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. [4-1] The textile product according to the above [3], wherein the deodorizing properties are deodorizing properties for axillary odor, sweat odor, aging odor, excrement odor, menstrual odor, or vaginal discharge 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 for deodorizing the odor of a textile product. [8] The deodorant according to the above [7], wherein the odor of the textile product is an axillary odor. [8-1] The deodorant according to the above [7], wherein the odor of the textile product is an axillary odor, a sweat odor, an aging odor, an excrement odor, a menstrual odor, or a vaginal discharge odor. [9] A method for deodorizing an odor, which comprises 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. [11-1] The deodorizing method according to the above [9] or

[10] , wherein the odor is axillary odor, sweat odor, aging odor, excrement odor, menstrual blood odor, or vaginal discharge 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. Fig. 2 is a schematic diagram of the test equipment used in the deodorizing property test in Test Example 18.

[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 present invention, the amount of the metal organic framework attached to the textile product is, for example, ２ In the present invention, the amount of the metal organic framework attached to the textile product is, for example, 0.1 mg or more, 0.15 mg or more, 0.18 mg or more, 0.2 mg or more, preferably 0.24 mg or more, more preferably 0.3 mg or more, and even more preferably 0.36 mg or more per 100 cm of the textile product. ２ In the present invention, the amount of the metal organic framework attached to the textile product is, for example, 10 mg or less, 9 mg or less, or 8 mg or less, preferably 7.5 mg or less, 7.4 mg or less, more preferably 7.3 mg or less, 7.2 mg or less, and even more preferably 7.1 mg or less per 100 cm of the textile product. ２ The metal organic framework is 0.1 to 10 mg, 0.15 to 8 mg, 0.18 to 7.1 mg, preferably 0.24 to 7.1 mg, more preferably 0.3 to 7.1 gm, and even more preferably 0.36 to 7.1 mg per 1000 particles.

[0028] 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, and socks; outerwear such as jackets, suits, and jumpers; 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 include plant fibers such as cotton and hemp (linen, etc.); 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 recycled fibers such as rayon and cupra. In the present invention, examples of the material of the textile product include woven fabrics, knitted fabrics, nonwoven fabrics, and felt. 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 absorb body odors, and therefore 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; hygiene products such as masks; FEMTECH products, and the like).

[0029] 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 adsorption of odors, it is expected that the deodorizing function can be restored (deodorizing properties can be reactivated) by heat treatment (for example, ironing, putting in a washer / dryer, etc.). The temperature for the heat treatment is, for example, 80°C or higher, preferably 80°C to 210°C, more preferably 80°C to 180°C, even more preferably 80°C to 160°C, and still more preferably 80°C to 120°C. The time for the heat treatment varies depending on the heating method, but is, for example, 1 second or more, 2 seconds or more, 3 seconds or more, 4 seconds or more, 5 seconds or more, 6 seconds or more, 7 seconds or more, 8 seconds or more, 9 seconds or more, about 10 seconds to 10 minutes, about 20 seconds to 10 minutes, about 30 seconds to 10 minutes, about 40 seconds to 10 minutes, about 50 seconds to 10 minutes, about 1 minute to 10 minutes, preferably about 2 minutes to 10 minutes, more preferably about 3 minutes to 10 minutes, even more preferably about 4 minutes to 10 minutes, and still more preferably about 5 minutes to 10 minutes.

[0030] 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, axillary odor, sweat odor, aging odor, cancer odor, excrement odor, flatulence odor, body odor, menstrual odor, vaginal discharge odor, etc. A textile product having the metal organic framework of the present invention attached thereto has an excellent deodorizing effect, in particular, against axillary odor (representative components thereof: 3-hydroxy-3-methylhexanoic acid (sometimes abbreviated as HMHA herein), 3-methyl-3-sulfanylhexanol (sometimes abbreviated as 3M3SH herein), or 3-methyl-2-hexenoic acid (sometimes abbreviated as 3M2H herein)). Furthermore, a textile product having the metal organic framework of the present invention attached thereto has an excellent deodorizing effect, in particular, against sweat odor, aging odor, and excrement odor (representative components thereof: acetic acid, isovaleric acid, nonenal, and indole). A textile product having the metal organic framework of the present invention attached thereto has a deodorizing effect against excrement odors, and therefore can be used as textile products where excrement odors are a problem, such as diapers (e.g., cloth diapers, disposable diapers (e.g., diapers made of nonwoven fabric, etc.)), nursing care sheets, pet sheets, etc. Furthermore, a textile product having the metal organic framework of the present invention attached thereto has an excellent deodorizing effect, particularly against menstrual blood odor and vaginal discharge odor (the typical components of these odors are dimethyl disulfide, acetoin, isoamyl alcohol, diacetyl, and isovaleraldehyde). Because a textile product having the metal organic framework of the present invention attached thereto has a deodorizing effect against menstrual blood odor and vaginal discharge odor, it can be used as FEMTECH products (products that use technology to solve women's health issues) (e.g., underwear (e.g., sanitary shorts), sanitary napkins, and panty liners), which have been attracting attention in recent years.

[0031] 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.

[0032] 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 deodorant of the present invention onto the textile product. According to the odor deodorizing method of the present invention, spraying, immersing, or the like onto 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 be imparted with deodorizing properties.

[0033] 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.

[0034] 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.

[0035]

[0036]

[0037]

[0038] 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 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 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 chamber at room temperature or 60°C for 24 hours to evaporate the axillary odor substances (Figure 1, left panel). 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 odor substance" was not placed in the glass bottle (right diagram in Figure 1).

[0039] (Calculation of the amount of axillary odor substance 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 odor substance adsorption of the evaluation sample) was divided by the amount of sample powder weighed out to calculate the amount of axillary odor substance adsorption per 1 mg of sample powder (mg / mg sample powder). The results are shown in Table 2.

[0040]

[0041] As shown in Table 2, MIP-206-OH (Example 1-1) successfully adsorbed all three types of axillary odor substances regardless of temperature.

[0042] 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 odor substances. (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 odor substances (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 odor substances (Figure 1, left diagram). After the above-mentioned standing period was completed, 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 odor substance" was not placed in the glass bottle (right panel of Figure 1).

[0043] (Calculation of the amount of axillary odor substance 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 odor substance adsorption of the evaluation sample. The results are shown in Table 3. The amount of the above-mentioned axillary odor substance 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.

[0044]

[0045] 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 the axillary odor substances well.

[0046] 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 odor substances. After pretreatment for measurement, the sample was subjected to fractional analysis of HMHA, 3M2H, and 3M3SH by LC / MS / MS to confirm the degree of adsorption of each axillary odor substance. LC / MS / MS conditions were set according to the method used for each axillary odor substance, and a calibration curve corrected using the internal standard was created to calculate the concentration. The results are shown in Table 4.

[0047]

[0048] 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 odor substances HMHA, 3M2H, and 3M3SH.

[0049] 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). 200 μL of an aqueous solution containing axillary odor substances (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 allow the axillary odor substances to evaporate. 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 odor substances 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.

[0050] <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

[0051] The average scores of the six panelists are shown in Table 5. The average scores were rounded to two decimal places.

[0052]

[0053] 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.

[0054] 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 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 the mixture was homogenous. Only the left half of a T-shirt was immersed in the resulting solution, air-dried, and then 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).

[0055] (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 area (MOF-processed area (Example 5-1)) and the right armpit area (area treated with processing agent only (Comparative Example 5-1)) over the T-shirt with the man's arms raised, and evaluated the odor according to the following sensory evaluation criteria. The results are shown in Table 6.

[0056] <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

[0057] The average scores of the three panelists are shown in Table 6. The average scores were rounded to two decimal places.

[0058]

[0059] 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).

[0060] 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).

[0061] (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).

[0062]

[0063] 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).

[0064] [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.

[0065] (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).

[0066]

[0067] 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.

[0068] 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.

[0069]

[0070] 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.

[0071] 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 structure with that before immersion or with that of the CIF. The results are shown in Table 10.

[0072]

[0073] 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.

[0074] 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.

[0075]

[0076] 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.

[0077] 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.

[0078]

[0079] 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.

[0080] 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.

[0081]

[0082] 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.

[0083]

[0084] 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.

[0085] <Deodorizing Maintenance Effect (MOF Stability in a State Where Armpit Odor Substances Have Been Adsorbed)> [Test Example 13] Stability Test (Stability Against Adsorption of Armpit Odor Substances) 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 samples before adsorption of armpit odor substances or with the CIF.

[0086]

[0087] 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 with respect to the adsorption of axillary odor substances. 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 odor substances. Since textile products having the MOF of the present invention attached thereto are highly stable at high temperatures, heating them can restore (reactivate) their deodorizing function against odorous substances. Since textile products having the MOF of the present invention attached thereto are excellent in both stability against the adsorption of odorous substances and stability at high temperatures, they can be expected to be repeatedly usable due to the adsorption of odorous substances (deodorization) and the restoration of the deodorizing function by heating (reactivation of deodorizing properties).

[0088] Test Example 14: Test of deodorizing ability of textile products with various MOFs attached against sweat odor, aging odor, and excrement odor (detector tube method) In order to confirm the deodorizing ability of textile products with various MOFs attached against sweat odor, aging odor, and excrement odor, the following test was carried out using acetic acid, a component of sweat odor, aging odor, and excrement odor, as the odorous substance. (Production of textile products with various MOFs attached) MOFs (1.8 mg) shown in Table 15 were poured into 100 cm ２The fabrics (nylon / polyurethane synthetic fiber) were coated with the MOFs of Examples 14-1 to 14-6 using a binder (acrylic resin (trade name "Parazol GH-908", manufactured by Ohara Palladium Chemical Co., Ltd.)), to obtain fabrics (textile products with MOFs of the present invention coated therewith) coated with the MOFs of Examples 14-1 to 14-6. (Test Method) The obtained fabrics coated with the MOFs of Examples 14-1 to 14-6 were conditioned at 20°C and 65% RH for 24 hours or more, and then placed in a 5 L sampling bag. The sampling bag was filled with acetic acid, an odorant (initial concentration of 30 ppm as detected by a detector tube), and sealed with a heat seal. After 2 hours, the odorous gas concentration was measured with a detector tube, and the reduction rate of the odorous components was calculated. The results are shown in Table 15.

[0089]

[0090] From the results in Table 15, it can be seen that the fabrics to which the MOFs of Examples 14-1 to 14-6 were attached exhibited excellent deodorizing effects against acetic acid. Therefore, it can be expected that the textile products to which the MOFs of the present invention are attached have excellent deodorizing properties against sweat odor, aging odor, and excrement odor.

[0091] Test Example 15: Test of deodorizing ability of textile products with various MOFs attached against sweat odor, aging odor, and excrement odor (GC method) In order to confirm the deodorizing ability of textile products with various MOFs attached against sweat odor, aging odor, and excrement odor, the following test was carried out using isovaleric acid, nonenal, and indole, which are components of sweat odor, aging odor, and excrement odor, as odorous substances. (Production of textile products with various MOFs attached) MOFs (0.9 mg) shown in Table 16 were poured into a 50 cm ２The MOFs were attached to a fabric (nylon / polyurethane synthetic fiber) using a binder (acrylic resin (trade name "Parazol GH-908", manufactured by Ohara Palladium Chemical Co., Ltd.)) to obtain fabrics to which the MOFs of Examples 15-1 to 15-6 were attached (textile products to which the MOFs of the present invention were attached). (Test Method) The fabrics to which the MOFs of Examples 15-1 to 15-6 were attached were conditioned at 20°C and 65% RH for 24 hours or more, and then placed in 500 mL Erlenmeyer flasks. Three odorous substances (isovaleric acid (initial concentration detected by gas chromatography: 38 ppm), nonenal (initial concentration detected by gas chromatography: 14 ppm), and indole (initial concentration detected by gas chromatography: 33 ppm)) were each charged into the Erlenmeyer flasks and sealed with sealing film. After 2 hours, the odorous gas concentrations were measured by gas chromatography, and the reduction rates of the odorous components were calculated. The results are shown in Table 16.

[0092]

[0093] From the results in Table 16, it can be seen that the fabrics to which the MOFs of Examples 15-1 to 15-6 were attached exhibited excellent deodorizing effects against isovaleric acid, nonenal, and indole. Therefore, it can be expected that the textile products to which the MOFs of the present invention are attached have excellent deodorizing properties against sweat odor, aging odor, and excrement odor.

[0094] Test Example 16: Test of deodorizing ability of textile products with various MOFs attached against menstrual blood odor and vaginal discharge odor (GC method) In order to confirm the deodorizing ability of textile products with various MOFs attached against menstrual blood odor and vaginal discharge odor, the following test was carried out using dimethyl disulfide, acetoin, and isoamyl alcohol, which are components of menstrual blood odor and vaginal discharge odor, as odorous substances. (Production of textile products with various MOFs attached) MOFs (1.8 mg) shown in Table 17 were poured onto 100 cm ２The MOFs were attached to a fabric (nylon / polyurethane synthetic fiber) using a binder (acrylic resin (trade name "Parazol GH-908", manufactured by Ohara Palladium Chemical Co., Ltd.)) to obtain fabrics to which the MOFs of Examples 16-1 to 16-6 were attached (textile products to which the MOFs of the present invention were attached). (Test Method) The fabrics to which the MOFs of Examples 16-1 to 16-6 were attached were conditioned at 20°C and 65% RH for 24 hours or more, and then placed in 500 mL Erlenmeyer flasks. Three odorous substances (dimethyl disulfide (initial concentration detected by gas chromatography: 41 ppm), acetoin (initial concentration detected by gas chromatography: 44 ppm), and isoamyl alcohol (initial concentration detected by gas chromatography: 44 ppm)) were each charged into the Erlenmeyer flasks and sealed with sealing film. After 2 hours, the odorous gas concentration was measured by gas chromatography, and the reduction rate of the odorous components was calculated. The results are shown in Table 17.

[0095]

[0096] From the results in Table 17, it can be seen that the fabrics to which the MOFs of Examples 16-1 to 16-6 were attached exhibited deodorizing effects against dimethyl disulfide, acetoin, and isoamyl alcohol. Therefore, it can be expected that the textile products to which the MOFs of the present invention are attached have excellent deodorizing properties against menstrual odor and vaginal discharge odor.

[0097] Test Example 17: Test of deodorizing ability of textile products with various MOFs attached against vaginal discharge odor To confirm the deodorizing ability of textile products with various MOFs attached against vaginal discharge odor, the following test was carried out using diacetyl and isovaleraldehyde, which are components of vaginal discharge odor, as odorous substances. (Production of textile products with various MOFs attached) MOFs (0.9 mg) shown in Table 18 were poured into 50 cm ２The MOFs were attached to fabrics (nylon / polyurethane synthetic fibers) using a binder (acrylic resin (trade name "Parazol GH-908", manufactured by Ohara Palladium Chemical Co., Ltd.)) to obtain fabrics (textile products with MOFs of the present invention attached) with the MOFs of Examples 17-1 to 17-6 attached. (Test Method) The fabrics with the MOFs of Examples 17-1 to 17-6 attached were conditioned at 20°C and 65% RH for 24 hours or more, and then placed in 500 mL Erlenmeyer flasks. Two odorous substances (diacetyl (solution adjusted to 45 ppm) and isovaleraldehyde (solution adjusted to 23 ppm)) were each charged into the Erlenmeyer flasks and sealed with sealing film. After 2 hours, the odorous gas concentrations were measured by gas chromatography, and the reduction rates of the odorous components were calculated. The results are shown in Table 18.

[0098]

[0099] From the results in Table 18, it can be seen that the fabrics to which the MOFs of Examples 17-1 to 17-6 were attached exhibited deodorizing effects against diacetyl and isovaleraldehyde. Therefore, it can be expected that textile products to which the MOFs of the present invention are attached have excellent deodorizing properties against vaginal discharge odor.

[0100] Test Example 18 Evaluation of the Deodorizing Ability Against Armpit Odor and Washing Durability of Textile Products Adhered with MOF The following test was carried out to confirm that textile products adhering with MOF (MIP-206-OH) maintain their deodorizing ability against armpit odor (have washing durability) even after being washed. (Production of Textile Products Adhering with MOF (MIP-206-OH)) MIP-206-OH was applied to a 100 cm ２ The MOF (MIP-206-OH) was attached to a fabric (nylon / polyurethane synthetic fiber) in an amount of 7.1 mg per fiber using a binder (acrylic resin (trade name "Parazol GH-908", manufactured by Ohara Palladium Chemical Co., Ltd.)) to obtain a fabric to which the MOF (MIP-206-OH) of Example 18-1 was attached (a textile product to which the MOF of the present invention was attached).

[0101] (Production of a Sample (Example 18-2) in Which a Textile Product to Which MOF (MIP-206-OH) Has Been Adhered and Has Been Laundered) Laundry detergent (product name "FaFa Free and Ultra-Compact Liquid Detergent, Unscented", NS FaFa Japan Co., Ltd.) was diluted with water according to the dilution ratio specified in the product to obtain an aqueous laundry detergent solution. Separately, an alkaline detergent (sodium percarbonate) was diluted with water to 1 g / L to obtain an aqueous alkaline detergent solution. A fabric to which MOF (MIP-206-OH) had been attached, produced in the same manner as in Example 18-1 above, was immersed in the aqueous laundry detergent solution and then the aqueous alkaline detergent solution for 48 hours each, and then left to dry at room temperature to obtain the sample of Example 18-2. The 48 hours of immersion was set to correspond to 50 washes. (Control Sample (Comparative Example 18-1)) The same fabric as in Example 18-1, except that MOF (MIP-206-OH) was not attached, was used as a control sample (Comparative Example 18-1).

[0102] (Test Method) The following test was carried out using the test apparatus shown in the schematic diagram of Figure 2. A mixture of three axillary odor substances (HMHA, 3M2H, 3M3SH) was heated and vaporized to serve as the supply gas. Fabric with MOF attached (Example 18-1), fabric with MOF attached and then washed (Example 18-2), and fabric without MOF attached (Comparative Example 18-1 (control)) were each tested in a test chamber with an effective area of ​​12.56 cm. ２ The tubes were cut to a diameter of 40 mm (effective diameter) and placed so as to block the flow path within each holder. Aeration of the supply gas was then initiated at a constant flow rate through the tube shown in the schematic diagram of Figure 2. The holder outlet gas was sampled into an adsorption tube at 1 to 1.5 hours, 2 to 2.5 hours, 3 to 3.5 hours, and 4 to 4.5 hours after the start of aeration. The adsorption tubes that collected the axillary odor substances were heated while aerating inert gas, and the axillary odor substances were thermally desorbed, cooled, and concentrated, after which they were measured using a gas chromatograph-mass spectrometer. The lower limits of quantitation were 200 ng for HMHA, 50 ng for 3M2H, and 40 ng for 3M3SH. The results are shown in Table 19.

[0103]

[0104] The results in Table 19 show that the fabric to which MIP-206-OH was attached (Example 18-1) and the fabric to which it was washed (Example 18-2) exhibited superior deodorizing effects against axillary odor substances compared to the control (Comparative Example 18-1). The washed fabric (Example 18-2) exhibited almost the same deodorizing effect as the fabric before washing (Example 18-2), confirming that textile products to which the MOF (MIP-206-OH) of the present invention is attached maintain their deodorizing properties against odorous substances (have washing resistance).

[0105] [Test Example 19] Evaluation of reactivation by heating of various MOFs (3M2H, 3M3SH GC method) A vial (3.8 mL volume) containing 20 mg of each of the MOFs shown in Table 20 and a vial (0.6 mL volume) containing axillary odor substances (3M2H (20 μL), or 3M3SH (20 μL)) were placed in a 30 mL vial, sealed, and left to stand, and the axillary odor substances were adsorbed to the MOF at 60 ° C. for 24 hours. The MOF adsorbed with the axillary odor substances was weighed, placed in a measurement vial, and heated at 180 ° C. for 10 minutes. The adsorbed substances released were measured using a gas chromatograph-mass spectrometer. The results are shown in Table 20.

[0106]

[0107] The results in Table 20 show that heating the MOF to which the axillary odor substances have been adsorbed releases the axillary odor substances from the MOF. From these results, it can be expected that the textile products of the present invention to which the MOFs shown in Table 20 have been attached can reactivate their deodorizing properties against odorous substances by heating.

[0108] Test Example 20: Evaluation of reactivation of MOF-attached textile products by heating (HMHA sensory evaluation method) The following test was carried out to confirm the reactivation of MOF (MIP-206-OH)-attached textile products by heating. (Production of textile products with MOF (MIP-206-OH) attached) MIP-206-OH was applied to a 100 cm ２The MOF (MIP-206-OH) was attached to fabric (nylon / polyurethane synthetic fiber) in an amount of 7.1 mg per unit area using a binder (acrylic) resin (product name "Parazol GH-908", Ohara Palladium Chemical Co., Ltd.) to obtain a fabric (textile product with MOF of the present invention attached) of Example 20-1. (Control Sample (Comparative Example 20-1)) The same fabric as in Example 20-1, except that MOF (MIP-206-OH) was not attached, was used as a control sample (Comparative Example 20-1). (Test Method) A solution of axillary odor substance (HMHA) was placed in a glass vial (volume: 20 mL) and allowed to stand in a 100 mL container. With the screw cap of the glass vial loosened, a 3 cm x 7 cm piece of fabric (Example 20-1 or Comparative Example 20-1) was placed in the container, and the container was sealed. After allowing the fabric to stand and allow the axillary odor substances to be fully absorbed, the fabric was removed from the container and immersed in a laundry detergent solution (trade name "Attack Antibacterial EX Super Clear Gel" (Kao Corporation) diluted with water according to the product's specified dilution ratio) to remove axillary odor substances nonspecifically adsorbed to the fabric surface. The fabric was air-dried, and a trained panelist (one person) brought their nose close to the fabric to smell the released odor and evaluated it according to the following sensory evaluation criteria (evaluation based on 0 iron presses). Next, a household iron (set at low temperature (approximately 80-120°C)) was pressed against the fabric for 10 seconds, and after pressing, the panelist brought their nose close to the fabric to smell the released odor and evaluated it according to the following sensory evaluation criteria. This iron press and sensory evaluation were repeated seven times consecutively (evaluation based on 1 to 7 iron presses). The results are shown in Table 21.

[0109] The fabrics of Example 20-1 and Comparative Example 20-1 after the above iron pressing were each placed on a small plate containing HMHA bulk, and trained panelists (two people (Panelists A and B)) brought their noses close to the fabric to smell the permeating odor and evaluated it according to the following sensory evaluation criteria. The results are shown in Table 22.

[0110] In order to confirm the effect of another heating method (hot plate heating), a fabric (a textile product with an MOF of the present invention attached) to which the MOF (MIP-206-OH) of Example 20-1 was attached was separately prepared. A solution of the axillary odor substance (HMHA) was placed in a glass vial (20 mL capacity) and allowed to stand in a 100 mL container. With the screw cap of the glass vial loosened, a 3 cm x 7 cm fabric (Example 20-1) was placed in the container and the container was sealed. After leaving it to stand and allowing the axillary odor substance to be sufficiently adsorbed, the fabric was removed from the container and air-dried until the HMHA odor on the fabric surface disappeared, and the axillary odor substance nonspecifically adsorbed to the fabric surface was removed. Subsequently, the fabric was left to stand on a hot plate (set at 100 ° C) for 10 minutes. The dough of Example 20-1 after the hot plate heating was placed on a small plate containing HMHA bulk, and two trained panelists (Panelists A and B) brought their noses close to the dough to smell the permeating odor and evaluated it according to the following sensory evaluation criteria. The results are shown in Table 22.

[0111] <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

[0112]

[0113]

[0114] From the results in Table 21, the fabric to which MIP-206-OH was attached (Example 20-1) adsorbed more axillary odor substances (HMHA) than the fabric to which MOF was not attached (Comparative Example 20-1 (control)), and gradually released the axillary odor substances (HMHA) upon heating. From the results in Table 22, the fabric to which MIP-206-OH was attached after iron pressing (Example 20-1 (sample after iron pressing)) had a sensory score of 0 (odorless), and showed a superior adsorption effect of axillary odor substances compared to the control. Furthermore, the results in Table 22 show that the fabric to which MIP-206-OH was attached after heating on a hot plate (Example 20-1 (sample after hot plate heating)) also had a sensory score of 0 (odorless), similar to the fabric to which MIP-206-OH was attached after pressing with an iron (Example 20-1 (sample after pressing with an iron)), demonstrating an excellent adsorption effect for axillary odor substances. From these results, it can be expected that the textile products to which the MOF of the present invention is attached can be heated to restore (reactivate) their deodorizing function against odorous substances, and can be used repeatedly.

[0115] This application is based on international application PCT / JP2024 / 031079, the contents of which are incorporated in their entirety herein.

Claims

A textile product having a metal organic framework attached thereto, the metal organic framework being formed by a coordinate bond between a metal ion and an organic ligand, the metal ion is a zirconium ion, The organic ligand is represented by formula (I): [In the formula, X represents 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.] A textile product comprising at least a compound represented by the formula:

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. 　 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 properties are for deodorizing armpit odor, sweat odor, body odor, excrement odor, menstrual blood odor, or vaginal discharge odor. 　 A deodorant containing a metal organic framework formed by a coordinate bond between a metal ion and an organic ligand, the metal ion is a zirconium ion, The organic ligand is represented by formula (I): [In the formula, X represents 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.] A deodorant comprising at least a compound represented by the formula:

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, sweat odor, body odor, excrement odor, menstrual blood odor, or vaginal discharge odor. 　 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, the metal ion is a zirconium ion, The organic ligand is represented by formula (I): [In the formula, X represents 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.] A deodorizing method comprising at least a compound represented by the formula:

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. 　 The deodorizing method according to claim 9 or 10, wherein the odor is axillary odor, sweat odor, body odor, excrement odor, menstrual blood odor, or vaginal discharge odor.

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