JP7227648B2 - Deodorant for daily life odor - Google Patents

Description

The present invention mainly belongs to the technical field of deodorant compositions. TECHNICAL FIELD The present invention relates to a deodorant containing a porous coordination polymer (PCP). The present invention also relates to an antibacterial or antiviral agent characterized by containing a porous coordination polymer (PCP).

Porous coordination polymers (PCPs), also called metal organic frameworks (MOFs), are artificially synthesized porous structures that utilize coordination bonds between metal ions and organic ligands. It is matter. A framework is constructed by bridging the organic ligands by the metal ions, and the voids within this framework serve as spaces for entrapping molecules.

Conventional porous materials include naturally occurring inorganic materials such as zeolites, silica gels and activated carbon. They each have pore functions such as separation, storage, adsorption, and discharge, but it is difficult to control fine pores, and they are somewhat limited. In this regard, PCP can be synthesized with various porous structures by molecular design, and can be used to construct very complicated structures and highly functional or multifunctional porous materials. As such, PCPs are used for storage of gases (hydrogen, methane, CO2, etc.); selective storage of molecules and ions; separation such as isomer separation; solid catalysts for oxidation reactions, addition reactions, hydrogenation reactions, etc.; A wide range of applications are expected, such as sequestration; transportation; nano-containers; and sensors.

On the other hand, 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.

PCP (MOF), which is an artificial porous material, is also disclosed in US Pat. Patent Literature 1 describes that malodors include fecal collection, bad breath, cigarette smoke, and the like, and that MOF can be used as a household deodorant. Patent Document 1 neither describes nor suggests that the MOF can be used as an antibacterial or antiviral agent.

WO2007/035596

Patent Document 1 describes that PCP (MOF) can be used as a household deodorant.
A main object of the present invention is to provide a novel deodorant that uses PCP (MOF) and can have higher deodorant performance against daily odors. Another object of the present invention is to provide molded articles such as fibers and filters containing such a deodorant.
Another object of the present invention is to provide a novel antibacterial agent or antiviral agent using PCP (MOF).

As a result of extensive studies, the present inventors have found that the use of PCP with a certain range of pore sizes can provide higher deodorant performance against daily odors, and have completed the present invention. I came to do it. In addition, the inventors have found that PCP can also have antibacterial properties, etc., and have completed the present invention.

Examples of the present invention include the following.

[1] A porous coordination polymer in which metal ions and organic ligands are alternately coordinated, the porous coordination polymer having a pore diameter in the range of 0.6 to 1.0 nm. A deodorant for daily life odors, characterized by containing a high molecular weight polymer.
[2] The deodorant for household odors according to [1] above, wherein the metal ion is a copper ion.
[3] The deodorant for household odors according to the above [1] or [2], wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or its ester.
[4] The household scent product according to any one of [1] to [3] above, wherein the porous coordination polymer forms a composite with a polymer having a glass transition point (Tg) of 70° C. or lower. Deodorants.
[5] The deodorant for household odors according to any one of [1] to [4] above, wherein the household odor is tobacco odor, animal odor, excrement odor, garbage odor, or sweat odor.

[6] A molded article comprising the deodorant for daily life odors according to any one of [1] to [5] above.
[7] The molded article according to [6] above, which is a fiber, textile product, resin molded article, or filter.

[8] An antibacterial or antiviral agent comprising a porous coordination polymer in which metal ions and organic ligands are alternately coordinated.
[9] The antibacterial or antiviral agent according to [8] above, wherein the porous coordination polymer has a pore diameter in the range of 0.6 to 1.0 nm.
[10] The antibacterial or antiviral agent according to [8] or [9] above, wherein the metal ion is a copper ion.
[11] The antibacterial or antiviral agent according to any one of [8] to [10] above, wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or an ester thereof.
[12] The antibacterial agent according to any one of [8] to [11] above, wherein the porous coordination polymer forms a complex with a polymer having a glass transition point (Tg) of 70° C. or less, or antiviral agent.

[13] A molded article comprising the antibacterial agent or antiviral agent according to any one of [8] to [12] above.
[14] The molded article according to [13] above, which is a fiber, textile product, resin molded article, or filter.

[15] A porous coordination polymer in which metal ions and organic ligands are alternately coordinated, and the porous coordination polymer has a pore diameter in the range of 0.6 to 1.0 nm. A method for producing a molded article containing a high-order polymer and having deodorant, antibacterial or antiviral properties,
A step of applying a treatment liquid containing a binder resin in a solvent (excluding those containing the porous coordination polymer) to an air-permeable thin film material, and the thin film material coated with the treatment liquid. after drying, spraying the porous coordination polymer or a composition containing the porous coordination polymer (excluding those containing a binder resin);
A method for manufacturing the molded article, comprising:
[16] The method for producing a molded article according to [15] above, wherein the metal ion is a copper ion.
[17] The method for producing a molded article according to [15] or [16] above, wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or its ester.
[18] The molded article according to any one of [15] to [17] above, wherein the porous coordination polymer forms a composite with a polymer having a glass transition point (Tg) of 70°C or lower. manufacturing method.
[19] The method for producing a molded article according to any one of [15] to [18] above, wherein the daily life odor is tobacco odor, animal odor, excrement odor, garbage odor, or sweat odor.
[20] The method for producing a molded article according to any one of [15] to [19] above, wherein the solvent of the treatment liquid is water.
[21] The method for producing a molded article according to any one of [15] to [20] above, wherein the thin film material is a textile product, a nonwoven fabric, a filter, or a sheet.
[22] The method for producing a molded article according to any one of [15] to [21] above, wherein the molded article is a fiber, textile product, resin molded product, or filter.

The deodorant or molded article of the present invention is excellent in instantly deodorizing daily life odors. Moreover, according to the present invention, bacteria or viruses can be effectively suppressed. Therefore, according to the present invention, it is possible to combine deodorization of daily life odors with antibacterial and antiviral properties.

A photograph of the instrument (modified detector tube) used in Test Example 1 and the like.

1. Deodorant for daily life odors of the present invention The deodorant for daily life odors of the present invention (hereinafter referred to as "the deodorant of the present invention") is composed of alternately coordinated metal ions and organic ligands. A porous coordination polymer comprising a porous coordination polymer having a pore diameter in the range of 0.6 to 1.0 nm.

1.1 Porous Coordination Polymer (PCP) The deodorant of the present invention contains a porous coordination polymer having a pore diameter within the range of 0.6 to 1.0 nm. Such a porous coordination polymer is composed of alternately coordinated metal ions and organic ligands.

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

1.1.1 Metal Ions Examples of metal ions that can constitute porous coordination polymers include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr4 ⁺ , Hf4+, ^{V4 +, V3+} , V2 ⁺ , Nb3 ⁺ , Ta3 ^{+ ,} Cr3 ⁺ , Mo3 ⁺ , W3 ⁺ , Mn3 ⁺ , ^Mn2 +, ^{Re3 +} , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ^{3+ , Ru 2+ ,} Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ⁺ , Ni ²⁺ , Ni ⁺ , Pd ²⁺ , Pd ⁺ , Pt ²⁺ , Pt ⁺ , Cu ²⁺ , Cu ⁺ , Ag ⁺ , Au ⁺ , Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Al ^{3 +} , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As3 ⁺ , As ⁺ , Sb5 ⁺ , Sb3 ⁺ , Sb ⁺ , ^Bi5+ , Bi3 ⁺ , Bi ⁺ . Among these, copper ions are particularly preferred.

1.1.2 Organic ligands Organic ligands that can constitute porous coordination polymers are aromatic compounds, aliphatic compounds, and alicyclic compounds that have multiple functional groups capable of coordinating with metal ions. , Heteroaromatic compounds, including heterocyclic compounds, aromatic compounds, aliphatic compounds, alicyclic compounds, heteroaromatic compounds, heterocyclic compounds having one functional group capable of coordinating with a metal ion They may be used together.

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. Functional groups that can coordinate to such metal ions include glycidyl groups, COOH, carboxylic anhydride groups, _CS2H , OH, SH, SO, _SO2 , _SO3H , _NO2 , -S-, - SS-, Si(OH) ₃ , Ge(OH) _{3 ,} Sn(OH) ₃ , Si(SH) _{4 ,} Ge(SH) ₄ , Sn(SH) ₄ , PO3H, AsO3H, _AsO4H , P(SH) ₃ , As(SH) ₃ , CH(SH) ₂ , C(SH) ₃ , CH( _NH2 ) ₂ , C( _NH2 ) ₃ , CH(OH) ₂ , C(OH) ₃ , CH(CN) ₂ , C(CN) ₃ , CH(RSH) ₂ , C(RSH) ₃ , CH( _RNH2 ) ₂ , C( _RNH2 ) ₃ , CH(ROH) ₂ , C(ROH) ₃ , CH(RCN) ₂ , C(RCN) ₃ , NH ₂ , NHR, NR ₂ , nitrogen atoms constituting aromatic rings (wherein R represents a C ₁ to C ₅ alkyl group or aryl group). . A nitrogen atom constituting an aromatic ring means an intracyclic nitrogen atom such as pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, thiazole, oxazole, phenanthroline, quinoline, isoquinoline, naphthyridine, purine, bipyridine, and terpyridine.

An aromatic compound means a monocyclic or polycyclic compound composed of a 5- or 6-membered aromatic hydrocarbon ring, and specific examples include benzene, naphthalene, 1,4-dihydronaphthalene, fluorene, anthracene, and phenanthrene. , biphenyl, triphenyl, acenaphthylene, acenaphthene, tetrahydronaphthalene, chroman, 2,3-dihydro-1,4-dioxanaphthalene, pyrene, indane, indene and phenanthrene.

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. Specific examples include furan, thiophene, pyrrole, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, pyridine, pyrazine, pyridazine, pyrimidine, pyridazine, indole, quinoline, isoquinoline, benzo[b]thiophene and benzimidazole. mentioned.

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, in particular 1 functional group capable of coordinating with a metal ion. It may have up to 2 substituents. Such substituents include chlorine, fluorine, bromine, iodine, methoxy, ethoxy, trifluoromethyl, methyl, ethyl, propyl, butyl, cyano, nitro, methylenedioxy, acetylamino, carbamoyl, acetyl , and formyl.

Specific examples of organic ligands constituting the porous coordination polymer include pyridine, 4,4'-bipyridine, ethylenediamine, propylenediamine, 2-aminoethanol, 3-aminopropanol, trimethylamine, triethylamine and tripropylamine. , 2-aminopropane, triethanolamine, ethylbutylamine, piperidine, cyclohexylamine, 2-methylpyridine, N,N-dimethylbenzylamine, N-methyldiethanolamine, N-methylethanolamine, N-methylpiperidine, 3-methyl Piperidine, 4-methylpiperidine, 1,4-diaminocyclohexane, morpholine, aniline, 1,4-diaminobenzene, 1,3,5-triaminobenzene, 1,3,5-triazine, imidazole, pyrazine, methanol, dihydroxy methane, trihydroxymethane, tetrahydroxymethane, ethanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,1,2,2-tetrahydroxyethane, 1-propanol, 2-propanol, 1,3-propanediol , glycerol, 1,1,3,3-tetrahydroxypropane, allyl alcohol, n-butanol, sec-butanol, isobutanol, tert-butanol, 1,4-butanediol, 1,3-butanediol, 1,1 ,4,4-tetrahydroxybutane, n-pentanol, sec-pentanol, isopentanol, tert-pentanol, neopentanol, 1,6-hexanediol, 1,5-hexanediol, 1,4- Hexanediol, 1,3-hexanediol, 1,3,6-trihydroxyhexane, cyclohexanol, 1,4-dihydroxycyclohexane, 1,3,5-trihydroxycyclohexane, phenol, benzyl alcohol, hydroquinone, catechol, resorcinol , 1,3,5-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4,5-tetrahydroxybenzene, thiomethane, thioethane, thiopropane, thio Cyclohexane, thiobenzene, 1,3-dithiopropane, 1,4-dithiopropane, 1,4-dithiobenzene, 1,3,5-trithiobenzene, 1,4-dicyanobenzene, 1,3,5-tricyano Benzene, 1,4-butanedicarboxylic acid, tartar acid, glutaric acid, oxalic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecane Dicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzene dicarboxylic acids, 1,3-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8 -dicarboxylic acid, diimidodicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, Tetrahydrofuran-4,4'-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, pururiol E200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2 -dicarboxylic acid, octanedicarboxylic acid, pentane-3,3'-dicarboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3, 3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis-(phenylamino)-benzene-2,5-dicarboxylic acid, 1,1'-binaphthyl-8,8'-dicarboxylic acid , 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4′-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis-(carboxymethyl)- piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1, 4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindane dicarboxylic acid, 1,3-dibenzyl-2-oxo-imi Dazoline-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazoline-4 ,5-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, O-hydroxybenzophenonedicarboxylic acid, pluriol E300-dicarboxylic acid, pluriol E400-dicarboxylic acid, pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4, 4'-diamino (diphenyl ether) diimide dicarboxylic acid, 4,4'-diaminodiphenylmethane diimide dicarboxylic acid, 4,4'-diamino (diphenyl sulfone) diimide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantane dicarboxylic acid acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3- naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′,3′-diphenyl-p-terphenyl-4,4″-dicarboxylic acid, (diphenyl ether)-4,4′-dicarboxylic acid, imidazole-4 ,5-dicarboxylic acid, 4(1H)-oxo-thiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl -9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorbin-4,11- Dicarboxylic acid, 7-chloro-3-methyl ruquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4- dicarboxylic acids, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1, 7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 2- Hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono- 1,2,4-butanedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo [ 2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methyl Benzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, 1,1-dioxidoperiro[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid , perylene-3,4,9,10-tetracarboxylic acid perylene-1.12-sulfone-3,4,9,10-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, meso-1 , 2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadiene-2,3,11, 12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7 ,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3′,4,4′-benzophenone Tetracarboxylic acid, Tetrahydrofurantetracarboxylic acid, Cyclopentane-1 , 2,3,4-tetracarboxylic acid and the like. Among these, 1,3,5-benzenetricarboxylic acid or its ester is preferred.

In this specification, the porous coordination polymer is composed of metal ions and organic ligands and may contain a counter anion. Metal ions include ions such as magnesium, calcium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, cadmium, titanium, vanadium, chromium, manganese, platinum, ruthenium, molybdenum, zirconium, and scandium. More preferred are ions of metals such as magnesium, manganese, iron, cobalt, nickel, copper and zinc. 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 porous coordination polymers include benzene, naphthalene, anthracene, phenanthrene, fluorene, indane, indene, pyrene, 1,4-dihydronaphthalene, tetralin, biphenylene, triphenylene, acenaphthylene, and acenaphthene. compounds in which 2, 3 or 4 carboxyl groups are bound to an aromatic ring such as , cyano group, hydroxyl group, methylenedioxy, ethylenedioxy, methoxy, ethoxy and other linear or branched C 1-4 alkoxy groups, methyl, ethyl, propyl, tert-butyl, isobutyl and other linear 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 , thiazole, oxazole, quinoline, isoquinoline, naphthyridine, and other nitrogen-containing aromatic compounds that can be coordinated by one or more ring nitrogen atoms, oxygen atoms or sulfur atoms (substituted 1, 2 or 3 by the above substituents) may be used.) and the like. If the ligand is neutral, it has the necessary counter anion to neutralize the metal ion. Examples of such counter anions 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 coordination polymer according to the present invention is a porous coordination polymer 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. For example, the following porous coordination polymers with one-dimensional pores can be used.

IRMOF-1, [ _Zn4O (1,4-BDC) ₃ ] _n ( _H2-1,4 -BDC= 1,4-benzenedicarboxylic acid)
MOF-69C, [ _Zn3 ( _OH2 )(1,4-BDC) ₂ ] _n
MOF-74, [ _M2 (DOBDC)] _n ( _H2DOBDC =2,5-dihydroxyterephthalic acid, M=Zn, Co, Ni, Mg)
HKUST-1, [ _Cu3 (1,3,5-BTC) ₂ ] _n ( _H3-1,3,5 -BTC=1,3,5-benzenetricarboxylic acid)
MOF-508, [Zn(1,4-BDC)(bpy) _0.5 ] _n (bpy = 4,4'-bipyridine)
Zn-BDC-DABCO, [Zn ₂ (1,4-BDC) ₂ (DABCO)] _n , (DABCO=1,4-diazabicyclo[2.2.2]-octane)
Cr-MIL-101, [ _Cr3F ( _H2O ) _2O (1,4-BDC) ₃ ] _n
Al-MIL-110, [ _Al8 (OH) ₁₂ {(OH) ₃ ( _H2O ) ₃ }(1,3-5-BTC) ₃ ] _n
Al-MIL-53, [Al(OH)(1,4-BDC)] _n
ZIF-8, [Zn(MeIM) ₂ ] _n , (H-MeIM=2-methylimidazole)
MIL-88B, [ _Cr3OF (1,4-BDC) ₃ ] _n
MIL-88C, [ _Fe3OX ( _O2CC10H6 - _{CO2 ) 3} ] _n (X = OH _, Cl)
MIL-88D, _{[Cr3OF(O2CC12H8 - CO2 ) 3 ] n}
CID-1 [ _Zn2 (ip) ₂ (bpy) ₂ ] _n ( _H2ip =isophthalic acid)

In addition, 1, such as [Zn ₄ (μ ₄ -O) ₂ (BTMB) ₂ ] (BTMB= 1,3,5-tris(3-carboxyphenyl)benzene) disclosed in WO 2015/129685, Porous coordination polymers based on 3,5-tris(3-carboxyphenyl)benzene can also be used.

Porous coordination polymers that can be used in the present invention are described, for example, in the following literature and reviews (Angew. Chem. Int. Ed. 2004, 43, 2334-2375; Angew. Chem. Int. Ed. 2008, 47, Rev., 2008, 37, 191-214.; PNAS, 2006, 103, 10186-10191.; Chem.Rev., 2011, 111, 688-764.; 423, 705-714.), Patent Documents (International Publication No. 2015/129685), etc., but not limited to these, known porous coordination polymers or porous coordination polymers that can be produced in the future Polymers can be widely used.

1.2 Composite of Porous Coordination Polymer and Polymer A porous coordination polymer forms a composite with a polymer having a glass transition point (Tg) of 70° C. or less (hereinafter simply referred to as “polymer”). You may have Therefore, the present invention also includes a deodorant for living odors, characterized by containing a composite of a porous coordination polymer and a polymer.

The polymer capable of forming a complex with the porous coordination polymer is not particularly limited as long as it has a functional group capable of coordinating with the metal ion, and can be produced by a known polymer or a known production method. Polymers may be mentioned. 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 a porous coordination polymer and an organic crosslinker 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, or 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 aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate and lysine diisocyanate; burette type adducts of these polyisocyanates, isocyanurate rings Adduct; isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4-(or 2,6-) diisocyanate, 1,3-(or 1,4-) di(isocyanatomethyl) Alicyclic diisocyanates such as cyclohexane, 1,4-cyclohexane diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate; burette type adducts of these diisocyanates, isocyanurate ring adducts; xyl diisocyanate, metaxylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4'-toluidine diisocyanate- 4,4'-diphenyl ether isocyanate, (m- or p-)phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, bis(4-isocyanatophenyl ) aromatic diisocyanate compounds such as sulfones and isopropylidenebis(4-phenylisocyanate); burette type adducts and isocyanurate ring adducts of these diisocyanate compounds; triphenylmethane-4,4',4' 1 such as '-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate polyisocyanates having 3 or more isocyanate groups in the molecule; burette type adducts and isocyanurate ring adducts of these polyisocyanates. Moreover, the compound which replaced said isocyanate (NCO) with isothiocyanate (NCS) is mentioned.

Monomers that can constitute polymers include olefins such as ethylene, propylene and butylene, halogenated olefins such as tetrafluoroethylene, vinylidene fluoride, trifluoroethylene and vinyl chloride, dienes such as butadiene and isoprene, acrylic acid and methacrylic acid. , acrylates or methacrylates (e.g. methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate , undecyl acrylate, dodecyl acrylate, tridecyl acrylate, stearyl acrylate, isostearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, stearyl methacrylate, isostearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate), aromatic ring-containing vinyl compounds such as styrene, vinyl toluene, and α-methylstyrene; Acrylonitrile, methacrylonitrile; (meth)acrylamide; epoxy group-containing vinyl such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, vinylcyclohexene monoepoxide, N-glycidyl acrylamide, allyl glycidyl ether Compounds; aminoethyl (meth)acrylate, Nt-butylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-di Propylaminoethyl (meth)acrylate amino group-containing (meth)acrylates such as lylate, N,N-dibutylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate; N, Amino group-containing such as N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dipropylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide (Meth)acrylamides; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glyceryl (meth)acrylate, cyclohexanedimethanol mono (meth)acrylate, N-hydroxyethyl (meth)acrylamide , polyhydric alcohols such as polyethylene glycol mono(meth)acrylate and monoesterified products of acrylic acid or methacrylic acid, and hydroxyl group-containing vinyl compounds such as reaction products of these with ε-caprolactone; acrylic acid, methacrylic acid, malein Carboxyl group-containing vinyl compounds such as acids, fumaric acid, itaconic acid, reaction products of hydroxyl group-containing compounds and acid anhydrides; acid anhydride group-containing vinyl compounds such as maleic anhydride, itaconic anhydride, and hymic acid anhydride; Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, octanediol, tricyclodecanedimethylol, cyclohexanedimethanol, hydrogenation Low molecular weight glycols such as bisphenol A, high molecular weight glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and polycarbonate glycol, polyhydric alcohols such as glycerin and monoesters of (meth)acrylic acid; maleic acid, chloromalein Acids, fumaric acid and its anhydrides.

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. In the case of polyester, the monomer having two or more carboxylic acid groups and two It can be obtained by polymerizing a monomer having a hydroxyl group, 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 temperature (Tg) of the polymer is about 70°C or less, preferably 50°C or less.
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 proportion (weight ratio) of the porous coordination polymer and the polymer varies depending on the type of the porous coordination polymer and the polymer. %, preferably 80-98% by weight of porous coordination polymer: 20-2% by weight of polymer, more preferably 85-97% by weight of porous coordination polymer: 15-3% by weight of polymer.

The composite may further contain a conductive agent and a lubricant. Conductive agents include carbon black, ketjen black, carbon nanofibers, acetylene black, channel black, lamp black, furnace black, graphite powder, fibrous carbon materials, metal powder, and metal fibers.

Lubricants include hexagonal boron nitride (hBN), graphite, molybdenum disulfide, tungsten disulfide, selenium sulfide, graphite fluoride, calcium fluoride, mica, talc, PTFE, Pb, PbO, ZnS, BaSO4, metal soap ( For example, solid lubricants such as stearates such as calcium stearate, barium stearate, magnesium stearate, zinc stearate, lithium stearate, sodium stearate) can be used alone or in combination.

1.3 Method for producing the deodorant of the present invention The porous coordination polymer according to the present invention is a known compound per se, and can be obtained by a known production method (manufacturing method described in the above literature, etc.). , and can be prepared with the above pore size by a conventional method. A composite of a porous coordination polymer and a polymer can be produced, for example, according to the description of WO2015/012373.

The deodorant of the present invention can be prepared, for example, by pulverizing, dissolving or suspending in a solvent, kneading under pressure, a porous coordination polymer or a composite of the polymer and the porous coordination polymer alone or using an appropriate carrier in a conventional manner. Alternatively, it can be produced by heating and kneading. Examples of carriers for powderization include activated carbon, zeolite, mesoporous silica, silica, and alumina. The average particle size of the powder is, for example, within the range of 0.1 to 5000 μm, preferably within the range of 0.5 to 1000 μm. Examples of the solvent include toluene, xylene, ethyl acetate, methanol, ethanol, and acetone.

The deodorant of the present invention can also be filled in a spray container or atomizer. The shape of such a spray container is not particularly limited, but examples thereof include trigger-type spray bottles, atomizers, atomizers, spray cans, and pumps. The method for filling the spray container with the deodorant of the present invention is not particularly limited, and known methods can be employed.

When the deodorant of the present invention is filled together with a propellant, the propellant is not particularly limited as long as it is commonly used, and examples thereof include liquefied gas and compressed gas. Specific examples include hydrocarbons, liquefied natural gas (LPG), dimethyl ether, diethyl ether, fluorocarbons, carbon dioxide, nitrogen, and nitrous oxide.

The deodorant 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. Other deodorant components include, for example, zeolite, activated carbon, silica gel, and cyclodextrin. Examples of additives include surfactants, water absorbing agents, penetrating agents, dispersing agents, and the like.

The content of the porous coordination polymer in the deodorant of the present invention is determined by the type of the porous coordination polymer, the content or amount of other deodorant ingredients and additives, the form of the deodorant of the present invention, and the daily odor. For example, it is appropriately set within the range of 0.1 to 100% by weight, preferably within the range of 1 to 100% by weight, although it varies depending on factors such as the above. If it is less than 0.1% by weight, there is a possibility that sufficient deodorizing performance cannot be obtained.

1.4 Living Smells The deodorant of the present invention is excellent in instantly deodorizing the following living odors, for example.
(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 Odors, tatami mat odors, floor odors, kitchen odors, toilet odors, bathroom odors, shoe box odors, drainage bad breath (3) General life odors-2: Body odors, sweat odors (4) General life odors-3: Cigarette odors, grilled meat Odor (5) Other household odors: Compost odor, animal odor, pet excrement odor, automobile interior odor

2 Antibacterial and antiviral agents of the present invention In the present invention, an antibacterial or antiviral agent characterized by comprising a porous coordination polymer in which metal ions and organic ligands are alternately coordinated. agent (hereinafter referred to as "the antibacterial agent of the present invention").

The meanings of "metal ion", "organic ligand", and "porous coordination polymer" are the same as above, but the pore diameter of the porous coordination polymer is appropriately adjusted. A preferred porous coordination polymer has a pore diameter in the range of 0.6 to 1.0 nm, more preferably in the range of 0.7 to 0.9 nm, particularly preferably 0.9 nm.
The antibacterial agent of the present invention can be produced in the same manner as described above in "1.3 Production method of the deodorant of the present invention".

Bacteria and viruses that can be targeted by the antibacterial agent 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), Vparahaemolyticus, Haemophilus
(2) Gram-negative aerobic bacilli Pseudomonas, Legionella, Bordetella, Brucella, Francisella tularensis
(3) Gram-negative anaerobic bacilli Bacteroides
(4) Gram-negative cocci Neisseria
(5) Gram-positive cocci Staphylococcus, Streptococcus, Enterococcus
(6) Gram-positive spore-forming bacilli, genus Bacillus, genus Clostridium
(7) Actinomycetes and related microorganisms Corynebacterium, Mycobacterium
(8) Mycoplasma Mycoplasma
(9) Spirochetes and spiral bacteria Borrelia recurrentis, B. burgdoferi, Treponema palidum, Campylobacter, Helicobacter
(10) Rickettsia Rickettsia
(11) Chlamydia Chlamydia

(12) Fungi Cryptococcosis, Candiasis, Aspergilosis, Pneumocystis carinii, Trichophyton, Tinea versicolor

<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

3. The molded article of the present invention The molded article characterized by containing the deodorant of the present invention or the antibacterial agent of the present invention (hereinafter collectively referred to as the "formulation of the present invention") (hereinafter referred to as the "formulation of the present invention"). (referred to as “articles”).

3.1 Molded article of the present invention The molded article of the present invention is not particularly limited as long as it can enclose the deodorant of the present invention. Examples thereof include fibers, textile products, resin molded articles, and filters.

The fibers may be synthetic fibers, regenerated fibers, or natural fibers.
Synthetic fibers include, for example, polyester, nylon, acrylic, and acetate. Regenerated fibers include, for example, rayon. Examples of natural fibers include cotton, hemp, wool, and silk. Cotton includes raw cotton itself, caustic mercerized cotton, cotton treated with liquid ammonia, and the like. Moreover, the fiber may be a blend of each fiber, or may be a primary processed product of each fiber, such as thread, cord, rope, woven fabric, knitted fabric, non-woven fabric, paper, and the like.

The above-mentioned textile products refer to products obtained by further processing the above-mentioned fibers, and are not particularly limited, but examples thereof include clothing such as outerwear, innerwear, and innerwear, bedding, interior goods, household goods, and car interior goods. Specifically, for example, coats, jackets, trousers, skirts, dress shirts, knit shirts, blouses, nightwear, underwear, sweaters, supporters, socks, tights, stockings, hats, scarves, clothing linings, clothing interlinings, Clothes such as batting, work clothes, uniforms, uniforms for school children; Bedding such as futon fabric, futon cotton, duvet covers, sheets, pillowcases; Interior items such as sheets, mats, curtains, carpets; Towels, handkerchiefs, dish towels , potholders, diapers, sanitary goods, and other daily necessities; and automobile interior products, such as seats, seat covers, and steering wheel covers.
The textile products also include those in the form of textile products used in the field of industrial materials, such as wall fabrics, ceiling fabrics, and floor coverings.

The above resin molded products include polyethylene, polypropylene, acrylic resin, urethane resin, fluorine resin, silicone resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyamide, polystyrene, polyester, aminoplast resin, glyoxal resin, ethylene urea. Molded products such as plate-shaped products, columnar products, and extruded products made of resins and blended resins thereof. Specific examples of molded resin articles include films, sheets, and containers of these resins.
Molding into films, sheets, containers, etc. can be carried out using various inflation devices, presses, calendars, extruders, spinning machines, blow molding machines, injection molding machines, vacuum molding machines, and the like.

Examples of the filter include deodorizing filters and antibacterial filters used in air purifiers and the like.

3.2 Method for producing the molded article of the present invention The molded article of the present invention can be produced by incorporating the formulation of the present invention by a conventional method depending on the desired molded article.
For example, when attaching or impregnating the preparation of the present invention to fibers or textile products, for example, a dipping method, a spray method, a coating method (including a method of applying with a brush, a sponge, etc.) can be used.

In order to prevent the formulation of the present invention from falling off from the fibers or textile products, it is preferable to use a binder resin to fix the zinc carbonate particles to the fibers or textile products. Such binder resins are not particularly limited as long as they are used in the relevant technical field. and flexible resins. The amount of the binder resin to be used may be such that the formulation of the present invention can be fixed to the fiber or textile product.

In the case of the immersion method, the fiber or fiber product to be treated can be immersed in a treatment liquid containing the formulation of the present invention and, if necessary, a binder resin, by a conventional method. The concentration of the formulation of the present invention in the treatment liquid can be set to a concentration calculated from the squeezing ratio of the treatment liquid and the required amount of support. Organic solvents such as alcohols such as toluene, xylene, ethyl acetate, and ethanol can be used as solvents constituting the treatment liquid.

The soaking time and bath temperature are not particularly limited because the treatment liquid permeates the fibers or textile products sufficiently quickly. Usually, the immersion time is in the range of 0.1 to 300 seconds and the bath temperature is in the range of 10 to 40.degree. Although the drawing differs depending on the product to be processed, a suitable drawing method and drawing ratio can be adopted for each product. Normally, it is better to draw with a mangle or the like so as to obtain a uniform drawing ratio.

The adhesion or impregnation amount of the formulation of the present invention is usually within the range of 0.01 to 50 g/m ² , preferably 0.05 to 20 g/m ² as the amount of PCP per 1 m ² of fabric. be.

After immersion and squeezing, drying is performed. Industrially, the drying temperature is in the range of 40 to 150° C., and the drying time can be appropriately selected according to the temperature.

When a binder resin is used, it is preferable to heat-treat after drying in order to fix it with the binder resin. The heat treatment temperature and time vary depending on the type of binder resin used, etc., but the heat treatment temperature is usually in the range of 100 to 250° C., preferably 120 to 200° C. The heat treatment time is Usually in the range of 20 seconds to 1 hour.

In the case of the coating method, it can be produced by coating the treatment liquid containing the formulation of the present invention and, if necessary, the binder resin on fibers or textile products by a conventional method. In the case of the spray method, it can be produced by spraying the treatment liquid containing the formulation of the present invention and, if necessary, the binder resin onto fibers or textile products in a conventional manner.

The molded article of the present invention can also be produced by first applying a treatment liquid containing a binder resin (not including the formulation of the present invention) to fibers or textile products, and then spraying the formulation of the present invention thereon after drying. be able to. The binder resin can be dissolved or dispersed by a conventional method, and water can be used as the solvent for the treatment liquid in addition to the above organic solvents. Safety and convenience can be achieved by using water.

Resin-processed products other than fibers and textile products, and moldings of the present invention such as filters can be basically produced in the same manner as the above-described production method for fibers or textile products.

Particularly preferred is the method for producing the molded article of the present invention, characterized by including each step in each of the following (1) to (3).
(1) The solid content weight ratio of the porous coordination polymer in which metal ions and organic ligands are alternately coordinated to the binder resin is 1:0.01 to 1:30 (porous coordination polymer: binder resin) in an organic solvent, applying the mixture dissolved in the organic solvent to an air-permeable thin film material, and drying the solvent and the like.
(2) A step of mixing a porous coordination polymer in which metal ions and organic ligands are alternately coordinated and a molten binder resin (eg, polyethylene resin) (in addition, the porous coordination high The solid content weight ratio of the molecule to the binder resin is preferably in the range of 1:0.1 to 1:20 (porous coordination polymer:binder resin), and the mixture is applied to an air-permeable thin film material. and a process of sandwiching with an air-permeable thin film material and performing high-temperature pressure bonding.

(3) A step of applying a binder resin to an air-permeable thin film material, and a step of sprinkling a porous coordination polymer in which metal ions and organic ligands are alternately coordinated onto the thin film material. .
In the above (1) and (2), the meanings of "metal ion", "organic ligand", "porous coordination polymer", "binder resin", "organic solvent", etc. are the same as above. is. "Breathable thin film material" includes, for example, textile products, nonwoven fabrics, filters, and sheets that are breathable. In addition, specific manufacturing conditions in the above manufacturing method of the molded product of the present invention can be appropriately set according to known techniques or well-known techniques in the relevant technical field.

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

[Example 1] Preparation of Cu-PCP (HKUST-1, pore size 0.9 nm) 57.6 mL (3 bottles) of 50 vol% ethanol aqueous solution was added to 1.01 g (3 bottles) of methyl acid), and the mixture was stirred for 10 minutes and reacted at 140°C for 60 minutes using microwaves. Ethanol was added to the solid collected by suction filtration, and the solid was washed with ultrasonic waves. The solid collected by suction filtration was vacuum dried to obtain 1.24 g of Cu-PCP with a pore diameter of 0.9 nm. The pore diameter was measured by a high-precision gas/vapor adsorption measuring device BELSORP-max12-NS manufactured by Microtrac Bell (the same shall apply hereinafter).

[Reference Example 1] Preparation of Cu-PCP (HKUST-1, pore diameter 0.5 nm) In the same manner as in Example 1, Cu-PCP with a pore diameter of 0.5 nm was obtained.

[Reference Example 2] Preparation of Ni-PCP (Ni-MOF74, pore size 1.1 nm) 72 mL of dimethylformamide and 3.6 mL of water were added and dissolved with ultrasonic waves. Using an autoclave, the reaction was carried out at 110° C. for 21 hours and 30 minutes. The solid collected by suction filtration was vacuum dried to obtain 2.44 g. After washing with methanol, the solid recovered by suction filtration was vacuum-dried to obtain 1.91 g of Ni-PCP with a pore diameter of 1.1 nm.

[Reference Example 3] Preparation of Cr-PCP (MIL-101 (Cr)) To 2.97 g of chromium (III) chloride hexahydrate and 1.85 g of terephthalic acid, 50 mL of water was added and stirred. °C for 6 hours. After centrifugation, the supernatant was taken and vacuum dried. After adding N,N-dimethylformamide and washing with ultrasonic waves, the supernatant was taken. After ethanol was added and ultrasonically washed, the supernatant was removed and vacuum-dried to obtain 1.59 g of Cr-PCP having a pore diameter of 2.0 to 2.7 nm.

[Test Example 1] Instant deodorant test (ammonia odor)
The tip of a commercially available detector tube was cut off, the sample powder was placed therein, and cotton (about 0.0045 g) was rolled up to form a lid so that the sample powder would not come out (see FIG. 1).
A 500 mL conical flask with a stopper was filled with the ammonia-smelling solution, sealed, and placed in a drying chamber at 60° C. for 15 minutes to evaporate. Then, it was taken out from the drying chamber and allowed to cool for 30 minutes. Then, the instantaneous deodorizing property of each sample powder was tested by inserting the detection tube into the flask and measuring the concentration of ammonia in the gas that passed through the detection tube. The results are shown in Table 1 (initial ammonia odor concentration: 83 ppm), Table 2 (initial ammonia odor concentration: 195 ppm) and Table 3 (initial ammonia odor concentration: 840 ppm).
Zinc oxide is a commercially available KD-211 mixture of silicon dioxide and zinc oxide, which is used to deodorize the four major odors (hydrogen sulfide, ammonia, trimethylamine, methyl mercaptan) and valeric acid, phenol, NOx, etc. (manufactured by Rasa Industry Co., Ltd.).

As shown in Tables 1 to 3, the deodorant of the present invention (Example 1) having a pore diameter of 0.9 nm can sufficiently reduce the concentration of ammonia and has excellent instantaneous deodorizing properties against ammonia odor. It is clear that

[Test Example 2] Instant deodorant test (acetic acid odor)
As for the acetic acid odor, the instantaneous deodorant performance was tested in the same manner as in Test Example 1. The results are shown in Tables 4 and 5.

As shown in Tables 4 and 5, the deodorant of the present invention (Example 1) having a pore diameter of 0.9 nm can sufficiently reduce the concentration of acetic acid and has excellent instantaneous deodorizing properties against the odor of acetic acid. It is clear that 1

[Test Example 3] Instant deodorant test (tobacco smell)
Tobacco (Mevius (registered trademark) Super Light (tar 6 mg, nicotine 0.5 mg)) was burned in a glass container (length 40 cm x width 25 cm x height 27 cm = 27000 cm ³ (27 L)), and the mixture was tightly closed. The one that was left in the sun was used as an odorant. On the other hand, a rubber tube was inserted into the tip of a commercially available disposable syringe, cotton was stuffed into the rubber tube, sample powder (about 0.025 g) was put in the center, and the cotton was capped.

A rubber tube attached to a syringe and containing the sample powder was inserted into a glass container that had been left for one day, and 10 mL or 30 mL of odor was collected. Immediately after that, the rubber tube was removed, and the odor in the syringe was sensory evaluated by three persons based on the following evaluation criteria. Table 6 shows the results.

Acetaldehyde deodorant A is a mixture of silicon dioxide and zirconium oxide, which is commercially available KD-511 (manufactured by Rasa Kogyo Co., Ltd.), and deodorant B is a mixture of silicon dioxide and zinc oxide. 211 (manufactured by Rasa Industry Co., Ltd.). It is used to deodorize sweat odors and aging odors (ammonia, acetic acid, isovaleric acid, nonenal). The zeolite is ABSCENTS-3000 (manufactured by Union Showa Co., Ltd.).

<Sensory Evaluation Criteria>
0: odorless, 1: barely perceptible odor, 2: identifiable odor, 3: easily perceivable odor, 4: strong odor, 5: strong odor

As shown in Table 6, it is clear that the deodorant of the present invention (Example 1) having a pore size of 0.9 nm is excellent in instantaneous deodorizing properties against cigarette odors compared to other deodorants. is.

[Test Example 4] Instant deodorant test (excretion odor)
As for excretion odor, the instantaneous deodorant performance was tested in the same manner as in Test Example 1. Table 7 shows the results. For the excretion odor, the excretion of a 1-year-old child was used.

As shown in Table 7, it is clear that the deodorant of the present invention (Example 1) having a pore size of 0.9 nm is superior in instant deodorant properties to excretion odors compared to zeolite deodorants. be.

[Example 4] Preparation of the formulation of the present invention and the molded article of the present invention Co., Ltd.) was dissolved in 6.1 parts by weight of toluene to prepare the formulation of the present invention. A cotton knit was immersed in the formulation of the present invention for 1 minute, dried in a box dryer at 60° C. for 5 minutes and then at 160° C. for 2 minutes to produce a molded product of the present invention.

[Test Example 5] Antibacterial Test The molded article of the present invention of Example 4 was subjected to an antibacterial test in accordance with the Textile Evaluation Technology Council (JIS L1902). Specifically, the following method was used.

(1) Test bacterium: Staphylococcus aureus (2) Test method: A test bacterium suspension containing a surfactant (Tween 80) is injected into the sterilized test material, and cultured at 37 ° C. for 18 hours in a sealed container. Measure post viable counts. After inoculation, the antibacterial count is evaluated by the bacteriostatic activity value against the unprocessed cloth count.
(3) Antibacterial activity value: (Mb-Ma) - (Mc-Mo) (Antibacterial activity value ≥ 2.2, passed)
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 on the antibacterial and deodorant fabric (molded article of the present invention) immediately after inoculation with the test bacteria solution Mc : Number of viable bacteria after 18-hour culture of antibacterial deodorant treated cloth (4) Test effectiveness: Mb-Ma>1.0

As a result, the results shown in Table 8 below were obtained. It is clear that the molded article has antibacterial properties. Since Mb-Ma=2.0, which exceeds 1.0, this test is effective.

The deodorant of the present invention is useful for imparting daily necessities with deodorant performance against daily life odors. The antibacterial agent of the present invention is useful for imparting antibacterial and antiviral properties to daily necessities. In addition, the molded article of the present invention containing them is useful as daily necessities because it has excellent deodorant properties against daily life odors and has the effect of suppressing the growth of bacteria and viruses.

Claims (8)

A porous coordination polymer in which metal ions and organic ligands are alternately coordinated, and whose pore diameter is in the range of 0.6 to 1.0 nm. A method for producing a molded article containing and having deodorant, antibacterial or antiviral properties,
A step of applying a treatment liquid containing a binder resin in a solvent (excluding those containing the porous coordination polymer) to an air-permeable thin film material, and the thin film material coated with the treatment liquid. After drying, the amount of the porous coordination polymer attached to the thin film material is within the range of 0.05 to 20 g / m ² , and the porous coordination polymer or the porous coordination polymer is included A step of spraying a composition (excluding one containing a binder resin) on the thin film material ;
A method for manufacturing the molded article, comprising: 2. The method of manufacturing a molded article according to claim 1, wherein the metal ions are copper ions. 3. The method for producing a molded article according to claim 1, wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or its ester. The method for producing a molded article according to any one of claims 1 to 3, wherein the porous coordination polymer forms a composite with a polymer having a glass transition point (Tg) of 70°C or less. The method for producing a molded article according to any one of claims 1 to 4, wherein the living odor is cigarette odor, animal odor, excrement odor, garbage odor, or sweat odor. The method for producing a molded article according to any one of claims 1 to 5, wherein the solvent of the treatment liquid is water. The method for producing a molded article according to any one of claims 1 to 5, wherein the thin film material is a textile product, nonwoven fabric, filter or sheet. The method for producing a molded article according to any one of claims 1 to 6, wherein the molded article is a fiber, textile product, resin molded article, or filter.

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