JP2019088499A - Deodorant for life smell - Google Patents

Abstract

To provide, as a main object, a novel deodorant using a porous coordination polymer; PCP (MOF), which can have higher deodorizing performance against life smell, and to provide molded products such as fibers or filters containing such a deodorant, and further to provide a novel antibacterial agent or an antiviral agent using the PCP (MOF).SOLUTION: Provided is a deodorant for life smell such as, for example, tobacco smell, animal smell, and excrement smell, or an antibacterial agent or an antiviral agent, which is a porous coordination polymer containing, for example, metal ions and organic ligands which are alternately coordinated, in which a pore diameter is in a range of 0.6 to 1.0 nm. Also provided are molded products containing the same.SELECTED DRAWING: None

Description

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

  The porous coordination polymer (PCP) is also called metal organic structure (MOF: Metal Organic Framework), and is an artificially synthesized porosity utilizing coordination bonds between metal ions and organic ligands. It is a substance. A metal ion crosslinks the organic ligand to construct a framework, and a void in the framework functions as a space for taking in a molecule.

  Conventional porous materials may include natural inorganic materials such as zeolite, silica gel, activated carbon and the like. Although each has pore functions such as separation, absorption, adsorption, and discharge, it is difficult to control fine pores, and is subject to some limitations. In this respect, PCP can synthesize various porous structures by molecular design, and can construct highly complex or highly functional or multifunctional porous materials. Therefore, PCP absorbs gases (hydrogen, methane, CO2, etc.); selective storage of molecules and ions; separation such as isomer separation; solid catalyst for oxidation reaction, addition reaction, hydrogenation reaction etc .; A wide range of applications such as isolation; transport; nano containers; sensors are expected.

On the other hand, life odors such as tobacco smell, animal smell and excrement smell overflow in the living environment such as at home, at work and in public facilities. Depending on the smell, it can be a social problem. Although the treatment of excrement becomes a problem with the aging of the population, it also causes the problem of odor. Some tobacco and animal odors can not be tolerated by humans. Other living odors are desired to be removed if possible in order to spend comfortably in the living environment.
Conventionally, porous materials such as zeolite, silica gel and activated carbon have been used as one of the means for removing the life odor. However, such a natural porous material can not always be said to have a sufficient deodorizing effect.

Patent Document 1 discloses a method for trapping malodor using PCP (MOF), which is an artificial porous material. In Patent Document 1, as an offensive odor, a collection of feces, bad breath, cigarette smoke and the like are mentioned, and it is described that the MOF can be used as a household deodorant. Patent Document 1 neither describes nor suggests that the MOF can be used as an antibacterial agent or an antiviral agent.

International Publication No. 2007/035596

Patent Document 1 describes that PCP (MOF) can be used as a household deodorant.
An object of the present invention is to provide a novel deodorant that can have higher deodorizing performance against household odor using PCP (MOF). Another object of the present invention is to provide molded articles such as fibers and filters containing such a deodorant.
Furthermore, another object of the present invention is to provide a novel antibacterial agent or antiviral agent using PCP (MOF).

  As a result of intensive studies, the present inventors have found that by using PCP having a pore size in a certain range, they can have higher deodorizing performance against household odor, and complete the present invention I came to In addition, they have found that PCP can also have antibacterial properties and the like, and have completed the present invention.

  Examples of the present invention include the following.

[1] A porous coordination polymer in which a metal ion and an organic ligand are alternately coordinated and bound, and the pore diameter is in the range of 0.6 to 1.0 nm. Deodorant for life odor characterized by containing a high molecular weight polymer.
[2] The household odor deodorant according to the above [1], wherein the metal ion is a copper ion.
[3] The household odor deodorizer according to the above [1] or [2], wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or an ester thereof.
[4] The living odor according to any one of the above [1] to [3], wherein the porous coordination polymer forms a complex with a polymer having a glass transition point (Tg) of 70 ° C. or less Deodorants.
[5] The household odor deodorant according to any one of the above [1] to [4], wherein the household odor is tobacco odor, animal odor, excretory odor, garbage odor, or sweat odor.

[6] A molded article comprising the household odor deodorant according to any one of the above [1] to [5].
[7] The molded article according to the above [6], wherein the molded article is a fiber, a fiber product, a resin molded article, or a filter.

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

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

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

The photograph of the apparatus (modified detection tube) used by Experiment 1 grade.

1 Deodorant for life odor of the present invention The deodorant for life odor of the present invention (hereinafter referred to as "deodorant for the present invention") comprises metal ions and organic ligands alternately coordinated. It is characterized by including the porous coordination polymer whose pore diameter is in the range of 0.6 to 1.0 nm.

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

The pore diameter of the porous coordination polymer is in the range of 0.6 to 1.0 nm, which is the area of micropores according to the definition of IUPAC, but is preferably in the range of 0.7 to 0.9 nm, 0 .9 nm is more preferred. The pore diameter (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 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-mentioned pore diameter.

1.1.1 Metal Ions As metal ions which can constitute the porous coordination polymer, Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ^{4 +} , Hf ^{4 +} , V ^{4 +} , V ^{3 +} , V 2 ⁺ , Nb ^{3 +} , Ta ^{3 +} , Ta ^{3 +} , Cr ^{3 +} , Mo ^{3 +} , W ^{3 +} , Mn ^{3 +} , Mn 2 ⁺ , Re ^{3 +} , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ^{2+ +, 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 ⁺ can be mentioned. Among these, copper ions are particularly preferred.

1.1.2 Organic Ligand The organic ligand which can constitute a porous coordination polymer is an aromatic compound, aliphatic compound or alicyclic compound having a plurality of functional groups capable of coordinating with metal ions And aromatic compounds, aliphatic compounds, alicyclic compounds, heteroaromatic compounds and heterocyclic compounds containing heteroaromatic compounds and heterocyclic compounds and further having one functional group capable of coordinating with metal ions You may use together.

The functional group that can be coordinated to the metal ion of the organic ligand is preferably 1 to 5, preferably 1 to, one aromatic compound, aliphatic compound, alicyclic compound, heteroaromatic compound, and heterocyclic compound. Two to four, more preferably two to three are included. Such functional groups capable of coordinating to metal ions include glycidyl group, COOH, carboxylic acid anhydride group, CS ₂ H, OH, SH, SO, SO ₂ , SO ₃ H, NO ₂ , -S-,- SS-, Si (OH) ₃ , Ge (OH) ₃ , Sn (OH) ₃ , Si (SH) ₄ , Ge (SH) ₄ , Sn (SH) ₄ , PO ₃ H, AsO ₃ H, AsO ₄ H , P (SH) ₃ , As (SH) ₃ , CH (SH) ₂ , C (SH) ₃ , CH (NH ₂ ) ₂ , C (NH ₂ ) ₃ , CH (OH) ₂ , C (OH) ₃ , CH (CN) ₂ , C (CN) ₃ , CH (RSH) ₂ , C (RSH) ₃ , CH (RNH ₂ ) ₂ , C (RNH ₂ ) ₃ , CH (ROH) ₂ , C (ROH) ₃ And CH (RCN) ₂ , C (RCN) ₃ , NH ₂ , NHR, NR ₂ , and a nitrogen atom constituting an aromatic ring (wherein R represents a C _{1 to} C ₅ alkyl group or an aryl group). . The nitrogen atom constituting the aromatic ring means a ring nitrogen atom such as pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, thiazole, oxazole, phenanthroline, quinoline, isoquinoline, naphthyridine, purine, bipyridine, terpyridine and the like.

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

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

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

  Heteroaromatic compound means a monocyclic or polycyclic compound consisting of a 5- or 6-membered aromatic ring containing 1 to 3 heteroatoms selected from N, O and S, and in a polycyclic system 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, pyrazine, pyridazine, pyrimidine, pyridazine, indole, quinoline, isoquinoline, benzo [b] thiophene and benzimidazole. It can be mentioned.

  As a heterocyclic compound, morpholine, pyrrolidine, piperidine, methyl piperazine, tetrahydridofuran and dioxane are mentioned.

  The aromatic compound, aliphatic compound, alicyclic compound, heteroaromatic compound and heterocyclic compound are each 1 to 5, preferably 1 to 3, and particularly preferably 1 to 3 in addition to the functional group capable of coordinating with the metal ion. It may have 2 to 2 substituents. As such a substituent, chlorine atom, fluorine atom, bromine atom, iodine atom, methoxy, ethoxy, trifluoromethyl, methyl, ethyl, propyl, butyl, cyano, nitro, methylenedioxy, acetylamino, carbamoyl, acetyl And formyl.

  Specific examples of the organic ligand constituting the porous coordination polymer include pyridine, 4,4'-bipyridine, ethylenediamine, propylenediamine, 2-aminoethanol, 3-aminopropanol, trimethylamine, triethylamine, 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 Dihydroxymethane, 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, tartarite 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, acetylene dicarboxylic 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 acid, 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'-dical 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-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, pentane-3,3'-dicarboxylic acid, 4,4'-diamino-1 , 1′-diphenyl-3,3′-dicarboxylic acid, 4,4′-diaminodiphenyl-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) phenyl pyrazolin-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 5,5-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, O-hydroxy benzophenone dicarboxylic acid, pulliol E300-dicarboxylic acid, Pururiol E400-dicarboxylic acid, Pururiol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 5,6-dimethyl-2,3-pyrazine dicarboxylic acid, 4, 4'-diamino (diphenyl ether) diimide dicarboxylic acid, 4, '-Diaminodiphenylmethanediimide dicarboxylic acid, 4,4'-diamino (diphenyl sulfone) diimide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantane dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3- Naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic 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-quinoline dicarboxylic acid, 4,5-imidazole dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontane dicarboxylic acid, tetradecane dicarboxylic acid, 1,7-heptane dicarboxylic acid, 5-hydroxy-1 , 3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic 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 Acid, 2,9-dichlorofluorbin-4,11-dicarboxylic acid, 7-chloro-3-methyl acid Quinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2 ', 5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4- Dicarboxylic acid, 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 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-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, 1,1-dioxideperilo [1 , 12-BCD] thiophene-3,4,9,10-tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid perylene-1.12-s Hong-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 2,2,11,12-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'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentane-1 And 2,3,4-tetracarboxylic acid. Among these, 1,3,5-benzenetricarboxylic acid or an ester thereof is preferable.

  In the present specification, the porous coordination polymer may be composed of a metal ion and an organic ligand, and may contain a counter anion. As metal ions, ions of magnesium, calcium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, cadmium, titanium, vanadium, chromium, manganese, platinum, ruthenium, molybdenum, zirconium, scandium, etc. Preferably, ions of metals such as magnesium, manganese, iron, cobalt, nickel, copper and zinc are more preferable. As the metal ion, a single metal ion may be used, or two or more types of metal ions may be used in combination.

  Preferred organic ligands which can constitute the porous coordination polymer include benzene, naphthalene, anthracene, phenanthrene, fluorene, indane, indene, pyrene, 1,4-dihydronaphthalene, tetralin, biphenylene, triphenylene, acenaphthylene, acenaphthene. Compounds in which two, three or four carboxyl groups are bonded to an aromatic ring such as (the above-mentioned ligand is a halogen atom such as F, Cl, Br, I etc., an acylamino group such as a nitro group, an amino group or an acetylamino group) Straight-chain or branched alkoxy group having 1 to 4 carbon atoms such as cyano, hydroxyl, methylenedioxy, ethylenedioxy, methoxy, ethoxy, etc., linear such as methyl, ethyl, propyl, tert-butyl, isobutyl or the like Branched C 1 -C 4 alkyl group, SH, tri It may be substituted by 1, 2 or 3 substituents such as trifluoromethyl group, sulfonic acid group, carbamoyl group, alkylamino group such as methylamino, dialkylamino group such as dimethylamino), fumaric acid, maleic acid, citraconic Acid, unsaturated divalent carboxylic acid such as itaconic acid, pyridine, pyrazine, pyridazine, pyrimidine, 4,4'-bipyridyl, diazapyrene, nicotinic acid, imidazole, thiazole, oxazole, quinoline, isoquinoline, naphthyridine, etc. And nitrogen-containing aromatic compounds (which may be substituted 1, 2 or 3 by the above-mentioned substituents), etc., which can be coordinated by the ring nitrogen atom, oxygen atom or sulfur atom of If the ligand is neutral, it has the counter anion necessary to neutralize the metal ion. As such counter anions, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, phosphate ion, trifluoroacetate ion, methanesulfonate ion, toluenesulfonate ion, benzenesulfonate ion, Chlorate ion etc. are mentioned.

  The porous coordination polymer according to the present invention has a porous arrangement having a three-dimensional pore such as a sheet-like two-dimensional pore or a bidentate ligand in which a plurality of sheets coordinate in an axial position as a component For example, porous coordination polymers having one-dimensional pores as described below can be used.

IRMOF-1, [Zn ₄ O (1,4-BDC) ₃ ] _n (H ₂ -1,4-BDC = 1,4-benzenedicarboxylic acid)
MOF-69C, [Zn ₃ (OH ₂ ) (1,4-BDC) ₂ ] _n
MOF-74, [M ₂ (DOBDC)] _n (H ₂ DOBDC = 2,5-dihydroxyterephthalic acid, M = Zn, Co, Ni, Mg)
HKUST-1, [Cu ₃ (1,3,5-BTC) ₂ ] _n (H ₃ -1,3,5-BTC = 1,3,5-benzeritricoxylic 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, [Cr ₃ F (H ₂ O) ₂ O (1,4-BDC) ₃ ] _n
Al-MIL-110, [Al ₈ (OH) ₁₂ {(OH) ₃ (H ₂ O) 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, [Cr ₃ OF (1,4-BDC) ₃ ] _n
MIL-88C, [Fe ₃ OX (O ₂ CC ₁₀ H ₆ -CO ₂ ) ₃ ] _n (X = OH, Cl)
MIL-88D, [Cr ₃ OF (O ₂ CC ₁₂ H ₈ -CO ₂ ) ₃ ] _n
CID-1 [Zn ₂ (ip) ₂ (bpy) ₂ ] _n (H ₂ ip = isophthalic acid)

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

  Porous coordination polymers which can be used in the present invention are described, for example, in the following documents, 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. Nature, 2003, 2-14. 423, 705-714.), Patent documents (WO 2015/129685), etc., but not limited thereto, and known porous coordination polymers or porous coordinations that can be manufactured in the future Polymers can be used widely.

1.2 Composite of Porous Coordination Polymer and Polymer The porous coordination polymer forms a complex with a polymer having a glass transition point (Tg) of 70 ° C. or less (hereinafter simply referred to as “polymer”). It may be done. Therefore, the present invention also includes a household odor deodorant characterized in that it comprises a complex 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 is a polymer having a functional group capable of coordinating to the metal ion, and can be produced by a known polymer or a known production method. Polymers can 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 crosslinking agent capable of reacting with the functional group further possessed by the polymer. For example, when the functional group possessed by the polymer is glycidyl group, an organic crosslinking agent having two or more of amino group, hydroxyl group, carboxyl group, thiol group etc., and when the functional group possessed by polymer is thiol group, vinyl group, acrylic group etc. Organic cross-linking agents having two or more double bonds, organic cross-linking agents having two or more isocyanate groups, formyl groups, carboxylic acid anhydride residues and the like when the functional group possessed by the polymer is a hydroxyl group, functional groups possessed by the polymer In the case of an amino group, an organic crosslinking agent having two or more isocyanate groups, formyl groups and the like, and in the case where the functional group possessed by the polymer is a carboxyl group, an organic group having two or more isocyanate groups, carbodiimide residues, oxazoline groups, epoxy groups and the like When the functional group possessed by the crosslinking agent or polymer is a carboxylic acid anhydride residue, it has two or more hydroxyl groups, amino groups, etc. The organic crosslinking agents and the like may be mentioned as a cross-linked structure that. When an organic crosslinking agent is used, a solvent which does not react with the organic crosslinking agent or which does not react with the organic crosslinking agent in which the organic crosslinking agent reacts with the polymer faster than the solvent is used.

  As an organic crosslinking agent having two or more isocyanate groups, aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate and the like; burette type adducts of these polyisocyanates, isocyanurate ring 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-cyclopentadiisocyanate, 1,2-cyclohexane diisocyanate, etc .; Biuret type adduct of isocyanate, isocyanurate cyclic adduct; xylylene diisocyanate, metaxylylene diisocyanate, tetramethyl xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate 1,4-naphthalene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenylether isocyanate, (m- or p-) phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'- Aromatic diisocyanate compounds such as dimethyl-4,4'-biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone and isopropylidene bis (4-phenylisocyanate) Buret type adducts of these diisocyanate compounds, isocyanurate cyclic adducts; triphenylmethane-4,4 ', 4' '-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4 Polyisocyanates having three or more isocyanate groups in one molecule, such as 6,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate; these polyisocyanates And burette type adducts of the following, and isocyanurate cycloadducts. Moreover, the compound which substituted said isocyanate (NCO) to the isothiocyanate (NCS) is mentioned.

  Monomers that can constitute the polymer include olefins such as ethylene, propylene and butylene, tetrafluoroethylene, vinylidene fluoride, trifluoroethylene, halogenated olefins such as vinyl chloride, dienes such as butadiene and isoprene, acrylic acid and methacrylic acid Acrylic acid ester or methacrylic acid ester (eg, 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, Chlorohexyl 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, Benzime Aromatic compounds containing aromatic rings such as styrene, vinyl toluene and α-methylstyrene; vinyl esters such as vinyl propionate and vinyl acetate; acrylonitrile and methacrylonitrile; (meth) acrylamide; glycidyl (meth) acrylate, Epoxy group-containing vinyl compounds such as 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene monoepoxide, N-glycidyl acrylamide, allyl glycidyl ether; aminoethyl (meth) acrylate, N-t-butylaminoethyl (meth) ) Acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N- Amino group-containing (meth) acrylates such as butylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate Amino group-containing (meth) acrylamides such as meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, etc .; Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glyceryl (meth) acrylate, cyclohexane dimethanol mono (meth) acrylate, N-hydroxyethyl (meth) a Hydroxyl group-containing vinyl compounds such as monoesters of acrylic acid or methacrylic acid with polyhydric alcohols such as chloramide, polyethylene glycol mono (meth) acrylate, etc., and reaction products of these with ε-caprolactone; acrylic acid, methacrylic acid, Carboxyl group-containing vinyl compounds such as maleic acid, 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, hymic acid anhydride Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, octanediol, tricyclodecane dimer Roll, low molecular weight glycols such as cyclohexanedimethanol, hydrogenated bisphenol A, high molecular weight glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate glycol etc., polyhydric alcohols such as glycerin and (meth) acrylic acid Examples include monoesters; maleic acid, chloromaleic acid, fumaric acid and acid anhydrides thereof.

  In the case where the polymer is a polyurethane, the monomer having two or more isocyanate groups may be reacted with the monomer having two or more hydroxyl groups, and in the case of polyester, the monomer having two or more carboxylic acid groups and It is obtained by polymerizing the above-mentioned 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 according to a conventional method such as use of a polymerization initiator or ultraviolet irradiation.

The glass transition point (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 the method of thermal analysis or the method calculated from the Fox equation.

  The ratio (weight ratio) of the porous coordination polymer to the polymer varies depending on the type of the porous coordination polymer, the polymer, etc. For example, 70 to 99% by weight of the porous coordination polymer: 30 to 1 weight of the polymer %, Preferably 80 to 98% by weight of porous coordination polymer: 20 to 2% by weight of polymer, more preferably 85 to 97% by weight of porous coordination polymer: 15 to 3% by weight of polymer.

  A conductive agent and a lubricant can be further blended in the composite. Examples of the conductive agent include carbon black, ketjen black, carbon nanofibers, acetylene black, channel black, lamp black, furnace black, graphite powder, fibrous carbon material, metal powder, metal fiber and the like.

  As lubricants, 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 calcium stearate, barium stearate, magnesium stearate, zinc stearate, lithium stearate, stearates such as 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 compound known per se and can be obtained by a known production method (the production method described in the above-mentioned documents etc.) Also, those of the above-mentioned pore diameter can be prepared by a conventional method. The complex of the porous coordination polymer and the polymer can be produced, for example, according to the description of WO 2015/012373.

  The deodorant according to the present invention may be, for example, powdered porous coordination polymer or a complex thereof with the polymer alone or using a suitable carrier, and powdered or dissolved or suspended in a solvent according to a conventional method, and pressure kneading Or can be produced by heating and kneading. Examples of carriers for powdering include activated carbon, zeolite, mesoporous silica, silica and alumina. As an average particle diameter of the said powder, the inside of the range of 0.1-5000 micrometers can be mentioned, for example, Preferably it is in the range of 0.5-1000 micrometers. Examples of the solvent include toluene, xylene, ethyl acetate, methanol, ethanol, acetone and the like.

  The deodorizer of the present invention can also be filled into a spray container or a sprayer. The shape of the spray container is not particularly limited, and examples thereof include a trigger type spray bottle, an atomizer, a sprayer, a spray can and a pump. There is no restriction | limiting in particular as a method to fill the spray container with the deodorizer of this invention, A well-known method is employable.

  When the deodorant of the present invention is charged together with the propellant, such a propellant is not particularly limited as long as it is usually used, and examples thereof include liquefied gas and compressed gas. Specific examples thereof include hydrocarbons, liquefied natural gas (LPG), dimethyl ether, diethyl ether, fluorinated hydrocarbons, 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. As another deodorant component, zeolite, activated carbon, silica gel, cyclodextrin can be mentioned, for example. As an additive, surfactant, a water absorbing agent, a penetrant, a dispersing agent etc. can be mentioned, for example.

  The content of the porous coordination polymer in the deodorant of the present invention is the type of porous coordination polymer, the combination or amount of other deodorant components and additives, the form of the deodorant of the present invention, life odor Although it differs depending on the situation, it is appropriately set, for example, in the range of 0.1 to 100% by weight, preferably in the range of 1 to 100% by weight. If the amount is less than 0.1% by weight, sufficient deodorizing performance may not be obtained.

1.4 Living odor The deodorizer of the present invention is excellent, for example, in instantaneously deodorizing the following living odor.
(1) Care / nursing odor, hospital odor: urine odor, excrement odor (2) general living odor-1: raw garbage odor, changing room odor, locker odor, fitting room odor, crowded odor (in crowded train odor), air conditioner Odor, tatami odor, floor odor, kitchen odor, toilet odor, bathroom odor, geta box odor, drained breath odor (3) general life odor-2: body odor, sweat odor (4) general life odor-3: tobacco odor, grilled meat Odor (5) Other life odor: Compost odor, animal odor, pet manure odor, odor inside car

2. Antibacterial agent / antiviral agent of the present invention The present invention includes an antibacterial agent or antiviral agent characterized by containing a porous coordination polymer in which metal ions and organic ligands are alternately coordinated. An agent (hereinafter referred to as "the antibacterial agent of the present invention").

The meanings of “metal ion”, “organic ligand”, and “porous coordination polymer” are as defined above, but the pore diameter of the porous coordination polymer is appropriately selected regardless of the diameter. Adjusted. The pore size of the preferred porous coordination polymer is in the range of 0.6 to 1.0 nm, more preferably in the range of 0.7 to 0.9 nm, and particularly preferably 0.9 nm.
The antibacterial agent of the present invention can be manufactured in the same manner as the manufacturing method described in the above-mentioned "1.3 Method of manufacturing a deodorant of the present invention".

  The bacteria and viruses to which the antibacterial agent of the present invention can be applied are not particularly limited, and examples thereof include the following bacteria and viruses. The fungus also includes fungi.

<Fungus>
(1) Gram-negative familial anaerobic bacilli E. coli (Eshericha coli), Shigella (Sigella), Salmonella (Salmonella), Klebsiella (Klebsiella), Proteus (Proteus), Yersinia (Yersinia), Vibrio cholerae (V) (Chlorae), Vibrio parahaemolyticus (Vparahaemolyticus), Haemophilus (Haemophilus)
(2) Gram-negative aerobic bacilli Pseudomonas (Pseudomonas), Legionella (Legionella), Bordetella (Bordetella), Brucella (Brucella), wild borage (Francisella tularensis)
(3) Gram-negative anaerobic bacilli Bacteroides
(4) Gram-negative coccus Neisseria (Neisseria)
(5) Gram-positive cocci Staphylococci (Staphylococcus sp., Streptococcus sp., Enterococcus sp.)
(6) Gram-positive spore bacillus Bacillus (Bacillus), Clostridium (Clostridium)
(7) Actinomycetes and Related Microorganisms Corynebacterium (Corynebacterium), Mycobacterium (Mycobacterium)
(8) Mycoplasma Mycoplasma (Mycoplasma)
(9) Spirochetes and Helicobacters relapsing fever Borrelia (Borrelia recurrentis), Lyme disease Borrelia (B. burgdoferi), Syphilis Treponema (Treponema palidum), Campylobacter genus (Hempobacter), Helicobacter genus (Helicobacter)
(10) Rickettsia Rickettsia
(11) Chlamydia Chlamydia (Clamydia)

(12) Fungus Cryptococosis (Cryptococcosis), Candidiasis (Candiasis), Aspergillosis (Aspergilosis), Pneumocystis carinii (Pneumocystis carinii), Trichophyton, Trichophyton (Tinea versicolor)

<Virus>
Infectious molluscoma virus, herpes simplex virus, varicella / zoster virus, rotavirus, human papilloma virus, polio virus, coxsackie virus, rhinovirus, rubella virus, measles (measles) virus, influenza virus, epidemic earwax Adenitis virus, RS virus, hepatitis virus, HIV

The molded article of the present invention The present invention is a molded article characterized by containing the present deodorant or the present antibacterial agent (hereinafter, also referred to as "the present preparation") (hereinafter referred to as "the present invention (Including molded 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 process the deodorant of the present invention, and examples thereof include fibers, fiber products, resin molded articles, and filters.

The fibers may be any of synthetic fibers, regenerated fibers and natural fibers.
Examples of synthetic fibers include polyester, nylon, acrylic and acetate. As a regenerated fiber, rayon can be mentioned, for example. As natural fiber, cotton, hemp, wool, silk can be mentioned, for example. Cotton includes not only raw cotton itself but also caustic mercerized cotton, cotton treated with liquid ammonia and the like. The fibers may be a blend of the fibers, or may be a primary processed product of the fibers, such as yarn, cord, rope, woven fabric, knitted fabric, non-woven fabric, paper and the like.

The above-mentioned textile goods mean those which processed the above-mentioned textile further, and although it is not restricted in particular, for example, clothing such as outer clothes, clothes, inner clothes, sleeping goods, interiors, household goods, car interior goods can be mentioned. Specifically, for example, coats, jackets, pants, skirts, shirts, knit shirts, blouses, nightwear, underwear, sweaters, supporters, socks, tights, stockings, hats, scarfs, clothing lining, clothing interlining, Clothing such as cotton batting, work clothes, uniforms, uniforms for school children; beddings such as duvets, duvets, duvet covers, sheets, pillow covers etc. interiors such as sheets, mats, curtains, carpets; towels, handkerchiefs, towel And household goods such as pot holders, diapers and sanitary products; and products such as automotive interior products such as sheets, seat covers and handle covers.
The textile products also include those in the form of textile products used in the field of industrial materials such as wall cloths, ceiling cloths, floor coverings and the like.

The above-mentioned resin molded products are 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 It refers to molded articles such as plate-like articles, columnar articles, and extrusion-molded articles made of resins and blend resins thereof. Specific examples of resin molded products include films, sheets, and containers of these resins.
The film, sheet, container and the like can be formed by various inflation devices, presses, calenders, extruders, spinning machines, blow molding machines, injection molding machines, vacuum molding machines and the like.

  As said filter, the deodorizing filter used for an air cleaner etc., an antibacterial filter can be mentioned, for example.

3.2 Process for Producing the Invented Article The inventive article can be produced by incorporating the inventive preparation according to a conventional method according to the desired article.
For example, when the preparation of the present invention is adhered to or impregnated into a fiber or fiber product, for example, an immersion method, a spray method, a coating method (including a method of applying using a brush, sponge or the like) can be used.

  In order to prevent the detachment of the inventive preparation from fibers or textiles, it is preferred to use binder resins to adhere the zinc carbonate particles to the fibers or textiles. The binder resin is not particularly limited as long as it is used in the relevant technical field, but various types of thermosetting such as urethane resin, silicone resin, acrylic resin, melamine resin, urea formalin resin, etc. Resin can be mentioned. The amount of binder resin used may be such an amount that the preparation of the present invention can be fixed to a fiber or fiber product.

  In the case of the immersion method, it can be produced by immersing a fiber or fiber product to be treated in a conventional manner in a treatment liquid containing the preparation of the present invention and optionally a binder resin. The concentration of the preparation of the present invention in the treatment liquid can be set to a concentration calculated from the throttling rate of the treatment liquid and the required loading amount. As a solvent which comprises the said process liquid, organic solvents, such as alcohols, such as toluene, xylene, ethyl acetate, and ethanol, can be mentioned.

  The penetration time of the above-mentioned treatment liquid into fibers or textiles is sufficiently fast, and the immersion time and bath temperature are not particularly limited. Usually, the immersion time is in the range of 0.1 seconds to 300 seconds, and the bath temperature is in the range of 10 to 40 ° C. Although the drawing varies depending on the product to be processed, an appropriate drawing method and drawing ratio can be adopted for each. In general, it is preferable to squeeze with a mangle or the like so as to obtain a uniform aperture ratio.

The adhesion or impregnation amount of the preparation of the present invention is usually in the range of 0.01 to 50 g / m ² , preferably in the range of 0.05 to 20 g / m ² as the amount of PCP relative to 1 m ² of the dough. is there.

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

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

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

  In addition, the molded article of the present invention is also manufactured by first applying a treatment liquid containing a binder resin (not including the preparation of the present invention) to fibers or fiber products and the like and then spraying the preparation of the present invention thereon after drying. be able to. As a solvent of the process liquid in that case, water can also be mentioned other than the said organic solvent. By using water, safety and simplicity can be achieved.

  Fibers and molded articles of the present invention, such as resin products other than fiber products and filters, can also be manufactured basically in the same manner as the above-mentioned manufacturing method of fibers or fiber products.

In particular, in each of the following (1) to (3), a method for producing a molded article of the present invention, which includes each step, is preferable.
(1) The solid content weight ratio of the porous coordination polymer in which the metal ion and the organic ligand are alternately coordinated and bound to the binder resin is 1: 0.01 to 1:30 (porous coordination A step of dissolving the mixture in the range of polymer: binder resin) in an organic solvent, a step of applying the mixture dissolved in the organic solvent to the breathable thin film material, and a step of 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, porous coordination height) 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 a breathable thin film material Process and process of sandwiching high temperature and pressure with thin film material having air permeability.

(3) A step of applying a binder resin to a breathable thin film material, and a step of spraying a porous coordination polymer in which metal ions and organic ligands are alternately coordinated and bonded 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" and the like are as defined above. It is. The "breathable thin film material" may include breathable, for example, textiles, non-woven fabrics, filters and sheets.

  EXAMPLES The present invention will be described by citing examples below, but the present invention is not limited by these examples.

[Example 1] Preparation of Cu-PCP (HKUST-1, pore diameter 0.9 nm) Copper (II) nitrate trihydrate 2.11 g (for three) and 1,3,5-benzenetri (carbonyl) An aqueous solution of 50 vol% ethanol (57.6 mL (three)) was added to 1.01 g (three) of methyl acid methyl), stirred for 10 minutes, and reacted at 140 ° C. for 60 minutes using a microwave. Ethanol was added to the solid collected by suction filtration and washed with ultrasonic waves. The solid recovered by suction filtration was vacuum dried to obtain 1.24 g of Cu-PCP having a pore diameter of 0.9 nm. The said pore diameter was measured by the high precision gas / vapor | steam adsorption amount measuring apparatus BELSORP-max12-N-S from Microtrac Bell (following same.).

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

[Reference Example 2] Preparation of Ni-PCP (Ni-MOF 74, pore diameter: 1.1 nm) Nickel (II) nitrate hexahydrate: 3.63 g and 0.72 g of 2,5-dihydroxyterephthalic acid N, N- 72 mL of dimethylformamide and 3.6 mL of water were added and dissolved by ultrasound. The reaction was carried out at 110 ° C. for 21 hours and 30 minutes using an autoclave. The solid collected by suction filtration was vacuum dried to obtain 2.44 g. After washing with methanol, the solid collected 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)) 50 mL of water is added to 2.97 g of chromium (III) chloride hexahydrate and 1.85 g of terephthalic acid, and the mixture is stirred, and an autoclave is used 210 It reacted for 6 hours at ° C. After centrifugation, the supernatant was taken and vacuum dried. Supernatant was taken after adding N, N-dimethylformamide and ultrasonic cleaning. After adding ethanol and ultrasonic cleaning, the supernatant was collected 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 deodorizing test (ammonia odor)
The tip of a commercially available detector tube was cut, sample powder was placed therein, and cotton (about 0.0045 g) was rolled into a lid to prevent sample powder from coming out (see FIG. 1).
The ammonia odor solution was put into a 500 mL stoppered Erlenmeyer flask, sealed, put into a drying chamber at 60 ° C. for 15 minutes, and evaporated. Then, the sample tube was taken out of the drying chamber and allowed to cool for 30 minutes, and then the detection tube was inserted into the flask and the ammonia concentration of the gas passed through the detection tube was measured to test the instantaneous deodorizing properties of each sample powder. 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, which is a mixture of silicon dioxide and zinc oxide, which is used for deodorizing four major malodors (hydrogen sulfide, ammonia, trimethylamine, methyl mercaptan) and valeric acid, phenol, NOx, etc. (Manufactured by Lassa Kogyo Co., Ltd.).

  As described 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 ammonia concentration, and is excellent in the instantaneous deodorizing property to the ammonia odor. It is clear that

[Test Example 2] Instantaneous deodorizing test (acetic acid odor)
Instantaneous deodorizing performance was tested also about an acetic acid smell like Example 1 of an examination. The results are shown in Tables 4 and 5.

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

[Test example 3] Instant deodorizing test (cigarette odor)
In a glass container (length 40 cm × width 25 cm × height 27 cm = 27000 cm ³ (27 L)), burn tobacco (Mebius® Superlight (6 mg tar, 0.5 mg nicotine)) and seal Those left for a day were regarded as odorous substances. On the other hand, a rubber tube was inserted into the tip of a commercially available disposable syringe, the rubber tube was packed with cotton, sample powder (about 0.025 g) was charged at the center, and the lid was covered with cotton.

  A rubber tube fitted with a sample powder was inserted into a glass container set for 1 day, and 10 mL or 30 mL of odor was collected. After that, the rubber tube was immediately removed, and the odor in the syringe was sensory-evaluated by three persons based on the following evaluation criteria. The results are shown in Table 6.

  In addition, acetaldehyde deodorant A is a commercially available KD-511 (made by Lasa Kogyo Co., Ltd.) which is a mixture of silicon dioxide and zirconium oxide, and deodorant B is a commercially available KD- which is a mixture of silicon dioxide and zinc oxide. 211 (manufactured by Lasa Kogyo Co., Ltd.). It is used for deodorizing sweat odor and aging odor (ammonia, acetic acid, isovaleric acid and nonenal). Zeolite is ABSCENTS-3000 (manufactured by Union Showa Co., Ltd.).

<Sensory evaluation criteria>
0: odorless, 1: barely perceptible smell, 2: perceptible smell what is 3: easily perceptible smell, 4: strong smell, 5: intense smell

  As described in Table 6, it is clear that the deodorant of the present invention having a pore diameter of 0.9 nm (Example 1) is superior in instantaneous deodorizing property to tobacco odor as compared with other deodorants. It is.

[Test Example 4] Instantaneous deodorizing test (excretion odor)
The odor eliminating performance was also tested in the same manner as in Test Example 1 for odor elimination. The results are shown in Table 7. In addition, the excretion odor used defecation of 1-year-old infants.

  As described in Table 7, it is clear that the deodorant of the present invention having a pore diameter of 0.9 nm (Example 1) is superior in instantaneous deodorizing property to excrement odor as compared with the zeolite deodorant. is there.

[Example 4] Preparation of the preparation of the present invention and the molded article of the present invention 0.025 parts by weight of Cu-PCP of Example 1 and acrylic acid ester resin (MC polymer RH-BK (solid content 40%), Murayama Chemical Laboratory The product of the present invention was prepared by dissolving 0.1 part by weight of the product in 6.1 parts by weight of toluene. A cotton knit was dipped in the preparation of the present invention for 1 minute and dried in a box drier at 60 ° C. for 5 minutes and then at 160 ° C. for 2 minutes to produce a molded article of the present invention.

Test Example 5 Antimicrobial Test The molded article of the present invention of Example 4 was subjected to an antibacterial test in accordance with the Fiber Evaluation Technology Council (JIS L1902). Specifically, it was carried out by the following method.

(1) Test fungus: Staphylococcus aureus (2) Test method: A test bacteria suspension to which a surfactant (Tween 80) is added is injected into a sterilized test material, and cultured in a closed container at 37 ° C. for 18 hours. Measure the number of viable bacteria later. After inoculation, the number of antibacterials is evaluated by the bacteriostatic activity value against the number of untreated fungi.
(3) Antibacterial activity value: (Mb-Ma)-(Mc-Mo) (Antibacterial activity value 2.2 2.2, pass)
Ma: Viable cell count immediately after contact with the test cell solution of the standard cloth Mb: Viable cell count after 18 hours incubation of the standard cloth Mo: Viable cell count immediately after the test cell liquid inoculation of the antibacterial deodorant treated cloth (the molded article of the present invention) : Viable cell count after incubation for 18 hours of antibacterial deodorant treated cloth (4) Test effectiveness: Mb-Ma> 1.0

  As a result, the results shown in the following Table 8 were obtained, and the antibacterial activity value of the molded article of the present invention which was subjected to the antibacterial and deodorizing processing was 6.1, and it was 2.2 or more. It is clear that the molded articles have antibacterial properties. In addition, since it is Mb-Ma = 2.0 and is over 1.0, this test is effective.

  The deodorizer of the present invention is useful for imparting a daily odor product with a deodorizing ability for daily life. The antimicrobial agent of the present invention is useful for imparting antimicrobial and antiviral properties to daily products. In addition, the molded articles of the present invention containing them are useful as household products because they are excellent in deodorizing property against household odor and have an effect of suppressing the growth of bacteria and viruses.

Claims (14)

A porous coordination polymer comprising a metal ion and an organic ligand alternately coordinated and having a pore size in the range of 0.6 to 1.0 nm. Deodorant for life odor characterized by including. The household odor deodorizer according to claim 1, wherein the metal ion is a copper ion. The household odor deodorizer according to claim 1 or 2, wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or an ester thereof. The household odor deodorizer according to any one of claims 1 to 3, wherein the porous coordination polymer forms a complex with a polymer having a glass transition point (Tg) of 70 ° C or less. The household odor deodorant according to any one of claims 1 to 4, wherein the household odor is tobacco odor, animal odor, excretory odor, garbage odor, or sweat odor. The molded article characterized by including the deodorizer for life odor as described in any one of Claims 1-5. The molded article according to claim 6, wherein the molded article is a fiber, a fiber product, a resin molded article, or a filter. An antimicrobial agent or an antiviral agent comprising a porous coordination polymer in which metal ions and organic ligands are alternately coordinated. The antibacterial agent or antiviral agent according to claim 8, wherein the pore size of the porous coordination polymer is in the range of 0.6 to 1.0 nm. The antibacterial agent or antiviral agent according to claim 8 or 9, wherein the metal ion is a copper ion. The antibacterial agent or antiviral agent according to any one of claims 8 to 10, wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or an ester thereof. The antimicrobial agent or antiviral agent according to any one of claims 8 to 11, wherein the porous coordination polymer forms a complex with a polymer having a glass transition point (Tg) of 70 ° C or less. An article or article comprising the antimicrobial agent or antiviral agent according to any one of claims 8 to 12. The molded article according to claim 13, wherein the molded article is a fiber, a fiber product, a resin molded article, or a filter.