JP7336089B2 - Method for producing porous metal complex granules - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing granules containing a porous metal complex that efficiently separates and recovers, or adsorbs and removes moisture, organic solvents, and malodorous components in the air.

A porous metal complex is also called a Porous Coordination Polymer or a Metal-Organic Framework (abbreviated as PCP/MOF), and is a porous material artificially synthesized using coordination bonds between metal ions and organic ligands. is. A framework is constructed by bridging metal ions with organic ligands, and the voids within this framework serve as spaces for capturing molecules.

Conventional porous materials include natural inorganic materials such as zeolite, silica gel, and activated carbon. Each has pore functions such as separation, storage, adsorption, and discharge, but it is difficult to control fine pores, and the pore functions are also affected. On the other hand, porous metal complexes can be synthesized with various porous structures by molecular design, and very complicated structures and highly functional or multifunctional porous materials can be constructed. Therefore, porous metal complexes can be used for gas (hydrogen, methane, CO2, etc.) storage, selective storage of molecules and ions, separation such as isomer separation, solid catalysts (oxidation reaction, addition reaction, hydrogenation reaction, etc.), removal A wide range of applications are expected, including release, isolation, transport, nanocontainers, and sensors.

Living odors such as tobacco odors, animal odors, and excretion odors are abundant in living environments such as homes, workplaces, and public facilities. Depending on the odor, it may become a social problem. Disposal of excrement becomes a problem with aging, but at the same time, the problem of excretion odor also arises. Tobacco odors and animal odors are also intolerable to some people. As for other life odors, it is desirable to remove them if possible in order to live comfortably in the living environment.

Porous materials such as zeolite, silica gel, and activated carbon have been conventionally used as one of the means for removing these living odors. However, it is difficult to say that such natural porous substances have a sufficient deodorizing effect.

Patent Document 1 also discloses a method for confining bad odors using a porous metal complex, which is an artificial porous material. Patent Literature 1 describes that fecal odors, bad breath, cigarette smoke, and the like are examples of offensive odors, and that porous metal complexes can be used as household deodorants. Note that Patent Document 1 neither describes nor suggests that the porous metal complex can be used as an antibacterial agent or an antiviral agent.

Patent document 2 proposes a deodorant and an antiviral agent using a porous metal complex. However, although the document describes the deodorant effect and antiviral effect of the porous metal complex, when the porous metal complex is actually used as it is, it is light because it contains voids, and the size is small. It easily becomes dust on the micron order and is difficult to handle. Moreover, there is no description of a method for producing granules.

WO2007/035596 JP 2019-088499

As described above, it has been found that when a deodorant or antiviral agent using a porous metal complex is to be effective, the use or non-use of the porous metal complex alone causes problems in actual handling. The present invention can provide a method for producing granules that use a porous metal complex and are excellent in handling.

The following items are important in the present invention. That is, a particulate material having an average particle size of 0.1 to 5000 μm is used as the carrier (A), and the porous metal complex (B) and the carrier (A) are adhered with the adhesive (C). Characterized by Examples of the present invention include the following.

[1] A structure in which a particulate matter having an average particle size of 0.1 to 5000 μm is used as the carrier (A), and the porous metal complex (B) and the carrier (A) are point-bonded with the adhesive (C). Method for producing granules (D).
[2] A particulate material having an average particle size of 0.1 to 5000 μm is used as the carrier (A), and the porous metal complex (B) and the carrier (A) are mixed at a solid content ratio of 1 to 30% by weight with respect to the carrier. % of the granules (D) film-bonded with the adhesive (C).

The granules obtained by the present invention can instantly deodorize daily life odors and effectively suppress bacteria and viruses. In addition, it also has good handleability. Therefore, by using the production method of the present invention, it is possible to obtain granules that have both deodorant properties, antibacterial and antiviral properties, and are easy to handle.

The granules of the present invention are the granules (D) in which the carrier (A) and the porous metal complex (B) are adhered with the adhesive (C), and the pore diameter thereof is 0.000. It is characterized by containing a porous metal complex (B) having a diameter in the range of 6 to 1.0 nm.

The granules of the present invention contain a porous metal complex (B) having a pore diameter within the range of 0.6 to 1.0 nm. The porous metal complex (B) is composed of alternately coordinated metal ions and organic ligands.

The pore diameter of the porous metal complex (B) is within the range of 0.6 to 1.0 nm, which is the range of micropores defined by IUPAC, preferably within the range of 0.7 to 0.9 nm, 0.9 nm is more preferred. The pore diameter is a diameter value measured by a gas/vapor adsorption measuring device, and can be measured, for example, by BELSORP-max manufactured by Microtrac Bell. Even if the pore diameter is smaller than 0.6 nm or larger than 1.0 nm, it is difficult to obtain a sufficient instantaneous deodorizing ability. The porous metal complex (B) (metal ion, organic ligand) in the deodorant of the present invention is not particularly limited as long as it has the above pore size.

Metal ions that can constitute the porous metal complex (B) include Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Y3+, Ti4+, Zr4+, Hf4+, V4+, V3+, V2+, Nb3+, Ta3+, Cr3+, Mo3+, W3+. , Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru2+, Os3+, Os2+, Co3+, Co2+, Rh2+, Rh+, Ir2+, Ir+, Ni2+, Ni+, Pd2+, Pd+, Pt2+, Pt+, Cu2+, Cu+, Ag+ , Au+, Zn2+, Cd2+, Hg2+, Al3+, Ga3+, In3+, Tl3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sb5+, Sb3+, Sb+, Bi5+, Bi3+, Bi+ are mentioned. Among these, copper ions are particularly preferred.

The organic ligand that can constitute the porous metal complex (B) is an aromatic compound, an aliphatic compound, an alicyclic compound, a heteroaromatic compound, a heterocyclic An aromatic compound, an aliphatic compound, an alicyclic compound, a heteroaromatic compound, or a heterocyclic compound containing a formula compound and further having one functional group capable of coordinating with a metal ion may be used in combination.

The functional group capable of coordinating to the metal ion of the organic ligand is 1 to 5 per aromatic compound, aliphatic compound, alicyclic compound, heteroaromatic compound, heterocyclic compound, preferably 2 to 4, more preferably 2 to 3 are included.

An aromatic compound means a monocyclic or polycyclic compound consisting of a 5- or 6-membered aromatic hydrocarbon ring.

Examples of aliphatic compounds include aliphatic compounds having 1 to 12 carbon atoms such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane and dodecane.

Cycloaliphatic compounds include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane.

Heteroaromatic compound means a mono- or polycyclic compound consisting of a 5- or 6-membered aromatic ring containing 1 to 3 heteroatoms selected from N, O and S; In some cases, at least one ring may be a heteroaromatic ring.

Heterocyclic compounds include morpholine, pyrrolidine, piperidine, methylpiperazine, tetrahydrotofuran, dioxane.

Aromatic compounds, aliphatic compounds, alicyclic compounds, heteroaromatic compounds, and heterocyclic compounds have 1 to 5, preferably 1 to 3, particularly 1 functional group capable of coordinating with a metal ion. It may have up to 2 substituents.

In this specification, the porous metal complex (B) is composed of a metal ion and an organic ligand, and may contain a counter ion. When counter anions are metal ions, magnesium, calcium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, cadmium, titanium, vanadium, chromium, manganese, platinum, ruthenium, molybdenum, zirconium, scandium. are preferred, and ions of metals such as magnesium, manganese, iron, cobalt, nickel, copper and zinc are more preferred. A single metal ion may be used as the metal ion, or two or more metal ions may be used in combination.

Preferred organic ligands that can constitute the porous metal complex (B) include benzene, naphthalene, anthracene, phenanthrene, fluorene, indane, indene, pyrene, 1,4-dihydronaphthalene, tetralin, biphenylene, triphenylene, acenaphthylene, Compounds in which 2, 3 or 4 carboxyl groups are bound to an aromatic ring such as acenaphthene (the above ligands are halogen atoms such as F, Cl, Br and I, nitro groups, amino groups and acylamino groups such as acetylamino groups). cyano group, hydroxyl group, methylenedioxy, ethylenedioxy, methoxy, ethoxy, and other straight-chain or branched C1-4 alkoxy groups; methyl, ethyl, propyl, tert-butyl, isobutyl, and other straight-chain or branched C 1-4 alkyl group, SH, trifluoromethyl group, sulfonic acid group, carbamoyl group, alkylamino group such as methylamino, dialkylamino group such as dimethylamino, etc. 1, 2 or optionally trisubstituted), unsaturated divalent carboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid, pyridine, pyrazine, pyridazine, pyrimidine, 4,4-bipyridyl, diazapyrene, nicotinic acid, imidazole, Nitrogen-containing aromatic compounds that can be coordinated by one or more ring nitrogen atoms, oxygen atoms or sulfur atoms such as thiazole, oxazole, quinoline, isoquinoline, naphthyridine (substituted 1, 2 or 3 times by the above substituents) is also good.) and the like. If the ligand is neutral, it has the necessary counter cations to neutralize the metal ion. Such counter cations include chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, phosphate ion, trifluoroacetate ion, methanesulfonate ion, toluenesulfonate ion, benzenesulfonate ion, peroxide ion, chlorate ion and the like.

The porous metal complex (B) according to the present invention is porous having two-dimensional pores such as a sheet or three-dimensional pores containing a bidentate ligand in which a plurality of sheets are coordinated at an axial position as a constituent element. Metal complexes (B) are included, but porous metal complexes (B) having, for example, one-dimensional pores can be used.

In addition, 1,3,5-tris such as [Zn4(μ4O)2(BTMB)2] (BTMB=1,3,5 tris(3 carboxyphenyl)benzene) disclosed in WO 2015/129685 (3-Carboxyphenyl)benzene-based porous metal complexes (B) can also be used.

Porous metal complexes (B) that can be used in the present invention are described, for example, in the following literatures and reviews (Angew.Chem.Int.Ed.2004,43,2334 2375. 2 14.; Chem.Soc.Rev., 2008, 37, 191 214.; PNAS, 2006, 103, 10186 10191.; Chem.Rev., 2011, 111, 688 764.; International Publication No. 2015/129685), etc., but is not limited thereto, and a known porous metal complex (B) or a porous metal complex (B) that can be produced in the future can be widely used. .

The carrier (A) forms a composite (intermediate) with a polymer (hereinafter referred to as "polymer") having a glass transition point (Tg) of 70° C. or less as an adhesive (C), and then forms a porous metal complex ( B) is point-bonded. The point adhesion means that the porous metal complex (B) is adhered to the carrier (A) in a point state, and the carrier (A) and the porous metal complex (B) to be adhered to each other At least part of the surface and the surface of the porous metal complex (B) is exposed without being adhered to the adhesive (C). In the case of film adhesion, a diluted adhesive (C) is applied to uniformly coat the surface of the carrier (A), and the type is not particularly limited as long as the solvent and water used for dilution can be removed. Considering the recent environmental load, a water-soluble resin that does not use an organic solvent is preferable, and for example, a water-soluble acrylic resin can be used.

The polymer used as the adhesive (C) is not particularly limited as long as it is a polymer having a functional group capable of coordinating with the metal ion, and examples include known polymers and polymers that can be produced by known production methods. can be done. The polymer may be a homopolymer or a copolymer obtained by polymerizing two or more monomers. The polymer may be a single polymer or a combination of two or more polymers. The copolymer may be either a random copolymer or a block copolymer.

The polymer may form a crosslinked structure using the porous metal complex (B) and an organic cross-linking agent capable of reacting with the functional groups of the polymer. For example, when the functional group of the polymer is a glycidyl group, an organic cross-linking agent having two or more amino groups, hydroxyl groups, carboxyl groups, thiol groups, etc., and when the functional group of the polymer is a thiol group, a vinyl group, an acrylic group, etc. When the functional group of the polymer is a hydroxyl group, an organic cross-linking agent having two or more isocyanate groups, formyl groups, carboxylic anhydride residues, etc., the functional group of the polymer is In the case of an amino group, an organic cross-linking agent having two or more isocyanate groups, formyl groups, etc. When the functional group of the polymer is a carboxyl group, an organic cross-linking agent having two or more isocyanate groups, carbodiimide residues, oxazoline groups, epoxy groups, etc. When the functional group of the cross-linking agent or polymer is a carboxylic anhydride residue, examples of the cross-linking structure include organic cross-linking agents having two or more hydroxyl groups, amino groups, and the like. When an organic cross-linking agent is used, the solvent should be one that does not react with the organic cross-linking agent or one that does not readily react with the organic cross-linking agent such that the organic cross-linking agent reacts with the polymer faster than the solvent.

Examples of organic cross-linking agents having two or more isocyanate groups include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and the like.

Monomers that can form the polymer include olefins such as ethylene, propylene and butylene, halogenated olefins such as tetrafluoroethylene, vinylidene fluoride, trifluoroethylene and vinyl chloride, and dienes such as butadiene and isoprene.

When the polymer is polyurethane, the monomer having two or more isocyanate groups and the monomer having two or more hydroxyl groups may be reacted. When the polymer is polyester, it has two or more carboxylic acid groups. It can be obtained by polymerizing a monomer and a monomer having two or more hydroxyl groups, or a monomer having a carboxylic acid group and a hydroxyl group.

When the monomer has a carbon-carbon double bond, a copolymer can be obtained by a conventional method such as using a polymerization initiator or irradiating ultraviolet rays.

The glass transition point (Tg) of the polymer is about 70°C or lower, preferably 50°C or lower, like the adhesive (C). The glass transition point of the polymer can be determined by a method based on thermal analysis or a method calculated from the Fox equation.

The mixing ratio of the carrier (A), the porous metal complex (B) and the adhesive (C) varies depending on the types of the porous metal complex (B) and the polymer. It is preferable that the proportion of B) is approximately the same as that of the adhesive (C) and does not exceed the proportion of the adhesive (C). For example, when 100 g of carrier (A) is used, 1 to 10 g of porous metal complex (B) and 1 to 12 g of adhesive (C) are used.

The granules may further contain a conductive agent and a lubricant. Conductive agents include carbon black, carbon nanofiber, graphite powder, and the like. Lubricants include hexagonal boron nitride (hBN), graphite, molybdenum disulfide, and the like, and particulate matter can also be used as a carrier.

The porous metal complex (B) according to the present invention is a compound known per se, can be obtained by a known production method (manufacturing method described in the above-mentioned literature, etc.), and can be obtained by a conventional method. can be prepared. A composite of a porous metal complex (B) and a polymer can be produced, for example, according to the description of WO2015/012373.

The pore diameter of the porous metal complex (B) is preferably within the range of 0.6 to 1.0 nm, more preferably within the range of 0.7 to 0.9 nm, and particularly preferably 0.9 nm.

Examples of the carrier (A) used in the present invention include activated carbon, zeolite, mesoporous silica, silica and alumina. The average particle size of the carrier (A) is, for example, in the range of 0.1-5000 μm, preferably in the range of 0.5-1000 μm. Examples of the solvent include toluene, xylene, ethyl acetate, methanol, ethanol, and acetone.

In the present invention, the adhesion form in which the porous metal complex (B) is point-bonded to the surface of the carrier (A) is important. For example, when the porous metal complex (B) is point-bonded, the performance of the porous metal complex (B) can be added while maintaining the performance of the carrier (A). In this case, the carrier (A) and the adhesive (C) are first point-bonded, and then the porous metal complex (B) is added and point-bonded to the surface of the adhesive (C). It is also possible to add the three raw materials of carrier (A), porous metal complex (B), and adhesive (C) at the same time. is adhered and the porous metal complex (B) is included therein, the obtained effect is inferior to that described above.

Further, when the adhesive (C) is properly coated on the surface of the carrier (A) first and the porous metal complex (B) is adhered, the performance of the carrier (A) is slightly deteriorated, but the porous metal The adhesion amount of the complex (B) increases. In this case, the performance of the porous metal complex (B) can be enhanced over the performance of the carrier (A). It can be defined by the mixing ratio of the solid content of the adhesive (C) to A). In order to uniformly coat the surface of the carrier (A), the diluted adhesive (C) is applied and the solvent and water used for dilution are removed. In a specific example, the water is removed by heating while dropping the water-soluble acrylic resin onto the carrier. In this case, the solid content of the adhesive (C) is 1 to 30% by weight with respect to the carrier (A) so that the deodorizing performance of the carrier (A) is not impaired. If it exceeds 30% by weight, the pores of the carrier (A) are clogged, and the original performance of the carrier (A) cannot be exhibited. On the other hand, if it is less than 1% by weight, the porous metal complex (B) will not be sufficiently adhered and performance will not be obtained.

Thermal bonding with the adhesive (C) uses a thermoplastic resin as the adhesive (C), and can be bonded by heating within the range from the glass transition point to the softening point and then cooling to the glass transition point or below. However, in consideration of adhesiveness such as falling off after adhesion and adhesion between adhesives (C), the temperature is preferably in the range of 20 to 50° C. higher than the glass transition point. The carrier (A) and the porous metal complex (B) are particulate, and the adhesive (C) is also preferably particulate to ensure uniformity. is preferably greater than and not greater than the carrier (A). If it is smaller than the porous metal complex (B), dust will be generated, and since the adhesion area is small, the adhesion of the porous metal complex (B) will be poor and the porous metal complex (B) will easily come off. If the average particle size is much larger than that of the porous metal complex (B), the adhesives (C) are likely to adhere to each other, and the locations where the porous metal complex (B) is adhered are reduced.

Stirring is required during heat treatment such as heating and cooling to eliminate temperature unevenness in order to bond the particles together. A stirring method is not particularly specified, and a commercially available mixer or the like may be used. The heating method is also not particularly limited and may be radiation (infrared heater, etc.), heat transfer (touch heater, etc.), or convection (hot air, etc.).

The granules of the present invention can be blended with other deodorant components and additives as long as the effects of the present invention are not impaired. Examples of deodorant components include zeolite, activated carbon, silica gel, and cyclodextrin. Examples of additives include surfactants, water absorbing agents, penetrating agents, dispersing agents, and the like. When these are added, as in the case of adding a conductive agent or a lubricant, after bonding the porous metal complex (B) to the carrier (A) with the adhesive (C), the glass transition point of the adhesive (C) Add with stirring at the following temperature. Moreover, if these are particulate matter, they may be used as a carrier.

The granules of the present invention are excellent, for example, in instantly deodorizing the following household odors.
(1) Nursing care/nursing odor, hospital odor: urine odor, excretion odor (2) General life odor-1: Garbage odor, changing room odor/locker odor, fitting room odor, congestion odor (crowded train odor), air conditioner Odor, tatami mat odor, floor odor, kitchen odor, toilet odor, bathroom odor, geta box odor, drainage bad breath (3) General life odor-2: Body odor, sweat odor (4) General life odor-3: Cigarette odor, grilled meat Odor (5) Other household odors: Compost odor, animal odor, pet excrement odor, automobile interior odor

Since the granules of the present invention contain the porous metal complex (B) in which metal ions and organic ligands are alternately coordinated, they are excellent in antibacterial and antiviral effects.

Bacteria and viruses that can be targeted by the granules of the present invention are not particularly limited, but include, for example, the following bacteria and viruses. Fungi are also included in fungi.

<Bacteria>
(1) Gram-negative facultative anaerobic bacilli Escherichia coli, Shigella, Salmonella, Klebsiella, Proteus, Yersinia, Vibrio cholerae (V. cholerae), Vibrio parahaemolyticus, Haemophilus
(2) Gram-negative aerobic bacilli Pseudomonas, Legionella, Bordetella, Brucella, Francisellatularensis
(3) Gram-negative anaerobic bacilli Bacteroides
(4) Gram-negative cocci Neisseria
(5) Gram-positive cocci Staphylococcus, Streptococcus, Enterococcus
(6) Gram-positive spore-forming bacilli, Bacillus, Clostridium
(7) Actinomycetes and related microorganisms Corynebacterium, Mycobacterium
(8) Mycoplasma Mycoplasma
(9) Spirochetes and spiral bacteria Borreliarecurrentis, Lyme disease Borrelia (B.burgdoferi), Treponemapalidum, Campylobacter, Helicobacter
(10) Rickettsia
(11) Chlamydia Chlamydia
(12) Fungal Cryptococcosis, Candiasis, Aspergilosis, Pneumocystiscarinii, Trichophyton, Tineaversicolor

<Virus>
Molluscum contagiosum virus, herpes simplex virus, varicella-zoster virus, rotavirus, human papillomavirus, poliovirus, coxsackievirus, rhinovirus, rubella virus, measles virus, influenza virus, epidemic parotid virus adenitis virus, respiratory syncytial virus, hepatitis virus, HIV

The present invention includes molded articles containing the granules of the present invention (hereinafter referred to as "molded articles of the present invention").

The molded product of the present invention is not particularly limited as long as the granulated product of the present invention can be encapsulated, and examples thereof include fibers, textile products, resin molded products, and filters.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

The following carrier (A), porous metal complex (B), and adhesive (C) were used.
[Carrier]
Product number: CW-360B (manufactured by Futamura Chemical Co., Ltd.)
[Porous metal complex 1]
Product number: AP002 (manufactured by Atomis Co., Ltd.)
[Porous metal complex 2]
Product number: AP004 (manufactured by Atomis Co., Ltd.)
[Adhesive 1]
PR F-920P (manufactured by Tokyo Ink Co., Ltd.)
[Adhesive 2]
Parsol GH-908 (manufactured by Ohara Palladium Chemical Co., Ltd.: solid content 50%) diluted with distilled water to a solid content of 33%

The adhesion method was performed by selecting one of the following.
[Adhesion method 1]
(1) A carrier (A) and an adhesive (C) are put into a 1 L glass container in a predetermined composition.
(2) Cover the glass container with a rubber stopper fitted with a perfect seal (a hole for propeller rotation) and a temperature probe (sensor).
(3) Stir at 170 rpm. Use a blade for stirring.
(4) The inside of the container is heated to 50°C while stirring, and the treatment is performed for 5 minutes after the temperature is raised.
(5) The inside of the container is heated to 85°C while stirring, and the treatment is performed for 5 minutes after the temperature is raised.
(6) Cool to room temperature (30° C. or less) while stirring to obtain an intermediate.
(7) Porous metal complex (B) is added to the intermediate, and operations (2) to (6) are carried out to obtain granules.
[Adhesion method 2]
(1) A carrier is put into a 1 L stainless steel container with a predetermined composition.
(2) Heat the inside of the container to 90° C. at 200 rpm while stirring with a blade.
(3) Dropping of the adhesive 2 is started when the inside of the container reaches 50° C. while stirring. After dropping a predetermined amount, the mixture is kept at 90° C. for 2 hours to completely evaporate the water.
(4) Cool to room temperature (30° C. or lower), add the porous metal complex (B), and stir until uniform.
(5) The inside of the container is heated to 90° C. while stirring, and the treatment is performed for 30 minutes.
(6) Cool to room temperature while stirring to obtain granules.
[Adhesion method 3]
(1) A carrier, a porous metal complex (B), and an adhesive (C) were put into a 1 L glass container in a predetermined composition, and a perfect seal (a hole for propeller rotation) and a temperature probe (sensor) were attached. Cap with a rubber stopper.
(2) Stir at 170 rpm. Use a blade for stirring.
(3) The inside of the container is heated to 50°C while stirring, and the treatment is performed for 5 minutes after the temperature is raised.
(4) The inside of the container is heated to 85° C. while stirring, and the treatment is performed for 5 minutes after the temperature is raised.
(5) Cool to room temperature (30° C. or less) while stirring to obtain granules.

The test was performed by the following method.
[Tobacco deodorant test: detector tube method]
(1) Attach the granules to an air purifier (fan: XFAN (Model: RDH1238B1: manufactured by Xinruilian & Technology (Shenzhen) Co. Ltd.), test equipment (completely sealed 27 L container, top open/close type: width 40 cm x depth) 25 cm x 27 cm high) When installing, spread a non-woven fabric on the filter frame (12 cm wide x 11 cm deep x 2 cm high), sprinkle 15 g of deodorant on it, and then cover it with a non-woven fabric.
(2) Burn one cigarette (Mobius original: 10 mg of tar, 0.8 mg of nicotine) while rotating a simple fan in the container. After burning, let it sit for 2 minutes.
(3) As an initial value, ammonia and pyridine are measured with a detector tube, and the air purifier is operated.
(4) After 1 hour, stop the fan and measure again with the detector tube.
[Tobacco deodorant test: sensory test]
(1) Immediately after the tobacco deodorization test using the detector tube, 100 mL of air in the container was sampled from the top of the container with a syringe, and three subjects judged the odor of 20 mL each. At that time, the average of the judgment values of the three subjects is taken.
(2) Evaluation was made by a 6-step odor method, and odor intensity grade 2 or less and discomfort index grade -2 or more (value closer to 0 (zero)) were considered acceptable. Describe the criteria below.
(odor intensity)
0: Odorless 1: Barely detectable odor (detection threshold)
2: Weak odor that makes it possible to identify what it is (cognitive threshold)
3: easily perceivable odor 4: strong odor 5: strong odor (discomfort index)
0: Neither pleasant nor unpleasant -1: Somewhat unpleasant
-2: Discomfort
-3: very uncomfortable
-4: Extremely uncomfortable

[Antibacterial test method: conforming to JIS L1902]
(1) Test material preparation method A test material was prepared by mixing 1 g of a deodorant with 2.5 g of agar and coating it on a fabric (cotton knit).
*Agar: Adjusted to 3 g of meat extract, 5 g of peptone, and 15 g of agar powder per liter of distilled water.
Test bacterium: Staphylococcus aureus (2) Test method: A bouillon suspension of the test bacterium is injected into the sterilized test material, and the number of viable bacteria is measured after culturing in a sealed container at 37°C for 18 hours. After inoculation, the antibacterial count is evaluated based on the antibacterial activity value against the unprocessed cloth count.
(3) Antibacterial activity value = (Mb-Ma) - (Mc-Mo) (accepted with antibacterial activity value ≥ 2.2)
Ma: Number of viable bacteria immediately after contact with the test bacteria solution on the standard cloth Mb: Number of viable bacteria on the standard cloth after 18 hours of culture Mo: Number of viable bacteria immediately after inoculation of the antibacterial and deodorant treated cloth with the test bacteria solution
Mc: Number of viable bacteria after 18-hour culture of antibacterial and deodorant treated cloth (4) Effectiveness: Test is valid due to Mb-Mo > 1.0

Antiviral test method: Tested according to ISO18184.
(1) Test method: Plaque method (2) Virus to be tested: Influenza (3) Antiviral effect: Passed with Mv ≥ 3.0

[Handleability]
Workers were interviewed about the generation of dust and the situation of fallen objects, and judgment was made by comparison with Comparative Example 1, which serves as a reference.
○: equal to or higher than standard ×: below standard

The present invention was implemented in the following manner. Table 1 shows the results of Examples 1 to 6 and Comparative Examples 1 to 3.

[Example 1]
100 g of the carrier (CW-360B) and 5 g of the organic adhesive 1 (PR F-920P) were sampled, and 5 g of the porous metal complex 1 (AP002) was added in the course of adhesion to bond them by the adhesion method 1. The obtained deodorant was subjected to tobacco deodorant test, tobacco deodorant sensory test, antibacterial test, and antiviral test, and effects were obtained in all cases. The handleability was also good.

[Example 2]
100 g of the carrier (CW-360B) and 5 g of the organic adhesive 1 (PR F-920P) were sampled, and 5 g of the porous metal complex 2 (AP004) was added during the adhesion, followed by adhesion by the adhesion method 1. The obtained deodorant was subjected to tobacco deodorant test, tobacco deodorant sensory test, antibacterial test, and antiviral test, and effects were obtained in all cases. The handleability was also good.

[Example 3]
250 g of the carrier (CW-360B) was sampled, adhesion was started by the adhesion method 2, 62.5 g of the organic adhesive 2 (GH-908 diluted solution) was dropped on the way, and 5 g of the porous metal complex 1 (AP002) was added. was added. The obtained deodorant was subjected to tobacco deodorant test, tobacco deodorant sensory test, antibacterial test, and antiviral test, and effects were obtained in all cases. The handleability was also good.

[Example 4]
250 g of the carrier (CW-360B) was collected, and adhesion was started by the adhesion method 2, 62.5 g of the organic adhesive 2 (GH-908 diluted solution) was dropped on the way, and 5 g of the porous metal complex 2 (AP004) was added. was added. The obtained deodorant was subjected to tobacco deodorant test, tobacco deodorant sensory test, antibacterial test, and antiviral test, and effects were obtained in all cases. The handleability was also good.

[Example 5]
100 g of carrier (CW-360B), 5 g of organic adhesive 1 (PR F-920P), and 5 g of porous metal complex 1 (AP002) were added and bonded by bonding method 3. The obtained deodorant was subjected to tobacco deodorant test, tobacco deodorant sensory test, antibacterial test, and antiviral test, and effects were obtained in all cases. The handleability was also good.

[Example 6]
100 g of carrier (CW-360B), 5 g of organic adhesive 1 (PR F-920P), and 5 g of porous metal complex 2 (AP004) were added and bonded by bonding method 3. The obtained deodorant was subjected to tobacco deodorant test, tobacco deodorant sensory test, antibacterial test, and antiviral test, and effects were obtained in all cases. The handleability was also good.

[Comparative Example 1]
100 g of the carrier (CW-360B) was collected and used as a deodorant as it was. The obtained deodorant was subjected to tobacco deodorant test, tobacco deodorant sensory test, antibacterial test, and antiviral test, but no effect was obtained. Handleability was standard and was good.

[Comparative Example 2]
5 g of porous metal complex 1 (AP002) was collected and used as a deodorant as it was. The obtained deodorant was subjected to tobacco deodorant test, tobacco deodorant sensory test, antibacterial test, and antiviral test. .

[Comparative Example 3]
250 g of the carrier (CW-360B) was collected, and adhesion was started by the adhesion method 2. In the middle, 125 g of organic adhesive 2 (GH-908 diluted solution) was added dropwise, and 5 g of porous metal complex 1 (AP002) was added. Ta. Tobacco deodorant test and tobacco deodorant sensory test were performed with the obtained deodorant, and no effect was obtained. The handleability was good.

INDUSTRIAL APPLICABILITY The present invention can provide daily necessities having deodorant, antibacterial and antiviral properties by producing granules that are excellent in handling while maintaining the performance of the porous metal complex.

Claims (2)

A particulate matter having an average particle diameter of 0.1 to 5000 μm is used as the carrier (A), and the porous metal complex (B) and the carrier (A) are point-bonded with the particulate adhesive (C). A method for producing a granulated product (D).
The average particle size of the adhesive (C) is larger than that of the porous metal complex (B) and does not exceed that of the carrier (A).
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