. Furthermore, using the above-mentioned method, the pyridine concentration in the bag was set to 12ppm, the trimethylamine concentration in the bag was set to 28ppm, the isovaleric acid concentration in the bag was set to 38ppm, and the nonenal concentration in the bag was set to 14ppm, and the deodorization evaluation was performed in the same manner as in the case of acetic acid. The results are shown in Table 8.

[0092] [Comparative Example 3] Instead of deodorizing material H, PET nonwoven fabric (05TH-80, manufactured by Hirose Paper Co., Ltd., basis weight 80 g / m²) was used. 2 ) 100cm 2 Except for the use of [specific material], the deodorization evaluation was performed in the same manner as in Example 4. The results are shown in Table 8.

[0093]

[0094] From Table 8, it can be seen that Example 4, which used a nonwoven fabric (deodorizing material H) containing odor removal catalyst A, which is the odor removal catalyst of the present invention, had a higher deodorizing rate for all odors, acetic acid, pyridine, trimethylamine, isovaleric acid, and nonenal, than Comparative Example 3, which used a nonwoven fabric that did not contain odor removal catalyst A, and that odor removal catalyst A can efficiently deodorize carboxylic acids, amines, and aldehydes even when coated on a material such as nonwoven fabric.

[0095] [Example 5] <Preparation of Odor Removal Catalyst I> MFI type zeolite (H-ZSM-5, HSZ 891HOA manufactured by Tosoh Corporation, silica / alumina ratio (SiO ２ / Al ２ O ３ Instead of the ratio (mol / mol): 1500, average particle size: 4 μm, use MFI type zeolite (H-ZSM-5, manufactured by Zeolist International, silica / alumina ratio (SiO2) ２ / Al ２ O ３ Odor removal catalyst I, a Pt / zeolite catalyst, was prepared in the same manner as in Example 1, except that a ratio (mol / mol) of 150 and an average particle size (measured value) of 2 μm were used. The measured average particle size of the MFI-type zeolite was obtained by measuring under the same measurement conditions as for odor removal catalysts M, N, and O described later. <Evaluation of propionaldehyde deodorization rate (80°C and 40°C)> The same procedure as in Example 1 was performed, except that odor removal catalyst I prepared above was used instead of odor removal catalyst A, and the propionaldehyde deodorization rate (80°C and 40°C) after 24 hours was evaluated. The results are shown in Table 9.

[0096] [Example 6] <Preparation of Odor Removal Catalyst J> MFI type zeolite (H-ZSM-5, HSZ 891HOA manufactured by Tosoh Corporation, silica / alumina ratio (SiO ２ / Al ２ O ３ ratio (mol / mol): 1500, average particle size: 4 μm), and silica / alumina ratio (SiO ２ / Al ２ O ３ Odor removal catalyst J, which is a Pt / zeolite catalyst, was prepared in the same manner as in Example 1, except that an MFI-type zeolite with a silica / alumina ratio (SiO₂) of 300 was used. ２ / Al ２ O ３ As the MFI zeolite having a zeolite ratio (mol / mol) of 300, MFI zeolite (NH ４ - ZSM-5, manufactured by Zeolyst International, silica / alumina ratio (SiO ２ / Al ２O ３ A material with a ratio (mol / mol): 300 and an average particle size (measured value): 4 μm was calcined at 550°C under air to produce H-ZSM-5, which was used. <Evaluation of propionaldehyde deodorization rate (80°C and 40°C)> Except for using the odor removal catalyst J prepared above instead of odor removal catalyst A, the same procedure as in Example 1 was performed, and the propionaldehyde deodorization rate (80°C and 40°C) after 24 hours was evaluated. The results are shown in Table 9.

[0097] [Example 7] <Preparation of odor removal catalyst K> MFI type zeolite (H-ZSM-5, HSZ 891HOA manufactured by Tosoh Corporation), silica / alumina ratio (SiO ２ / Al ２ O ３ ratio (mol / mol): 1500, average particle size: 4 μm), and silica / alumina ratio (SiO ２ / Al ２ O ３ An odor removal catalyst K, which was a Pt / zeolite catalyst, was prepared in the same manner as in Example 1, except that an MFI zeolite with a silica / alumina ratio (SiO ２ / Al ２ O ３ As the MFI zeolite having a zeolite ratio (mol / mol) of 500, MFI zeolite (NH ４ - ZSM-5, manufactured by Süd-Chemie, silica / alumina ratio (SiO ２ / Al ２ O ３ A material with a ratio (mol / mol): 500 and an average particle size (measured value): 15 μm was calcined at 550°C under air to produce H-ZSM-5. <Evaluation of propionaldehyde deodorization rate (80°C and 40°C)> Except for using the odor removal catalyst K prepared above instead of odor removal catalyst A, the same procedure as in Example 1 was performed, and the propionaldehyde deodorization rate (80°C and 40°C) after 24 hours was evaluated. The results are shown in Table 9.

[0098]

[0099] Example 8 Preparation of Odor Removal Catalyst L 0.0292 g of hexachloroplatinic (IV) acid hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a platinum-containing compound was weighed and dissolved in 80 mL of distilled water to obtain a solution. This solution was placed in a 300 mL eggplant-shaped flask, and then MFI-type zeolite (H-ZSM-5, manufactured by Tosoh Corporation; HSZ 891HOA, silica / alumina ratio (SiO ２ / Al ２ O ３ The platinum compound solution was impregnated into the zeolite so that the platinum (Pt) loading ratio was 0.1 mass%. The eggplant-shaped flask was then attached to a rotary evaporator, and the water was evaporated at 70°C under vacuum, and the remaining powder was recovered. The recovered powder was placed in an electric furnace and calcined in air at 400°C for 12 hours to obtain a powdery calcined product.

[0100] Next, the powdered calcined body obtained by the calcination was subjected to hydrogen reduction using a catalyst analyzer BELCAT-B (manufactured by Microtrac-Bell Corporation) as a heating furnace. This catalyst analyzer includes an electric furnace, a cooling fan for cooling the electric furnace, and a gas port capable of supplying various gases. First, the powdered calcined body was placed in a quartz tube, and the quartz tube was set in the electric furnace portion of the catalyst analyzer. Next, the powdered calcined body was heated to 400°C at a rate of 10°C per minute under a helium gas flow, then held at 400°C for 2 hours under a 5% hydrogen / argon gas flow, and then cooled under a helium gas flow while rotating the cooling fan attached to the catalyst analyzer (it took about 1 hour to cool from 400°C to 40°C). This hydrogen reduction was performed to prepare odor removal catalyst L, which is a Pt / zeolite catalyst.

[0101] <Evaluation of propionaldehyde deodorization rate (40°C)> The same procedure as in Example 1 was performed, except that odor removal catalyst L prepared above was used instead of odor removal catalyst A, and the propionaldehyde deodorization rate (40°C) after 24 hours was evaluated. The results are shown in Table 10.

[0102] <Evaluation of Toluene Deodorization Rate (20°C and 100°C)> 10 mg of the odor removal catalyst L prepared above was weighed and wrapped in a nylon mesh (manufactured by AS ONE Corporation, mesh size: 10 μm), and the nylon mesh was placed in a 5 L sampling bag (manufactured by Omi Odor Air Service Co., Ltd., material: vinyl alcohol-based polymer film). A sampling bag without the odor removal catalyst was used as a blank. 3 L of air passed through an activated carbon filter was introduced into the sampling bag, and then toluene was injected so that the toluene concentration in the sampling bag became 100 ppm. After standing for 2 hours at 20°C (room temperature) and 100°C, the toluene concentration was measured, and the deodorization rate was calculated using the following formula. The toluene concentration was measured using a toluene detector tube "Toluene 122L" (manufactured by Gastec Corporation). The results are shown in Table 11. Deodorization rate (%) = (X1 - Y1) / X1 × 100 X1: Toluene concentration in the blank sampling bag Y1: Toluene concentration in the sampling bag containing odor removal catalyst L

[0103] <Evaluation of Trimethylamine Deodorization Rate (20°C and 100°C)> 10 mg of the odor removal catalyst L prepared above was weighed and wrapped in a nylon mesh (manufactured by AS ONE Corporation, mesh size: 10 μm), and the nylon mesh was placed in a 5 L sampling bag (manufactured by Omi Odor Air Service Co., Ltd., material: vinyl alcohol-based polymer film). A sampling bag without the odor removal catalyst was used as a blank. 3 L of air passed through an activated carbon filter was introduced into the sampling bag, and then a trimethylamine solution was poured into the sampling bag so that the trimethylamine concentration in the sampling bag was 9 ppm. After standing for 2 hours at room temperature (20°C) and 100°C, the trimethylamine concentration was measured, and the deodorization rate was calculated using the following formula. The trimethylamine concentration was measured using an amines detector tube "Amines 180L" (manufactured by Gastec Corporation). The results are shown in Table 11. Deodorization rate (%) = (X² - Y²) / X² × 100 X²: Trimethylamine concentration in the blank sampling bag Y²: Trimethylamine concentration in the sampling bag containing odor removal catalyst L

[0104] [Examples 9-10, Comparative Example 4] <Preparation of odor removal catalysts M, N, and O> Odor removal catalyst L obtained in Example 8 was crushed using a Super Jet Mill (SJ-500, manufactured by Nisshin Engineering) to prepare odor removal catalyst M (Example 9) with an average particle size of 2.5 μm, odor removal catalyst N (Example 10) with an average particle size of 0.6 μm, and odor removal catalyst O (Comparative Example 4) with an average particle size of 0.4 μm. In preparing each odor removal catalyst, the crushing conditions and average particle size measurement conditions were as follows:

[0105] Grinding conditions: A slurry mixture of 40 g of odor removal catalyst L and 160 g of distilled water was used, and pulverized using a bead mill LMZ015 manufactured by Ashizawa Finetech Co., Ltd. under the following conditions: Mill capacity: 0.15 L; Beads: 0.5 mm diameter zirconia beads; Bead filling rate (apparent): 85%; Mill peripheral speed: 10 m / s; Slurry flow rate: 150 mL / min. In the preparation of odor removal catalyst M, the slurry was collected after three passes; in the preparation of odor removal catalyst N, the slurry was collected after 13 passes; and in the preparation of odor removal catalyst O, the slurry was collected after 13 passes and 20 minutes of circulation operation. Each of the collected slurries was dried at 400°C for 12 hours to obtain odor removal catalyst M, odor removal catalyst N, and odor removal catalyst O, respectively.

[0106] Measurement conditions for average particle size: Apparatus: Laser diffraction particle size distribution analyzer Mastersizer 3000 (manufactured by Malvern Panalytical) Dispersion unit: Hydro MV Dispersion medium: Water Particle refractive index: 1.473 Dispersion medium refractive index: 1.330

[0107] <Evaluation of propionaldehyde deodorizing property (40°C)> The same procedures as in Example 1 were carried out, except that the odor removal catalysts M to O prepared above were used instead of odor removal catalyst A, and the propionaldehyde deodorizing property (40°C) was evaluated after 24 hours. The results are shown in Table 10.

[0108]

[0109] Example 11 Preparation of Odor Removal Catalyst P Odor removal catalyst A (1% Pt-supported zeolite) prepared in Example 1 and MFI-type zeolite (H-ZSM-5, manufactured by Tosoh Corporation, HSZ 891HOA, silica / alumina ratio (SiO ２ / Al ２ O ３ The odor removal catalyst P was prepared as a Pt / zeolite catalyst with a Pt content of 0.1%.

[0110] <Evaluation of Toluene Deodorization Rate (20°C and 100°C)> The toluene deodorization rate (20°C and 100°C) was evaluated in the same manner as the evaluation of the toluene deodorization rate in Example 8, except that the odor removal catalyst P prepared above was used instead of the odor removal catalyst L. The results are shown in Table 11. <Evaluation of Trimethylamine Deodorization Rate (20°C and 100°C)> The trimethylamine deodorization rate (20°C and 100°C) was evaluated in the same manner as the evaluation of the trimethylamine deodorization rate in Example 8, except that the odor removal catalyst P prepared above was used instead of the odor removal catalyst L. The results are shown in Table 11.

[0111] [Example 12] <Preparation of Odor Removal Catalyst Q> Except for changing the amount of hexachloroplatinic acid hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) used to 1.46 g, odor removal catalyst Qa, which is a Pt / zeolite catalyst, was obtained in the same manner as the preparation of odor removal catalyst A in Example 1. When the obtained odor removal catalyst Qa was measured by wavelength-dispersive X-ray fluorescence analysis using Rigaku ZSX Primus IV, the actual amount of Pt was found to be 3.66%. 0.27 g of the obtained odor removal catalyst Qa and MFI type zeolite (H-ZSM-5, HSZ 891HOA manufactured by Tosoh Corporation, silica / alumina ratio (SiO ２ / Al ２ O ３ The resulting mixture was uniformly mixed with 9.73 g of zeolite powder (ratio (mol / mol)): 1500, average particle size: 4 μm) to prepare odor removal catalyst Q, which was a Pt / zeolite catalyst with a Pt content of 0.1%.

[0112] <Evaluation of Toluene Deodorization Rate (20°C and 100°C)> The toluene deodorization rate (20°C and 100°C) was evaluated in the same manner as in the evaluation of the toluene deodorization rate in Example 8, except that the odor removal catalyst Q prepared above was used instead of the odor removal catalyst L. The results are shown in Table 11. <Evaluation of Trimethylamine Deodorization Rate (20°C and 100°C)> The trimethylamine deodorization rate (20°C and 100°C) was evaluated in the same manner as in the evaluation of the trimethylamine deodorization rate in Example 8, except that the odor removal catalyst Q prepared above was used instead of the odor removal catalyst L. The results are shown in Table 11.

[0113]

Claims

1. An odor removal catalyst in which a metal component including Pt is supported on zeolite, wherein the silica / alumina ratio of the zeolite (SiO ２ / Al ２ O ３ (mol / mol)) is 50 or more and 3000 or less.

2. The odor removal catalyst according to claim 1, wherein the metal component comprises Pt and at least one metal element selected from Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Cu, Ag, and Au.

3. The odor removal catalyst according to claim 1, wherein the zeolite is an MFI type zeolite.

4. The odor removal catalyst according to claim 1, wherein the zeolite is an alkali metal-free zeolite.

5. The odor removal catalyst according to claim 1, having an average particle size of 0.5 μm or more and 20 μm or less.

6. The odor removal catalyst according to claim 1, wherein the amount of the metal component supported is 0.01 to 10 mass % in terms of the metal amount of the total metal components.

7. The odor removal catalyst according to claim 1 and a silica / alumina ratio (SiO ２ / Al ２ O ３ and an MFI zeolite having a molecular weight (mol / mol) of 20 or more and 45 or less.

8. The odor removal catalyst according to claim 1 and a silica / alumina ratio (SiO ２ / Al ２ O ３ and an MFI zeolite having a molecular weight (mol / mol) of 50 or more and 3,000 or less.

9. The odor removal catalyst according to claim 1 and a silica / alumina ratio (SiO ２ / Al ２ O ３ 8. The deodorant composition according to claim 7, wherein a mass ratio of the zeolite to the MFI zeolite having a molecular weight (mol / mol) of 20 or more and 45 or less is 99 / 1 or more and 1 / 99 or less.

10. The odor removal catalyst according to claim 1 and a silica / alumina ratio (SiO ２ / Al ２ O ３ 9. The deodorant composition according to claim 8, wherein a mass ratio of the zeolite having a molecular weight of 50 or more and an MFI type ...

11. A deodorizing product comprising the odor removal catalyst according to any one of claims 1 to 6 or the deodorizing composition according to any one of claims 7 to 10.

12. The deodorizing product according to claim 11, which is a deodorizing fiber, a deodorizing paint, or a deodorizing sheet.

13. The deodorizing product according to claim 11, which is used for clothing, wigs, shoes, gloves, rubber gloves, upholstery, curtains, carpets, tiles, wallpaper, deodorizing air filters, or vehicle interior materials.

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