Textile product imparted with deodorizing properties

Abstract

The purpose of the present invention is to provide a textile product to which a metal-organic framework has been adhered, the textile product having excellent deodorizing properties and excellent washing resistance (stability against sweat and laundry detergent).　A textile product to which is adhered a metal-organic framework structure, in which metal ions and organic ligands form coordinate bonds, wherein the metal ions are zirconium ions, and the organic ligands contain at least a compound represented by formula (I). [In the formula, X is as defined in the description.]

Description

Deodorizing textile products

[0001] The present invention relates to textile products to which deodorizing properties have been imparted, a deodorizer for textile products, and a method for eliminating odors.

[0002] Metal organic frameworks (MOFs) (sometimes referred to as "MOFs" in this specification) are also called porous coordination polymers (PCPs), and are substances having a porous structure formed by coordination bonds between metal ions and organic ligands (see Non-Patent Documents 1 to 8). Metal organic frameworks are known to have deodorizing effects (Patent Documents 1 to 4). However, there has been no research to date into the washing resistance (stability against sweat and laundry detergent) of textile products to which metal organic frameworks have been attached in order to impart deodorizing properties.

[0003] DE102016220085A1WO2016 / 207385WO2018 / 228760CN111514043A

[0004] SCIENCE, VOL 309, 23 SEPTEMBER 2005, pp. 2040-2042Microporous and Mesoporous Materials, 122 (2009), pp. 93-98Microporous and Mesoporous Materials, 157 (2012), pp. 50-55Inorg. Chem. 2019, 58, 14107-14111CrystEngComm, 2019, 21, pp. 1857-1861SCIENCE, VOL 336, 25 MAY 2012, pp. 1018-1023Matter, vol.4, January 6, 2021, pp. 182-194J. Am. 2014, 136, pp. 4369-4381

[0005] An object of the present invention is to provide a textile product to which a metal-organic framework is attached, which has excellent deodorizing properties and excellent washing resistance (stability against sweat and laundry detergent). Another object of the present invention is to provide a method for deodorizing an odor by previously attaching a metal-organic framework to a textile product or by attaching a metal-organic framework to an odorous textile product, and a deodorizer that can be used in the method.

[0006] As a result of intensive research to solve the above problems, the present inventors have found that a metal organic framework in which the metal ion is zirconium and the organic ligand includes at least a compound represented by formula (I) described below has excellent deodorizing effect and, when attached to a textile product, has excellent washing resistance (stability against sweat and laundry detergent). The present inventors have further advanced their research and have completed the present invention.

[0007] That is, the present invention is as follows: [1] A textile product having attached thereto a metal organic framework formed by a coordination bond between a metal ion and an organic ligand, wherein the metal ion is a zirconium ion, and the organic ligand is represented by formula (I):

[0008]

[0009] [wherein X is a hydroxy group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.] [2] The textile product according to the above [1], wherein in formula (I), X is a hydroxy group, a fluorine atom, a methoxy group, or a methyl group. [3] The textile product according to the above [1] or [2], to which deodorizing properties have been imparted. [4] The textile product according to the above [3], wherein the deodorizing properties are deodorizing properties for axillary odor. [5] A deodorant containing a metal organic framework formed by coordination bonding between a metal ion and an organic ligand, wherein the metal ion is a zirconium ion, and the organic ligand is represented by formula (I):

[0010]

[0011] [wherein X is a hydroxy group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.] [6] The deodorant according to the above [5], wherein in formula (I), X is a hydroxy group, a fluorine atom, a methoxy group, or a methyl group. [7] The deodorant according to the above [5] or [6], which is used for deodorizing the odor of textile products. [8] The deodorant according to the above [7], wherein the odor of the textile product is axillary odor. [9] A method for deodorizing an odor, comprising attaching to a textile product a metal-organic framework formed by a coordination bond between a metal ion and an organic ligand, wherein the metal ion is a zirconium ion, and the organic ligand is a compound represented by formula (I):

[0012]

[0013] [In the formula, X is a hydroxy group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.]

[10] The deodorizing method according to the above [9], wherein in formula (I), X is a hydroxy group, a fluorine atom, a methoxy group, or a methyl group.

[11] The deodorizing method according to the above [9] or

[10] , wherein the odor is axillary odor.

[0014] According to the present invention, it is possible to provide a textile product to which a metal-organic framework is attached, which has excellent deodorizing properties and excellent washing resistance (stability against sweat and laundry detergent). Furthermore, according to the present invention, it is possible to provide a method for deodorizing an odor by attaching a metal-organic framework to a textile product in advance or by attaching a metal-organic framework to a textile product that has an odor, and a deodorizer that can be used in the method.

[0015] FIG. 1 is a diagram illustrating the test method for the adsorptive deodorizing property test in Test Examples 1 and 2.

[0016] The metal organic framework used in the present invention is formed by a coordinate bond between a zirconium ion and an organic ligand containing at least a compound represented by the following formula (I): Formula (I):

[0017]

[0018] [wherein X is a hydroxy group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms] (hereinafter also referred to as compound (I)).

[0019] In compound (I), examples of the "halogen atom" include fluorine, chlorine, bromine and iodine, with fluorine being preferred.

[0020] In compound (I), the "alkoxy group having 1 to 6 carbon atoms" may be linear or branched, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, 1-ethylpropoxy, hexyloxy, isohexyloxy, 1,1-dimethylbutoxy, 2,2-dimethylbutoxy, 3,3-dimethylbutoxy, and 2-ethylbutoxy. In compound (I), the "alkoxy group having 1 to 6 carbon atoms" is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, still more preferably methoxy or ethoxy, and particularly preferably methoxy. In compound (I), the "alkoxy group having 1 to 4 carbon atoms" includes those having 1 to 4 carbon atoms from the above-mentioned "alkoxy groups having 1 to 6 carbon atoms." In compound (I), examples of the "alkoxy group having 1 to 3 carbon atoms" include those having 1 to 3 carbon atoms among the above-mentioned "alkoxy groups having 1 to 6 carbon atoms".

[0021] In compound (I), the "alkyl group having 1 to 6 carbon atoms" may be linear or branched, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 2-ethylbutyl. In compound (I), the "alkyl group having 1 to 6 carbon atoms" is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, further preferably methyl or ethyl, and particularly preferably methyl. In compound (I), the "alkyl group having 1 to 4 carbon atoms" includes those having 1 to 4 carbon atoms among the above-mentioned "alkyl groups having 1 to 6 carbon atoms." In compound (I), the "alkyl group having 1 to 3 carbon atoms" includes those having 1 to 3 carbon atoms among the above-mentioned "alkyl groups having 1 to 6 carbon atoms."

[0022] Compound (I) is preferably a compound in which X is a hydroxy group, a fluorine atom, a methoxy group, or a methyl group.

[0023] The organic ligand in the metal organic framework used in the present invention may be compound (I) alone, or may be a combination of compound (I) and an organic ligand other than compound (I) (for example, pyrazole-3,5-dicarboxylic acid (sometimes referred to as "PDA" in this specification) or furan-2,5-dicarboxylic acid (sometimes referred to as "FDA" in this specification).

[0024] Specific examples of the metal organic framework used in the present invention include the following (i) to (vi): (i) MIP-206-OH (CAS number: 2453250-08-1): a metal organic framework formed by a coordinate bond between a zirconium ion and a compound (I) in the formula (I) where X is a hydroxy group; (ii) MIP-206-F (CAS number: 2453252-63-4): a metal organic framework formed by a coordinate bond between a zirconium ion and a compound (I) in the formula (I) where X is a fluorine atom; and (iii) MIP-206-OCH ３(CAS number: 2453252-64-5): A metal organic framework formed by a coordinate bond between a zirconium ion and a compound (I) in which X is a methoxy group in the formula (I). (iv) MIP-206-CH ３ (CAS number: 2453252-65-6): A metal organic framework formed by a coordinate bond between a zirconium ion and a compound (I) in the formula (I) where X is a methyl group. (v) MIP-206-OH / PDA (CAS number: 2453252-61-2) A metal organic framework formed by a coordinate bond between a zirconium ion and a compound (I) in the formula (I) where X is a hydroxy group, and PDA (the molar ratio of the compound (I) to PDA (the compound (I):PDA) is 1:4). (vi) MIP-206-OH / FDA (CAS number: 2453258-26-7) A metal organic framework formed by a coordinate bond between a zirconium ion and a compound (I) in the formula (I) where X is a hydroxy group, and FDA (the molar ratio of the compound (I) to FDA (the compound (I):FDA) is 1:4).

[0025] Compound (I) can be produced, for example, by the method described in Matter, vol. 4, January 6, 2021, pp. 182-194, or a method analogous thereto.

[0026] The present invention relates to a textile product having the above-described metal-organic framework attached thereto (also referred to herein as a "textile product having the metal-organic framework of the present invention attached thereto"). In the present invention, the method for attaching the metal-organic framework to the textile product is not particularly limited, and can be performed by a known method. For example, a textile product having the metal-organic framework attached thereto can be obtained by immersing a textile product (e.g., a T-shirt) in a liquid obtained by dispersing a metal-organic framework in a solution (e.g., an aqueous solution) of a binder (acrylic resin (e.g., trade name "Parazol GH-908" manufactured by Ohara Palladium Chemical Co., Ltd.), silicone resin (e.g., trade name "Parasilicone PS-210" manufactured by Ohara Palladium Chemical Co., Ltd.), urethane resin (e.g., trade name "Parazol PN-14" manufactured by Ohara Palladium Chemical Co., Ltd.), vinyl acetate resin (e.g., trade name "Parazol 570" manufactured by Ohara Palladium Chemical Co., Ltd.), acrylic-silicone resin, or melamine resin) and drying the resulting liquid.

[0027] In the textile product of the present invention having the metal-organic framework attached thereto, examples of the "textile product" include clothing such as T-shirts, dress shirts, blouses, underwear, socks, etc.; outerwear such as jackets, suits, jumpers, etc.; clothing accessories such as hats, shoe and boot linings, bedding such as sheets, blankets, and futon fabrics, interior fabrics such as curtains, rugs, cushion covers, bed covers, sofa upholstery, and chair upholstery, daily necessities such as towels, handkerchiefs, dishcloths, and aprons, and sanitary goods such as gauze, bandages, and masks. In the present invention, the material of the textile product is not particularly limited as long as it is a material to which the metal-organic framework can be attached via a binder, and examples thereof include plant fibers such as cotton, hemp (linen, etc.), and the like; animal fibers such as silk, wool, and cashmere; synthetic fibers such as nylon, polyester, polyurethane, and acrylic; semi-synthetic fibers such as acetate and triacetate; and regenerated fibers such as rayon and cupra. The textile products to which the metal-organic framework of the present invention is attached have excellent deodorizing properties and excellent washing resistance (stability against sweat and laundry detergent), and are therefore particularly effective in textile products that come into contact with human skin and are prone to body odor and require frequent washing (for example, clothing such as T-shirts, dress shirts, blouses, underwear, socks, and the like; outerwear such as jackets, suits, and jumpers; clothing accessories such as hats; bedding such as sheets, blankets, and futon fabrics; daily necessities such as cushion covers, bed covers, towels, handkerchiefs, dishcloths, and aprons; and hygiene products such as masks).

[0028] Even if the deodorizing function of a textile product to which the metal-organic framework of the present invention is attached is reduced due to the absorption of odors, it is expected that the deodorizing function can be restored by high-temperature treatment (for example, ironing, etc.).

[0029] A textile product having the metal organic framework of the present invention attached thereto can be expected to have a deodorizing effect against, for example, armpit odor, sweat odor, aging odor, cancer odor, excrement odor, fart odor, body odor, etc. The textile product having the metal organic framework of the present invention attached thereto has an excellent deodorizing effect, in particular, against armpit odor (representative components of which are 3-hydroxy-3-methylhexanoic acid (sometimes abbreviated as HMHA in this specification), 3-methyl-3-sulfanylhexanol (sometimes abbreviated as 3M3SH in this specification), or 3-methyl-2-hexenoic acid (sometimes abbreviated as 3M2H in this specification)).

[0030] The present invention also relates to a deodorizer containing the above-described metal-organic framework (also referred to in this specification as "the deodorizer of the present invention"). The deodorizer of the present invention can be produced according to a known method using a carrier (e.g., a solvent) known in the field of deodorizers. The formulation of the deodorizer of the present invention is not particularly limited, and examples thereof include a spray and a liquid. The deodorizer of the present invention is expected to have a deodorizing effect on the odor of textile products (e.g., axillary odor) by spraying or immersing textile products in the deodorizer. The deodorizer of the present invention is expected to impart deodorizing properties to textile products by previously attaching the metal-organic framework to the textile products by spraying, immersing, or the like.

[0031] The present invention also relates to a method for deodorizing an odor (also referred to in this specification as the "odor deodorizing method of the present invention"), which comprises attaching the above-described metal-organic framework to a textile product. In the odor deodorizing method of the present invention, the step of attaching the metal-organic framework to a textile product can be carried out in accordance with the above-described method for producing a textile product to which the metal-organic framework of the present invention is attached. Furthermore, in the odor deodorizing method of the present invention, the step of attaching the metal-organic framework to a textile product can be carried out by spraying, immersing, or the like, the textile product with the deodorant of the present invention. According to the odor deodorizing method of the present invention, spraying, immersing, or the like, the textile product can be expected to have a deodorizing effect on the odor of the textile product (e.g., axillary odor). According to the odor deodorizing method of the present invention, by attaching the metal-organic framework to the textile product in advance by spraying, immersing, or the like, it can be expected that the textile product will have deodorizing properties.

[0032] The present invention will be explained in more detail below with reference to examples and test examples, but the present invention is not limited to these examples and test examples.

[0033] The samples used in the following Examples and Comparative Examples were produced by the method described in Table 1-1 or a method similar thereto. The organic ligands and metal ions in the MOFs used in the Examples and Comparative Examples are shown in Tables 1-2 and 1-3.

[0034]

[0035]

[0036]

[0037] Test Example 1: Adsorption Deodorizing Property Test (Axillary Odor) The following test was conducted to confirm the deodorizing properties of the various MOFs shown in Table 2 against axillary odor-causing substances. (Test Method) Evaluation Sample: Glass vials (3 mL volume) containing the sample powders shown in Table 2 (various MOFs, activated carbon (highly activated coconut shell activated carbon, Yusco), or zinc oxide (Fujifilm Wako Pure Chemical Industries)) in the amounts shown in Table 2, and glass vials (3 mL volume) containing axillary odor-causing substances (HMHA (50 μL), 3M2H (35 μL), or 3M3SH (50 μL)) were placed in a glass bottle (50 mL volume), sealed, and left to stand in a thermostatic device at room temperature or 60°C for 24 hours to evaporate the axillary odor-causing substances (Figure 1, left). After the above-mentioned standing time was completed, the glass vial containing the sample powder was removed from the glass bottle, capped, and left to cool to prepare an evaluation sample. Control (Blank): This control was prepared by conducting the same test as the evaluation sample, except that the "vial containing the axillary odorant" was not placed in the glass bottle (right diagram in Figure 1).

[0038] (Calculation of the amount of axillary odorant adsorption) The masses of the evaluation sample vial and the control vial were measured before and after the test to calculate the amount of mass increase. The value obtained by subtracting the mass increase of the control from the mass increase of the evaluation sample (the amount of axillary odorant adsorption of the evaluation sample) was divided by the amount of sample powder weighed out to calculate the amount of axillary odorant adsorption per mg of sample powder (mg / mg sample powder). The results are shown in Table 2.

[0039]

[0040] As shown in Table 2, MIP-206-OH (Example 1-1) successfully adsorbed all three types of axillary odorants regardless of temperature.

[0041] Test Example 2: Adsorption Deodorizing Property Test (Axillary Odor) The following test was conducted to confirm the deodorizing properties of the various MOFs shown in Table 3 against axillary odorants. (Test Method) Evaluation Sample: Glass vials (3 mL volume) containing 50 mg of each sample powder (MOF) shown in Table 3 and glass vials (3 mL volume) containing axillary odorants (HMHA (2 μL), 3M2H (50 mg), and 3M3SH (20 μL)) were placed in a glass bottle (50 mL volume), sealed, and left to stand on a hot plate at 32°C for 24 hours to vaporize the axillary odorants (Figure 1, left diagram). After the above-mentioned standing period was over, the glass vials containing the samples were removed from the glass bottles, capped, and allowed to cool to prepare evaluation samples. Control (Blank): This control was tested in the same manner as the evaluation sample, except that the "vial containing the axillary odorant" was not placed in the glass bottle (right diagram in Figure 1).

[0042] (Calculation of the amount of axillary odorant adsorption) The masses of the evaluation sample vial and the control vial were measured before and after the test to calculate the amount of mass increase. The value obtained by subtracting the mass increase of the control from the mass increase of the evaluation sample was taken as the amount of axillary odorant adsorption of the evaluation sample. The results are shown in Table 3. The amount of the above-mentioned axillary odorant added was set to an amount that would fill the sealed glass bottle with a saturated state upon vaporization based on the saturated vapor pressure of each substance.

[0043]

[0044] As shown in Table 3, MIP-206-OH (Example 2-1), MIP-206-F (Example 2-2), MIP-206-OCH ３ (Example 2-3), MIP-206-CH ３ The evaluation samples of (Example 2-4), MIP-206-OH / PDA (Example 2-5), and MIP-206-OH / FDA (Example 2-6) all adsorbed axillary odorants well.

[0045] Test Example 3: Adsorption Deodorizing Test (Axillary Odor) A mixed solvent of methanol and acetonitrile (1:1) containing an internal standard was added to the remainder of each evaluation sample (MOF) produced in Test Example 2 in an amount of 500 μL per 35 mg of MOF to extract axillary odorants. After pretreatment for measurement, the degree of adsorption of each axillary odorant was confirmed by fractional analysis of HMHA, 3M2H, and 3M3SH using LC / MS / MS. LC / MS / MS conditions were set according to the method for each axillary odorant, and a calibration curve corrected using the internal standard was created to calculate the concentration. The results are shown in Table 4.

[0046]

[0047] As shown in Table 4, MIP-206-OH (Example 3-1), MIP-206-F (Example 3-2), MIP-206-OCH ３ The MOFs of MIP-206-OH / PDA (Example 3-3), MIP-206-OH / PDA (Example 3-4), and MIP-206-OH / FDA (Example 3-5) all effectively adsorbed the axillary odorants HMHA, 3M2H, and 3M3SH.

[0048] Test Example 4: Deodorizing Test (Axillary Odor) The following test was conducted to confirm the deodorizing properties of various MOFs shown in Table 5 against the odor (axillary odor) of textile products (T-shirts). (Test Method) Evaluation Sample: 2 mg of the sample powder (MOF) shown in Table 5 and a piece of T-shirt (circular, 5 cm diameter) were placed in a plastic petri dish (outer diameter 90 × 15 mm, volume 60 mL), and 200 μL of an aqueous solution containing axillary odorants (an aqueous solution with a final HMHA concentration of 7.9 μg / mL, a final 3M2H concentration of 1.9 μg / mL, and a final 3M3SH concentration of 0.03 μg / mL) was added to the T-shirt piece, and the dish was sealed and left for 1 hour to evaporate the axillary odorants. Control: This control was tested in the same manner as the evaluation sample, except that the sample powder (MOF) was not placed in the petri dish and no axillary odorants were added. Blank: A blank was prepared in the same manner as the evaluation sample, except that no sample powder (MOF) was added to the dish. (Sensory evaluation) After leaving the dish for one hour, the lids of the dishes were slightly opened, and the odors were smelled by six trained panelists, who evaluated the odors according to the following sensory evaluation criteria. The results are shown in Table 5.

[0049] <Sensory evaluation criteria> Six-level odor intensity rating system: 0: No odor 1: Barely detectable odor 2: Weak odor that is easy to identify 3: Easily detectable odor 4: Strong odor 5: Overpowering odor

[0050] The average scores of the six panelists are shown in Table 5. The average scores were rounded to two decimal places.

[0051]

[0052] As shown in Table 5, MIP-206-OH (Example 4-1) exhibited a deodorizing effect even on weak odors that could not be easily detected.

[0053] Test Example 5: Deodorizing Property Test (Axillary Odor) The following test was conducted to confirm the deodorizing property of a textile product (T-shirt) to which MIP-206-OH had been attached. (Production of a T-Shirt to which MIP-206-OH had been attached) A 50% binder reagent (trade name "Parazol GH-908", manufactured by Ohara Palladium Chemical Co., Ltd.) was used as a processing agent for attaching MIP-206-OH to the T-shirt. 8 mg of the 50% binder reagent (equivalent to 4 mg of the processing agent), 200 mL of water, and 40 mg of sample powder MIP-206-OH were placed in a 500 mL beaker and stirred with a stirrer for several tens of seconds until homogenous. Only the left half of a T-shirt was immersed in the resulting solution, air-dried, and spread. Subsequently, 8 mg of a 50% binder reagent (equivalent to 4 mg of a processing agent) and 200 mL of water were placed in another 500 mL beaker, and the mixture was stirred using a stirrer for several tens of seconds until homogeneous. Only the right half of the T-shirt was immersed in the resulting solution, air-dried, and spread. After the excess that could not be spread was rinsed in a washing machine, the T-shirt was air-dried again, producing a T-shirt with MIP-206-OH attached to the left half and no MIP-206-OH attached to the right half (hereinafter referred to as a MOF-processed T-shirt).

[0054] (Test Method) After a day's work, a man (20 years old) with armpit odor changed into a MOF-processed T-shirt at 4:00 PM. Immediately after changing, trained panelists (3 people) sniffed the left armpit (MOF-processed portion (Example 5-1)) and the right armpit (portion treated with processing agent only (Comparative Example 5-1)) over the T-shirt of the man with his arms raised, and evaluated the odor according to the following sensory evaluation criteria. The results are shown in Table 6.

[0055] <Sensory evaluation criteria> Six-level odor intensity rating system: 0: No odor 1: Barely detectable odor 2: Weak odor that is easy to identify 3: Easily detectable odor 4: Strong odor 5: Overpowering odor

[0056] The average scores of the three panelists are shown in Table 6. The average scores were rounded to two decimal places.

[0057]

[0058] As shown in Table 6, the left half of the T-shirt to which MIP-206-OH was attached as a MOF (Example 5-1) significantly suppressed the odor of the T-shirt immediately after wearing, compared to the right half of the T-shirt to which MIP-206-OH was not attached (Comparative Example 5-1).

[0059] Test Example 6: Deodorizing property test (axillary odor) The following test was carried out to confirm the deodorizing property of a textile product (T-shirt) to which MIP-206-OH had been attached. (Production of T-shirt to which MIP-206-OH had been attached) Using the same method as in Test Example 5, a T-shirt was produced in which MIP-206-OH had been attached to the left half and no MIP-206-OH had been attached to the right half (hereinafter referred to as MOF-processed T-shirt).

[0060] (Test Method) After a day's work, a man (20 years old) with armpit odor changed into a MOF-processed T-shirt at 4:00 PM and went to work at his part-time job. After returning home, after 10:00 PM (wearing time: 6 hours), four panelists, including the man himself and three trained panelists, sniffed the left armpit area (MOF-processed area (Example 6-1)) and the right armpit area (area treated with processing agent only (Comparative Example 6-1)) over the man's T-shirt with his arms raised, and evaluated the odor according to the same sensory evaluation criteria as in Test Example 5. As a reference example, a man with his arms raised after removing his T-shirt was also sniffed according to the same sensory evaluation criteria as in Test Example 5. The results are shown in Table 7. The judgment and processing methods were the same as those in Test Example 5, except that the sensory test results were the average values ​​of the sensory evaluations of four people, including the subject and three panelists (the average values ​​were rounded to three decimal places and displayed to two decimal places).

[0061]

[0062] As shown in Table 7, the left half of the T-shirt to which MIP-206-OH was attached as a MOF (Example 6-1) significantly suppressed the odor of the T-shirt after being worn for a long period of time (6 hours) compared to the right half of the T-shirt to which MIP-206-OH was not attached (Comparative Example 6-1).

[0063] [Test Example 7] Deodorizing Property Test (Body Odor) The following test was carried out to confirm the deodorizing property of a textile product (T-shirt) to which MIP-206-OH had been attached. (Production of T-Shirt to which MIP-206-OH had been attached) A T-shirt to which MIP-206-OH had been attached (hereinafter referred to as a MOF-processed T-shirt) was produced in the same manner as in Test Example 5, except that MIP-206-OH was attached to the entire T-shirt.

[0064] (Test Method) A man (44 years old) with sweat odor and body odor wore either a 100% cotton T-shirt (without MOF processing) or a MOF-processed T-shirt as underwear to bed on two separate days (wearing time: 12 hours). He also went out wearing the MOF-processed T-shirt for a day (wearing time: 14 hours). Immediately after putting on each T-shirt and at the end of the wearing time, four people, including the man himself and three trained panelists, sniffed the T-shirt over the man's armpits and evaluated it according to the same sensory evaluation criteria as in Test Example 5. The results are shown in Table 8. The evaluation and processing methods were the same as in Test Example 5, except that the sensory test results were the average of the sensory evaluations of the man himself and the three panelists (the average was rounded to two decimal places).

[0065]

[0066] As shown in Table 8, the MOF-processed T-shirts (Examples 7-1 and 7-2) using MIP-206-OH as the MOF significantly suppressed odor during wear, compared with the 100% cotton T-shirt (Comparative Example 7-1) to which MIP-206-OH was not attached.

[0067] Test Example 8: Stability Test (Stability of MOFs in Water) The following test was conducted to confirm the stability of various MOFs shown in Table 9 in water. 100 mg of the sample powder (MOF) shown in Table 9 was placed in a glass vial (20 mL capacity), and 10 mL of water was added. The sample was immersed and allowed to stand at room temperature. For four samples treated in the same manner, the supernatant was discarded 1, 7, 14, or 28 days after immersion, and the MOFs were vacuum-dried at room temperature. The structures of the resulting MOFs were confirmed by PXRD (Powder X-ray Diffraction) (PXRD measurement device: MiniFlex 600 (trade name), Rigaku Corporation). PXRD analysis was performed at room temperature under atmospheric pressure, using Cu—Ka as the X-ray source. In the following test examples, PXRD analysis was performed under the same conditions as described above. The presence or absence of structural changes after immersion was evaluated by comparing with the structure before immersion or with the CIF (Crystalographic Information File, crystal analysis data published in a paper). The results are shown in Table 9.

[0068]

[0069] As shown in Table 9, MIP-206-OH (Example 8-1) showed no structural change in water and was stable. MIP-206 (Comparative Example 8-3) showed the possibility of becoming unstable in water.

[0070] Test Example 9: Stability Test (Stability of MOFs Against Sweat) The following test was conducted to confirm the sweat stability of the various MOFs shown in Table 10. 250 mg of sample powder (MOF) listed in Table 10 was placed in a glass vial (50 mL capacity), and 25 mL of artificial sweat (a 10-fold dilution of PBS buffer (phosphate-buffered saline)) was added and the sample was immersed and left at room temperature. For two samples that had been treated in the same way, the supernatant was discarded 6 and 12 hours after immersion, and the structure of the MOF that had been vacuum-dried at room temperature was confirmed by PXRD. The presence or absence of structural changes after immersion was evaluated by comparing the sample with the sample before immersion or with the CIF. The results are shown in Table 10.

[0071]

[0072] As shown in Table 10, it was confirmed that MIP-206-OH (Example 9-1) did not undergo any structural change in response to sweat and was stable.

[0073] Test Example 10: Stability Test (Stability of MOF (single) in Laundry Detergent, etc.) The following test was conducted to confirm the stability of the various MOFs shown in Table 11 in laundry detergent, etc. (Stability in Laundry Detergent) The laundry detergent used was Attack Antibacterial EX Super Clear Gel (Kao, hereinafter referred to as Attack), which conforms to the ingredients of Standard Detergent 2 and Standard Detergent 6 described in JIS L1930:2014, Home Laundry Test Methods for Textile Products, and was diluted with water according to the test method. 250 mg of the sample powder (MOF) listed in Table 11 was placed in a glass vial (50 mL capacity), and 25 mL of diluted laundry detergent (Standard Detergent 2 or Attack) was added, followed by immersion and leaving at room temperature. For two samples treated in the same manner, the supernatant was discarded 1 or 48 hours after immersion, and the structure of the MOF vacuum-dried at room temperature was confirmed by PXRD. The presence or absence of structural changes after immersion was evaluated by comparing with the sample before immersion or with the CIF. The results are shown in Table 11. The evaluation after 48 hours of immersion was set as a stability test for 50 washes. (Stability against alkaline detergent) The test was conducted in the same manner as the "Stability against laundry detergent" above, except that sodium percarbonate (diluted to 0.89 g / L with water), an alkaline detergent, was used instead of laundry detergent, and the evaluation was conducted only after 1 hour of immersion. The results are shown in Table 11.

[0074]

[0075] As shown in Table 11, MIP-206 (Comparative Example 10-3) was shown to be unstable in all of the evaluated detergents. IR-MOF-74-II (Comparative Example 10-2) was confirmed to be unstable in the samples evaluated 1 hour after immersion in Standard Detergent 2 and Attack. MIP-206-OH (Example 10-1) did not undergo any structural change in any of the evaluated detergents and for any immersion time, confirming its stability.

[0076] Test Example 11: Stability Test (Stability of MOFs in Laundry Detergent) The following test was conducted to confirm the stability of the various MOFs shown in Table 12 in laundry detergent. The laundry detergent used was Attack Antibacterial EX Super Clear Gel (Kao, hereinafter referred to as Attack), which conforms to the ingredients of Standard Detergent 6 described in JIS L1930:2014, Home Laundry Test Methods for Textile Products, and was diluted with water according to the test method. 250 mg of the sample powder (MOF) listed in Table 12 was placed in a glass vial (50 mL capacity), and 25 mL of diluted laundry detergent (Attack) was added. The sample was immersed and allowed to stand at room temperature for 48 hours. The supernatant was then discarded, and the structure of the MOF, which had been vacuum-dried at room temperature, was confirmed by PXRD. The presence or absence of structural changes after immersion was evaluated by comparing it with that before immersion or with CIF. The results are shown in Table 12. The evaluation after 48 hours of immersion was set as a stability test for 50 washes.

[0077]

[0078] As shown in Table 12, MIP-206-OH (Example 11-1), MIP-206-F (Example 11-2), MIP-206-OCH ３ (Example 11-3), MIP-206-CH ３ (Example 11-4), MIP-206-OH / PDA (Example 11-5), and MIP-206-OH / FDA (Example 11-6) showed no structural change when used with the evaluated detergents and were stable. MOF-808 (Comparative Example 11-2) and MIP-206 (Comparative Example 11-1) showed structural change when used with the evaluated detergents, indicating the possibility of instability.

[0079] Test Example 12: Stability test (stability against laundry detergent) Sample powders (MOF-74(Mg), MIP-206, MIP-206-OH, MIP-206-F, MIP-206-OCH) were placed in glass vials (50 mL capacity). ３ , MIP-206-CH ３, MIP-206-OH / PDA, MIP-206-OH / FDA, or MOF-808) were placed in a container. 25 mL of diluted laundry detergent was added, and the container was left at room temperature for 48 hours. After immersion, the filtrate (A: water-soluble fraction) was collected by filter filtration, and the solid on the filter was recovered and immersed in 25 mL of methanol for 1 hour. After immersion, the filtrate (B: organic solvent-soluble fraction) was collected by filter filtration and analyzed by HPLC to confirm the presence or absence of decomposition products of the deodorant of the present invention. 250 mg of untreated sample powder was immersed in 25 mL of methanol for 1 hour, and the filtrate (C) was used as a control, obtained by washing the existing decomposition products in the sample powder with methanol. HPLC conditions were set according to the characteristics of each decomposition product, and a calibration curve was created for quantification. The evaluation of the decomposition products (decomposition rate) was calculated according to the following formula. Note that negative values ​​were considered to be 0% decomposition rate (no decomposition). The results are shown in Table 13.

[0080]

[0081] The laundry detergent used was Attack Antibacterial EX Super Clear Gel (Kao, hereinafter referred to as Attack), which conforms to the ingredients of standard detergent 6 described in JIS L1930:2014, Home Laundry Test Methods for Textile Products, and was diluted with water in accordance with the test method.

[0082]

[0083] As shown in Table 13, MIP-206-OH (Example 12-1), MIP-206-OCH ３ (Example 12-3), MIP-206-CH ３ (Example 12-4) did not produce decomposition products for the evaluated detergents and times examined, and was stable. MIP-206-F (Example 12-2), MIP-206-OH / PDA (Example 12-5), and MIP-206-OH / FDA (Example 12-6) produced decomposition products for the evaluated detergents examined, but the degree was very small, at 1% or less after 50 washes, and they were stable. MOF-74(Mg) (Comparative Example 12-1) and Zn ２ (dobpdc) (Comparative Example 12-6) produced decomposition products in an amount far exceeding 1% relative to the evaluated detergent, indicating the possibility of instability.

[0084] <Deodorizing Maintenance Effect (MOF Stability in a State Where Armpit Odor Substances Have Been Adsorbed)> [Test Example 13] Stability Test (Stability Against Armpit Odor Substance Adsorption) The samples produced in Test Examples 1 and 2 were examined by PXRD to determine whether or not there was any structural variation, and the results are shown in Table 14. The results were evaluated for the presence or absence of deterioration in comparison with the results before immersion or with CIF.

[0085]

[0086] As shown in Table 14, MIP-206 adsorbed with 3M2H (the sample adsorbed with 3M2H in Comparative Example 13-3), and MOF-808 adsorbed with a mixture of HMHA, 3M2H, and 3M3SH (Comparative Example 13-5) showed structural changes, indicating the possibility that they were unstable to the adsorption of axillary odorants. The MOF samples of Examples 13-1 to 13-7 did not undergo structural changes regardless of the temperature during adsorption, and it was confirmed that they were stable even when adsorbing axillary odorants. The deodorizing ability can be restored by reactivating the samples to desorb axillary odorants, and they can be used repeatedly.

Claims

1. A textile product having attached thereto a metal-organic framework formed by a coordinate bond between a metal ion and an organic ligand, wherein the metal ion is a zirconium ion, and the organic ligand is represented by the formula (I): [wherein X is a hydroxy group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms].

2. The textile product according to claim 1, wherein in formula (I), X is a hydroxy group, a fluorine atom, a methoxy group, or a methyl group.

3. The textile product according to claim 1 or 2, which has been given deodorizing properties.

4. The textile product according to claim 3, wherein the deodorizing property is a deodorizing property for armpit odor.

5. A deodorant containing a metal organic framework formed by a coordinate bond between a metal ion and an organic ligand, wherein the metal ion is a zirconium ion, and the organic ligand is represented by formula (I): [wherein X is a hydroxy group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms].

6. The deodorant according to claim 5, wherein in formula (I), X is a hydroxy group, a fluorine atom, a methoxy group, or a methyl group.

7. The deodorizer according to claim 5 or 6, which is used to eliminate odors from textile products.

8. The deodorant according to claim 7, wherein the odor of the textile product is axillary odor.

9. A method for deodorizing an odor, comprising attaching to a textile product a metal-organic framework formed by a coordination bond between a metal ion and an organic ligand, wherein the metal ion is a zirconium ion, and the organic ligand is represented by formula (I): [wherein X is a hydroxy group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms].

10. The deodorizing method according to claim 9, wherein in formula (I), X is a hydroxy group, a fluorine atom, a methoxy group, or a methyl group.

11. The deodorizing method according to claim 9 or 10, wherein the odor is axillary odor.

Images