JP2022009369A - Life smell deodorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel manufacturing method of a molding containing a porous coordination polymer and having a life smell deodorant.

SOLUTION: The present invention relates to a manufacturing method of a molding that includes a porous coordination polymer formed by alternately coordination bonding, for example, metal ions and organic ligands and has its fine pore diameter in the range of 0.6 to 1.0 nm, and has life smell deodorant or antibacterial property or antiviral property and includes the steps of: coating a treatment liquid (excluding one containing the porous coordination polymer) containing a binder resin in a solvent; and after drying a thin film material on which the treatment liquid was coated, dispersing the composition (excluding one containing the binder resin) containing the porous coordination polymer or the porous coordination polymer.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

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

Porous coordination polymer (PCP) is also called a metal-organic framework (MOF), and is artificially synthesized by utilizing the coordination bond between a metal ion and an organic ligand. It is a substance. A framework is constructed by cross-linking metal ions with organic ligands, and the voids in this framework function as spaces for taking up molecules.

Examples of conventional porous substances include natural inorganic substances such as zeolite, silica gel, and activated carbon. Each has pore functions such as separation, occlusion, adsorption, and discharge, but it is difficult to control fine pores, and there are some restrictions. In this respect, PCP can synthesize various porous structures by molecular design, and can construct very complicated structures and highly functional or multifunctional porous substances. Therefore, PCP is an occlusion of gas (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 .; sustained release; It is expected to have a wide range of applications such as isolation; transportation; nano-containers; sensors.

On the other hand, living odors such as tobacco odor, animal odor, and excretion odor are overflowing in the living environment such as home, workplace, and public facilities. Depending on the odor, it may become a social problem. With the aging of the population, the treatment of excrement becomes a problem, but at the same time, the problem of excrement odor also arises. Some humans cannot tolerate the odor of tobacco and animals. It is desirable to remove other living odors if possible in order to spend comfortably in the living environment.
As one of the means for removing these living odors, porous substances such as zeolite, silica gel, and activated carbon have been conventionally used. However, it is not always possible to say that such a natural porous substance has a sufficient deodorizing effect.

Patent Document 1 discloses a method for confining a bad odor using PCP (MOF), which is an artificial porous substance. Patent Document 1 includes fecal collection, halitosis, cigarette smoke and the like as malodors, and describes that MOF can be used as a household deodorant. It is neither described nor suggested in Patent Document 1 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.
The main object of the present invention is to provide a novel deodorant using PCP (MOF), which can have higher deodorizing performance for daily odors. Another issue is to provide molded products such as fibers and filters containing such deodorants.
Furthermore, it is also an object of the present invention to provide a novel antibacterial agent or antiviral agent using PCP (MOF).

As a result of diligent studies, the present inventors have found that by using a PCP having a pore size in a certain range, it is possible to have higher deodorizing performance for living odors, and completed the present invention. I came to do it. Further, 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 metal ions and organic ligands are alternately coordinated and bonded, and the pore diameter is in the range of 0.6 to 1.0 nm. A deodorant for daily odors, which is characterized by containing a coordination polymer.
[2] The deodorant for daily odors according to the above [1], wherein the metal ion is a copper ion.
[3] The deodorant for daily odor according to the above [1] or [2], wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or an ester thereof.
[4] The household odor according to any one of the above [1] to [3], wherein the porous coordination polymer forms a complex together with the polymer having a glass transition point (Tg) of 70 ° C. or lower. Deodorants.
[5] The deodorant for living odor according to any one of the above [1] to [4], wherein the living odor is a tobacco odor, an animal odor, an excretory odor, a swill odor, or a sweat odor.

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

[8] An antibacterial agent or an antiviral agent, which comprises a porous coordination polymer in which metal ions and organic ligands are alternately coordinated and bonded.
[9] The antibacterial agent or antiviral agent according to the above [8], wherein the pore diameter 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 [8] to [11], wherein the porous coordination polymer forms a complex together with the polymer having a glass transition point (Tg) of 70 ° C. or lower. Antiviral agent.

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

[15] A porous coordination polymer in which metal ions and organic ligands are alternately coordinated and bonded, and the pore diameter is in the range of 0.6 to 1.0 nm. A method for producing a molded product containing a coordination polymer and having a living odor deodorant property, an antibacterial property, or an antiviral property.
A step of applying a treatment liquid containing a binder resin in a solvent (excluding those containing the porous coordination polymer) to a breathable thin film material, and a thin film material to which the treatment liquid is applied. After drying, the step of spraying the porous coordination polymer or the composition containing the porous coordination polymer (however, excluding those containing a binder resin).
The method for producing a molded product, which comprises the above.
[16] The method for producing a molded product according to the above [15], wherein the metal ion is a copper ion.
[17] The method for producing a molded product according to the above [15] or [16], wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or an ester thereof.
[18] The molded product according to any one of [15] to [17] above, wherein the porous coordination polymer forms a complex together with the polymer having a glass transition point (Tg) of 70 ° C. or lower. Manufacturing method.
[19] The method for producing a molded product according to any one of the above [15] to [18], wherein the living odor is a tobacco odor, an animal odor, an excretory odor, a swill odor, or a sweat odor.
[20] The method for producing a molded product according to any one of the above [15] to [19], wherein the solvent of the treatment liquid is water.
[21] The method for producing a molded product according to any one of the above [15] to [20], wherein the thin film material is a textile product, a non-woven fabric, a filter, or a sheet.
[22] The method for producing a molded product according to any one of the above [15] to [21], wherein the molded product is a fiber, a textile product, a resin molded product, or a filter.

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

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

1 Deodorant for living odors of the present invention In the deodorant for living odors of the present invention (hereinafter referred to as "the deodorant of the present invention"), metal ions and organic ligands are alternately coordinated and bonded. It is a porous coordination polymer, characterized in that it contains a porous coordination polymer whose pore diameter is 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 in the range of 0.6 to 1.0 nm. In such a porous coordination polymer, metal ions and organic ligands are alternately coordinated and bonded.

The pore size of the porous coordination polymer is in the range of 0.6 to 1.0 nm, which is the region of micropores as defined by IUPAC, but is preferably in the range of 0.7 to 0.9 nm, and is 0. 9.9 nm is more preferable. The pore diameter (diameter) is a diameter value measured by a gas / vapor adsorption amount measuring device, and can be measured by, for example, 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 pore diameter.

1.1.1 Metal Ions Metal ions that can constitute porous coordination polymers include 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⁺ , 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 ⁺ , 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⁺ , Examples include As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ , Bi ⁺ . Of these, copper ions are particularly preferable.

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

The number of the functional groups capable of coordinating to the metal ion of the organic ligand is 1 to 5, preferably 1 to 5 per aromatic compound, an aliphatic compound, an alicyclic compound, a heteroaromatic compound, or a heterocyclic compound. 2 to 4, more preferably 2 to 3 are included. Functional groups that can be coordinated to such 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 , CH (RCN) ₂ , C (RCN) ₃ , NH ₂ , NHR, NR ₂ , and nitrogen atoms constituting the aromatic ring (in the formula, R indicates a C ₁ to C ₅ alkyl group or aryl group). .. The nitrogen atom constituting the aromatic ring means an intracellular nitrogen atom such as pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, thiazole, oxazole, phenanthroline, quinoline, isoquinoline, diazanaphthalene, purine, bipyridine, and terpyridine.

The aromatic compound means a monocyclic or polycyclic compound consisting of a 5- or 6-membered aromatic hydrocarbon ring, and specific examples thereof include benzene, naphthalene, 1,4-dihydronaphthalene, fluorene, anthracene, and phenanthrene. , Biphenyl, triphenyl, acenaphthalene, acenaphthalene, tetrahydronaphthalene, chromane, 2,3-dihydro-1,4-dioxanaphthalene, pyrene, indan, inden 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.

A 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, which is a polycyclic compound. 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, indol, quinoline, isoquinoline, benzo [b] thiophene and benzimidazole. Can be mentioned.

Examples of the heterocyclic compound include morpholine, pyrrolidine, piperidine, methylpiperazine, tetrahydrotofuran, and dioxane.

The aromatic compound, the aliphatic compound, the alicyclic compound, the heteroaromatic compound, and the heterocyclic compound have 1 to 5, preferably 1 to 3, and particularly 1 in addition to the functional group capable of coordinating with the metal ion. It may have up to two substituents. Such substituents include chlorine atom, fluorine atom, bromine atom, iodine atom, methoxy, ethoxy, trifluoromethyl, methyl, ethyl, propyl, butyl, cyano, nitro, methylenedioxy, acetylamino, carbamoyl and acetyl. , Holmil.

Specific examples of the 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-methylpiperidin, 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 , Gglycerol, 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- Hexadiol, 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, decandicarboxylic 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 acid, 1,3-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxalin-2,3-dicarboxylic acid, 6-Chloroquinoxalin-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinolin-2,8 -Dicarboxylic acid, diimidedicarboxylic 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, Perrylen-3,9-dicarboxylic acid, Perryrangecarboxylic acid, Pluriol 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, polytetratetra-250-dicarboxylic acid, 1,4-bis- (carboxymethyl)- Piperazin-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1- (4-carboxy) phenyl-3- (4-chloro) phenylpyrazolin-4,5-dicarboxylic acid, 1, 4,5,6,7,7-Hexachloro-5-norbornen-2,3-dicarboxylic acid, phenylindandicarboxylic 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-oxoimidazolin-4 , 5-Dicarboxylic acid, 2,2'-biquinolin-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-naphthalenedicarboxylic acid, 1,3-adamantan 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, (diphenylether) -4,4'-dicarboxylic acid, imidazole-4 , 5-Dicarboxylic acid, 4 (1H) -oxo-thiochromen-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolindicarboxylic acid, 4,5-imidazole dicarboxylic acid Acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontandicarboxylic 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-nonen-6,9-dicarboxylic acid, eicosendicarboxylic 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-methi Lucinoline-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-pyrazoldicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1, 7-Dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornan-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 2- Hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolintricarboxylic 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] Kinolin-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-dioxide perilo [1,12-BCD] thiophene-3,4,9,10-tetracarboxylic acid , Perrylen-3,4,9,10-tetracarboxylic acid Perrylen-1.12-sulfon-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-hexoxacyclooctadien-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, tetrahydrofuran tetracarboxylic acid, cyclopentane-1 , 2,3,4-tetracarboxylic acid and the like. Of these, 1,3,5-benzenetricarboxylic acid or an ester thereof is preferable.

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

Preferred organic ligands that can constitute the porous coordination polymer include benzene, naphthalene, anthracene, phenanthrene, fluorene, indan, inden, pyrene, 1,4-dihydronaphthalene, tetraline, biphenylene, triphenylene, acenaphtylene and acenaphthene. A compound in which two, three or four carboxyl groups are bonded to an aromatic ring such as (the ligand is a halogen atom such as F, Cl, Br, I, an acylamino group such as a nitro group, an amino group or an acetylamino group). , Cyano group, hydroxyl group, methylenedioxy, ethylenedioxy, methoxy, ethoxy and other linear or branched alkoxy groups with 1 to 4 carbon atoms, methyl, ethyl, propyl, tert-butyl, isobutyl and other linear or A branched alkyl group having 1 to 4 carbon atoms, SH, a trifluoromethyl group, a sulfonic acid group, a carbamoyl group, an alkylamino group such as methylamino, a substituent such as a dialkylamino group such as dimethylamino, 1, 2 or (May be 3 substituted), 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. , Thiazol, oxazole, quinoline, isoquinoline, naphthylidine and the like, a nitrogen-containing aromatic compound that can be coordinated with one or more intracyclical nitrogen atoms, oxygen atoms or sulfur atoms (one, two or three substituted with the above substituents). May be mentioned.) And the like. If the ligand is neutral, it has the counter anion needed 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, methanesulfonic acid ion, toluenesulfonic acid ion, benzenesulfonic acid ion, and excess. Examples include chlorate ion.

The porous coordination polymer according to the present invention has two-dimensional pores such as a sheet or three-dimensional pores containing a bidentate ligand in which a plurality of sheets are coordinated in the axial position as a component. Coordination polymers are included, but for example, porous coordination polymers having the following one-dimensional pores 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-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, [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, 1, such as [Zn ₄ (μ ₄ -O) ₂ (BTMB) ₂ ] (BTMB = 1,3,5-tris (3-carboxyphenyl) benzene) disclosed in International Publication No. 2015/129685, 1, 3,5-Tris (3-carboxyphenyl) benzene-based porous coordination polymers can also be used.

The porous coordination polymers that can be used in the present invention include, for example, the following documents and reviews (Angew. Chem. Int. Ed. 2004, 43, 2334-2375 .; Angelw. Chem. Int. Ed. 2008, 47, 2-14 .; Chem. Soc. Rev., 2008, 37, 191-214 .; PNAS, 2006, 103, 10186-10191 .; Chem. Rev., 2011, 111, 688-764.; Nature, 2003, 423, 705-714.), Patent Documents (International Publication No. 2015/129685), etc., but not limited to these, known porous coordination polymers or porous coordinations that can be manufactured in the future. Polymers can be widely used.

1.2 Composite of Porous Coordination Polymer and Polymer The porous coordination polymer forms a complex together with a polymer having a glass transition point (Tg) of 70 ° C. or lower (hereinafter, simply referred to as “polymer”). You may be doing it. Therefore, the present invention also includes a deodorant for daily odors, which 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 with 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 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. An organic cross-linking agent having two or more double bonds, an organic cross-linking agent having two or more isocyanate groups, formyl groups, anhydrous carboxylic acid residues, etc. when the functional group of the polymer is a hydroxyl group, and a functional group of the polymer In the case of an amino group, an organic cross-linking agent having two or more isocyanate groups, formyl groups, etc., and in the case of a functional group having a carboxyl group, an organic 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 an anhydrous carboxylic acid residue, an organic cross-linking agent having two or more hydroxyl groups, amino groups and the like can be mentioned as the cross-linking structure. When an organic cross-linking agent is used, the solvent used is one that does not react with the organic cross-linking agent or one that does not easily react with the organic cross-linking agent such that the organic cross-linking agent reacts with the polymer faster than the solvent.

As organic cross-linking agents having two or more isocyanate groups, aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimerate diisocyanate, and lysine diisocyanate; burette-type adducts of these polyisocyanates, isocyanurate rings. Additives; isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4- (or 2,6-) diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) Alicyclic diisocyanates such as cyclohexane, 1,4-cyclohexanediisocyanate, 1,3-cyclopentanediisocyanate, 1,2-cyclohexanediisocyanate; Bulet-type adducts of these diisosocyanates, isocyanurate ring adducts; Range isocyanate, Metaxylylene diisocyanate, Tetramethylxylylene diisocyanate, Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalenedi isocyanate, 1,4-naphthalenediocyanate, 4,4'-toluidin diisocyanate- , 4,4'-diphenyl ether isocyanate, (m- or p-) phenylenedi isocyanate, 4,4'-biphenylenedi isocyanate, 3,3'-dimethyl-4,4'-biphenylenedi isocyanate, bis (4-isosianatophenyl) ) Aromatic diisocyanate compounds such as sulfone, isopropylidenebis (4-phenylisocyanate); bullet-type adducts of these diisocyanate compounds, isocyanurate ring adducts; triphenylmethane-4,4', 4' 1 such as'-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane-2,2', 5,5'-tetraisocyanate, etc. Polyisocyanates having three or more isocyanate groups in the molecule; examples thereof include burette-type adducts and isocyanurate ring adducts of these polyisocyanates. In addition, a compound in which the above-mentioned isocyanate (NCO) is replaced with isothiocyanate (NCS) can be mentioned.

Examples of the monomers constituting the polymer include olefins such as ethylene, propylene and butylene, halogenated olefins such as tetrafluoroethylene, vinylidene fluoride, trifluoroethylene and vinyl chloride, diene such as butadiene and isoprene, acrylic acid and methacrylic acid. , Acrylate or methacrylate (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, 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. Aromatic ring-containing vinyl compounds such as methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate), styrene, vinyltoluene, α-methylstyrene; vinyl esters such as vinyl propionate and vinyl acetate. Classes; acrylonitrile, methacrylonitrile; (meth) acrylamide; glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene monoepoxide, N-glycidyl acrylamide, allyl glycidyl ether and other epoxy group-containing vinyl. Compounds; Aminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-di Acrylate (meth) acrylic Amino group-containing (meth) acrylates such as Ester, N, N-dibutylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate; N, Contains amino groups such as N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide. (Meta) 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 monoesterides 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, hydroxyl group-containing compounds and reaction products of acid anhydride; acid anhydride group-containing vinyl compounds such as maleic anhydride, itaconic anhydride, and hymic anhydride, Ester glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, octanediol, tricyclodecanedimethylol, cyclohexanedimethanol, hydrogenated Low molecular weight glycols such as bisphenol A, high molecular weight glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate glycol, polyhydric alcohols such as glycerin and monoester of (meth) acrylic acid; maleic acid, chloromalein. Examples include acids, fumaric acids and their acid anhydrides.

When the polymer is polyurethane, the above-mentioned monomer having 2 or more isocyanate groups may be reacted with the monomer having 2 or more hydroxyl groups, and in the case of polyester, the monomer having 2 or more carboxylic acid groups and 2 It can be 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 irradiation with ultraviolet rays.

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

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

A conductive agent and a lubricant can be further added to the complex. Examples of the conductive agent include carbon black, ketjen black, carbon nanofiber, acetylene black, channel black, lamp black, furnace black, graphite powder, fibrous carbon material, metal powder, metal fiber and the like.

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

1.3 Method for Producing 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 manufacturing method (manufacturing method described in the above-mentioned documents and the like). In addition, the above-mentioned pore diameter can be prepared by a conventional method. The composite of the porous coordination polymer and the polymer can be produced, for example, according to the description of International Publication No. 2015/01/2373.

In the deodorant of the present invention, for example, a porous coordination polymer or a composite thereof is powdered by a conventional method alone or using a suitable carrier, dissolved or suspended in a solvent, and kneaded under pressure. Alternatively, it can be produced by heating and kneading. Examples of the carrier for pulverization include activated carbon, zeolite, mesoporous silica, silica, and alumina. The average particle size of the powder can be, for example, in the range of 0.1 to 5000 μm, preferably in the range of 0.5 to 1000 μm. Examples of the solvent include toluene, xylene, ethyl acetate, methanol, ethanol, acetone and the like.

The deodorant of the present invention can also be filled in 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. The method for filling the spray container with the deodorant of the present invention is not particularly limited, and a known method can be adopted.

When the deodorant of the present invention is filled together with the propellant, the propellant is not particularly limited as long as it is normally 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 may contain other deodorant components and additives as long as the effects of the present invention are not impaired. Examples of other deodorant components include zeolite, activated carbon, silica gel, and cyclodextrin. Examples of the additive include a surfactant, a water absorbing agent, a penetrant, a dispersant and the like.

The content of the porous coordination polymer in the deodorant of the present invention includes the type of the porous coordination polymer, the blending or amount of other deodorant components and additives, the form of the deodorant of the present invention, and the living odor. Although it varies depending on the above, 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. If it is less than 0.1% by weight, sufficient deodorizing performance may not be obtained.

1.4 Living odor The deodorant of the present invention is excellent for instantaneously deodorizing the following living odors, for example.
(1) Nursing / nursing odor, hospital odor: urine odor, excretion odor (2) general life odor-1: garbage odor, changing room odor / rocker odor, fitting room odor, crowded odor (crowded train odor), air conditioner Odor, tatami odor, floor odor, kitchen odor, toilet odor, bathroom odor, shoe rack odor, drainage odor (3) General life odor-2: Body odor, sweat odor (4) General life odor-3: Tobacco odor, roasted meat Odor (5) Other living odors: compost odor, animal odor, pet manure odor, car interior odor

2. Antibacterial agent / antiviral agent of the present invention The present invention contains an antibacterial agent or an antivirus, which comprises a porous coordination polymer in which metal ions and organic ligands are alternately coordinated and bonded. Agents (hereinafter referred to as "antibacterial agents of the present invention") are included.

The meanings of "metal ion", "organic ligand", and "porous coordination polymer" are synonymous with the above, but the pore diameter of the porous coordination polymer is appropriate regardless of the diameter. It will be adjusted. The pore diameter 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 produced in the same manner as in the production method described in "1.3 Method for producing the deodorant of the present invention".

The bacteria and viruses that can be targeted by the antibacterial agent of the present invention are not particularly limited, and examples thereof include the following bacteria and viruses. The fungus also includes a fungus.

<Bacteria>
(1) Gram-negative anaerobic rod Eshericha coli, Shigella, Salmonella, Klebsiella, Proteus, Yersinia, Vibrio cholerae (V) .cholerae), Vibrio enteritis (Vparahaemolyticus), Yersinia (Haemophilus)
(2) Gram-negative aerobic rods 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 Bacillus, Clostridium
(7) Actinomycetes and related microorganisms Corynebacterium, Mycobacterium
(8) Mycoplasma Mycoplasma
(9) Spirochetes and spiral fungi Borrelia recurrentis, Lyme disease Borrelia (B.burgdoferi), Treponema pallidum, Campylobacter, Helicobacter
(10) Rickettsia Rickettsia
(11) Chlamydia Chlamydia

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

<Virus>
Infectious soft tumor virus, simple herpes virus, varicella / herpes zoster virus, rotavirus, human papilloma virus, poliovirus, coxsackie virus, rhinovirus, ruin virus, measles virus, influenza virus, epidemic under ear Adenitis virus, RS virus, hepatitis virus, HIV

3. Molded product of the present invention The present invention is characterized by containing the deodorant of the present invention or the antibacterial agent of the present invention (hereinafter, also referred to as “the formulation of the present invention”) (hereinafter, “the present invention”. "Molded product") is included.

3.1 Molded product of the present invention The molded product of the present invention is not particularly limited as long as it can be sealed with the deodorant of the present invention, and examples thereof include fibers, textile products, resin molded products, and filters.

The fiber may be any of synthetic fiber, regenerated fiber, and natural fiber.
Examples of the synthetic fiber include polyester, nylon, acrylic and acetate. Examples of the recycled fiber include rayon. Examples of natural fibers include cotton, linen, wool and silk. In addition to the raw cotton itself, the cotton includes caustic mercerized cotton, cotton treated with liquid ammonia, and the like. Further, the fiber may be a blended spinning of each fiber, or may be a primary processed product of each fiber, for example, a thread, a string, a rope, a woven fabric, a knitted fabric, a non-woven fabric, paper or the like.

The textile product refers to a product obtained by further processing the fiber, and is not particularly limited, and examples thereof include clothing such as outer garments, inner garments, and inner garments, bedding, interior goods, household goods, and car interiors. Specifically, for example, coats, jackets, trousers, skirts, shirts, knit shirts, blouses, nightwear, underwear, sweaters, supporters, socks, tights, stockings, hats, scarves, clothing linings, clothing cores, etc. Clothing such as batting, work clothes, uniforms, school uniforms; bedding such as duvets, duvet cotton, duvet covers, sheets, pillowcases; interiors such as sheets, mats, curtains, carpets; towels, handkerchiefs, towels , Potholders, diapers, sanitary goods, and other household goods; products such as automobile interiors such as seats, seat covers, and handle covers can be mentioned.
In addition, the textile products include those in the form of textile products used in the field of industrial materials such as wall cloths, ceiling cloths, and floor exteriors.

The resin molded products include polyethylene, polypropylene, acrylic resin, urethane resin, fluororesin, silicon resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyamide, polystyrene, polyester, aminoplast resin, glioxal resin, and ethylene urea. It refers to a molded product such as a plate-shaped product, a columnar product, or an extrusion-molded product made of a resin and a blended resin thereof. Specific examples of the resin molded product include films, sheets, and containers of these resins.
Molding into films, sheets, containers and the like can be performed by various inflation devices, presses, calendars, extrusion molding machines, spinning machines, blow molding machines, injection molding machines, vacuum forming machines and the like.

Examples of the filter include a deodorizing filter and an antibacterial filter used in an air purifier and the like.

3.2 Method for producing a molded product of the present invention The molded product of the present invention can be produced by containing the pharmaceutical product of the present invention in a conventional manner according to a desired molded product.
For example, when the pharmaceutical product of the present invention is adhered or impregnated into a fiber or a textile product, for example, a dipping method, a spraying method, or a coating method (including a method of applying using a brush, a sponge, or the like) can be used.

In order to prevent the pharmaceutical product of the present invention from falling off from the fiber or the textile product, it is preferable to use a binder resin to fix the zinc carbonate particles to the fiber or the textile product. The binder resin is not particularly limited as long as it is used in the art, but for example, various thermosetting resins such as urethane resin, silicon resin, acrylic resin, melamine resin, and ureaformal resin are used. The sex resin can be mentioned. The amount of the binder resin used may be such that the pharmaceutical product of the present invention can be adhered to the fiber or the textile product.

In the case of the dipping method, it can be produced by immersing the fiber or textile product to be treated in the treatment liquid containing the present invention preparation and, if necessary, the binder resin by a conventional method. The concentration of the pharmaceutical product of the present invention in the treatment liquid can be set to a concentration calculated from the drawing ratio of the treatment liquid and the required loading amount. Examples of the solvent constituting the treatment liquid include organic solvents such as alcohols such as toluene, xylene, ethyl acetate and ethanol.

The permeation time of the treatment liquid into the fiber or the textile product is sufficiently fast, and the immersion time and the bath temperature are not particularly limited. Usually, the soaking time is in the range of 0.1 to 300 seconds, and the bath temperature is in the range of 10 to 40 ° C. The drawing differs depending on the product to be processed, but an appropriate drawing method and drawing ratio can be adopted for each. Normally, it is better to squeeze with a mangle or the like so that the squeezing ratio is uniform.

The adhered or impregnated amount of the pharmaceutical product 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 with respect to 1 m ² of the dough. be.

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

When a binder resin is used, it is preferable to perform heat treatment after drying in order to fix the binder resin. The temperature and time of the heat treatment vary depending on the type of binder resin used and the like, but 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 set. It is usually in the range of 20 seconds to 1 hour.

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

The molded product of the present invention can also be produced by first applying a treatment liquid containing a binder resin (not including the pharmaceutical product of the present invention) to fibers or textile products, drying the product, and then spraying the pharmaceutical product of the present invention on the treatment liquid. be able to. The binder resin can be dissolved or dispersed by a conventional method, and the solvent of the treatment liquid in that case may include water in addition to the organic solvent. By using water, safety and convenience can be achieved.

Resin processed products other than fibers and textile products and molded products of the present invention such as filters can also be manufactured basically in the same manner as the above-mentioned manufacturing method for fibers or textile products.

In particular, in each of the following (1) to (3), the method for producing a molded product of the present invention, which comprises each step, is preferable.
(1) Porous coordination formed by alternating coordination bonds between metal ions and organic ligands The solid content weight ratio of the polymer and the binder resin is 1: 0.01 to 1:30 (porous coordination). A step of dissolving a mixture within the range of polymer: binder resin) in an organic solvent, a step of applying the mixture dissolved in an organic solvent to a breathable thin film material, and a step of drying the solvent and the like.
(2) A step of mixing a molten binder resin (eg, polyethylene resin) with a porous coordination polymer in which metal ions and organic ligands are alternately coordinated (note that the porous coordination is 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 (preferably in the range of porous coordination polymer: binder resin), and the mixture is applied to a breathable thin film material. The process and the process of sandwiching and high temperature crimping with a breathable thin film material.

(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 synonymous with the above. Is. Examples of the "breathable thin film material" include breathable textile products, non-woven fabrics, filters, and sheets. Further, the specific manufacturing conditions in the above-mentioned manufacturing method of the molded product of the present invention can be appropriately set according to a known technique or a well-known technique in the art.

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 diameter 0.9 nm) 2.11 g (3 bottles) of copper (II) nitrate trihydrate and 1,3,5-benzenetri (carboxylic acid) To 1.01 g (3 bottles) of methyl acid) was added 57.6 mL (3 bottles) of a 50 vol% aqueous ethanol solution, stirred for 10 minutes, and reacted at 140 ° C. for 60 minutes using a microwave. Ethanol was added to the solid recovered 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 pore diameter was measured by a high-precision gas / vapor adsorption amount 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) Cu-PCP having a pore diameter of 0.5 nm was obtained in the same manner as in Example 1.

[Reference Example 2] Preparation of Ni-PCP (Ni-MOF74, pore diameter 1.1 nm) N, N- in 3.63 g of nickel (II) nitrate hexahydrate and 0.72 g of 2,5-dihydroxyterephthalic acid. 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 recovered 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 having a pore diameter of 1.1 nm.

[Reference Example 3] Preparation of Cr-PCP (MIL-101 (Cr)) Add 50 mL of water to 2.97 g of chromium (III) chloride hexahydrate and 1.85 g of terephthalic acid, stir, and use an autoclave to stir 210. It reacted at ° C for 6 hours. After centrifugation, the supernatant was removed and vacuum dried. N, N-dimethylformamide was added, and after ultrasonic cleaning, the supernatant was removed. After ultrasonic cleaning with the addition of ethanol, 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, sample powder was placed therein, and cotton (about 0.0045 g) was rolled into a lid so that the sample powder did not come out (see FIG. 1).
Ammonia odor solution was placed in a 500 mL Erlenmeyer flask with a stopper, sealed, and placed in a drying chamber at 60 ° C. for 15 minutes for vaporization. Then, after taking out from the drying chamber and allowing to cool for 30 minutes, the detection tube was inserted into a flask and the ammonia concentration of the gas passing through the detection tube was measured to test the instantaneous deodorization property 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 mixture of silicon dioxide and zinc oxide used for deodorizing the four major odors (hydrogen sulfide, ammonia, trimethylamine, methyl mercaptan) and valerate, phenol, NOx and the like. (Made by Rasa Industries, 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 ammonia concentration and is excellent in instantaneous deodorizing property against ammonia odor. It is clear that there is.

[Test Example 2] Instant deodorant test (acetic acid odor)
As for the acetic acid odor, the instantaneous deodorizing 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 having a pore diameter of 0.9 nm (Example 1) can sufficiently reduce the acetic acid concentration and has excellent instantaneous deodorizing property against acetic acid odor. It is clear that there is. 1

[Test Example 3] Instant deodorant test (cigarette odor)
In a glass container (length 40 cm x width 25 cm x height 27 cm = 27,000 cm ³ (27 L)), cigarettes (Mevius (registered trademark) Superlite (tar 6 mg, nicotine 0.5 mg)) are burned, sealed and sealed. The one left in the sun was used as an odorous substance. 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 a lid was covered with cotton.

A rubber tube containing a sample powder attached to a syringe was inserted into a glass container 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 3 people based on the following evaluation criteria. The results are shown in Table 6.

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

<Sensory evaluation criteria>
0: Odorless, 1: Smell that can be finally perceived 2: Smell that can be understood what smell 3: Smell that can be easily perceived 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 diameter of 0.9 nm is superior in instantaneous deodorizing property to tobacco odor as compared with other deodorants. Is.

[Test Example 4] Instant deodorant test (excretion odor)
As for the excreted odor, the instantaneous deodorizing performance was tested in the same manner as in Test Example 1. The results are shown in Table 7. For the excretory odor, defecation of a 1-year-old baby was used.

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

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

[Test Example 5] Antibacterial test The molded product 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 bacterium: Staphylococcus aureus (2) Test method: A sterilized test material is injected with a suspension of the test bacterium to which a surfactant (Tween80) is added, and cultured in a closed container at 37 ° C. for 18 hours. The later viable cell count is measured. After inoculation, the antibacterial number is evaluated by the bacteriostatic activity value with respect to the unprocessed cloth number.
(3) Antibacterial activity value: (Mb-Ma)-(Mc-Mo) (Antibacterial activity value ≧ 2.2, pass)
Ma: Number of viable bacteria immediately after contact with the test bacterial solution of the standard cloth Mb: Number of viable cells immediately after incubating the standard cloth for 18 hours Mo: Number of viable bacteria immediately after inoculation with the test bacterial solution of the antibacterial deodorant processed cloth (molded product of the present invention) Mc : Viable cell count after 18-hour culture of antibacterial and deodorant cloth (4) Test effectiveness: Mb-Ma> 1.0

As a result, the results shown in Table 8 below were obtained, and the antibacterial activity value of the molded product of the present invention subjected to the antibacterial and deodorant treatment was 6.1, which was well 2.2 or more. It is clear that the molded product has antibacterial properties. Since Mb-Ma = 2.0, which exceeds 1.0, this test is valid.

The deodorant of the present invention is useful for imparting the deodorizing performance of daily odors to daily necessities. 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 a daily necessities because it has excellent deodorizing properties against daily odors and has an 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 bonded, and the pore diameter is in the range of 0.6 to 1.0 nm. A method for producing a molded product containing, and having a living odor deodorant property, an antibacterial property, or an antiviral property.
A step of applying a treatment liquid containing a binder resin in a solvent (excluding those containing the porous coordination polymer) to a breathable thin film material, and a thin film material to which the treatment liquid is applied. After drying, the step of spraying the porous coordination polymer or the composition containing the porous coordination polymer (however, excluding those containing a binder resin).
The method for producing a molded product, which comprises the above. The method for producing a molded product according to claim 1, wherein the metal ion is a copper ion. The method for producing a molded product according to claim 1 or 2, wherein the organic ligand is 1,3,5-benzenetricarboxylic acid or an ester thereof. The method for producing a molded product according to any one of claims 1 to 3, wherein the porous coordination polymer forms a complex together with the polymer having a glass transition point (Tg) of 70 ° C. or lower. The method for producing a molded product according to any one of claims 1 to 4, wherein the living odor is a tobacco odor, an animal odor, an excretory odor, a swill odor, or a sweat odor. The method for producing a molded product according to any one of claims 1 to 5, wherein the solvent of the treatment liquid is water. The method for producing a molded product according to any one of claims 1 to 5, wherein the thin film material is a textile product, a non-woven fabric, a filter, or a sheet. The method for producing a molded product according to any one of claims 1 to 6, wherein the molded product is a fiber, a textile product, a resin molded product, or a filter.

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