Zirconium phosphate particles, a basic gas deodorizer using the same, and a method for manufacturing the same

Abstract

Zirconium phosphate particles obtained by contacting α-zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then further contacting them with an acidic liquid with a pH of 6 or lower, or zirconium phosphate particles having an ammonia gas reduction rate of 50% or more in a test bag containing said zirconium phosphate particles after placing 10 mg of zirconium phosphate particles and 3 L of air containing 1000 ppm of ammonia gas into a test bag at room temperature and pressure and leaving it for 10 minutes.

Description

Technology Field

[0001] The present invention relates to zirconium phosphate particles, and a finely shaped basic gas deodorizer using the same, a deodorizer for textiles, a composition for deodorizing processing, a deodorizing resin composition, and a deodorizing fiber, and belongs to the fields of adsorbent technology, deodorizer technology, and resin and fiber technology. Background Technology

[0002] In recent years, amidst the demand for safer and more pleasant living environments, deodorizing products such as deodorizing sheets, deodorizing curtains, and deodorizing filters designed to adsorb and eliminate harmful or odorous gases, as well as clothing and bedding equipped with deodorizing functions against sweat odor, elderly odor, fatigue odor, etc., have been released.

[0003] Representative adsorbent and deodorizing gases include acidic gases such as acetic acid, basic gases such as ammonia, sulfur gases such as methyl mercaptan, aldehyde gases such as formaldehyde, and ketone gases such as acetone, and deodorizing agents or deodorizing products suitable for each of these gases are being developed. Recently, basic gas adsorbents or basic gas deodorizing products capable of adsorbing basic gases such as ammonia, which are the causative substances of sweat odor and fatigue odor, have been developed. For example, inorganic solid acids such as zirconium phosphate are used as basic gas adsorbents, and deodorizing products are being developed by supporting or kneading this into fibers.

[0004] For example, the development of clothing using deodorizing fibers is being considered to eliminate sweat odor or fatigue odor; however, for this purpose, it is required to deodorize basic gases such as ammonia, which are the causative substances, as quickly as possible.

[0005] Japanese Patent Publication No. 3896327 discloses an ammonia gas adsorption filter in which 0.5 to 4 parts by weight of α-type zirconium phosphate is supported per 1 part by weight of fibrillated fiber, and the propylene glycol monomethyl ether acetate decomposition rate is less than 4%.

[0006] In Japanese Patent Publication No. 2018-178313, as a particle diameter, the median diameter is 0.2 to 0.7 μm, and the maximum particle diameter is 5.0 μm or less, D 10 A deodorizing agent for textiles containing zirconium α-phosphate with a diameter of 0.1 μm or more is disclosed. The problem to be solved

[0007] However, in the filter for adsorbing ammonia gas disclosed in Japanese Patent Publication No. 3896327, a flat-plate adsorption filter is manufactured by mixing 2.34 parts by weight of α-type zirconium phosphate with an average particle size of 0.9 μm with 1.0 part by weight of a fibril compound of aramid fiber, and in order to achieve sufficient high-speed deodorization performance, it was necessary to use a large amount of α-type zirconium phosphate with respect to the fiber. Furthermore, it was not practical to apply this technology to deodorizing fibers or deodorizing clothing.

[0008] In addition, the deodorizing fiber described in Japanese Patent Publication No. 2018-178313 improves spinnability and deodorizing properties by controlling the particle diameter of the deodorizing agent mixed into the fiber to a value below a certain value, but there is no description or suggestion whatsoever regarding the problem of high-speed deodorizing properties and the solution thereof.

[0009] According to one embodiment of the present invention, the objective is to provide zirconium phosphate particles having high deodorizing performance against basic gases such as ammonia and trimethylamine, and particularly excellent deodorizing speed of ammonia, a deodorizing agent using the same, a composition for deodorizing processing, a deodorizing resin composition, and a deodorizing fiber, and a method for manufacturing the same. means of solving the problem

[0010] The present invention includes the following [1] to

[21] .

[0011] [1] Zirconium phosphate particles obtained by contacting α-zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then further contacting them with an acidic liquid with a pH of 6 or lower.

[0012] [2] Zirconium phosphate particles described in [1], wherein the above basic liquid contains alkali metals and / or alkaline earth metals.

[0013] [3] Zirconium phosphate particles, 10 mg of which is ammonia gas reduction rate (X; unit %) in the test bag containing the zirconium phosphate particles, which is 50% or more, as shown by the following formula (1), after placing 3 L of air containing 1000 ppm of ammonia gas into the test bag at room temperature and pressure and leaving it for 10 minutes.

[0014] X={(A0-A1) / A0)}×100 (1)

[0015] [In Equation (1), A0 represents the ammonia gas concentration of a test bag without zirconium phosphate particles, and A1 represents the ammonia gas concentration of a test bag with zirconium phosphate particles.]

[0016] [4] Zirconium phosphate particles described in any one of [1] to [3], with a median diameter of 0.1 to 10 μm of primary particles.

[0017] [5] Zirconium phosphate particles described in any one of [1] to [4], having a drying loss fraction (Y; unit weight%) represented by the following formula (2) after heating at 150°C for 2 hours, of 5.0 weight% or less.

[0018] Y={(B0-B1) / B0}×100 (2)

[0019] [In Equation (2), B0 represents the weight of the zirconium phosphate particles before heating, and B1 represents the weight of the zirconium phosphate particles after heating.]

[0020] [6] A basic gas deodorizer containing zirconium phosphate particles as described in any one of [1]~[5].

[0021] [7] A basic gas deodorizer for fibers containing zirconium phosphate particles as described in any one of [1]~[5].

[0022] [8] Basic gas deodorizer for fiber dough containing zirconium phosphate particles as described in any one of [1]~[5].

[0023] [9] A composition for deodorizing basic gases containing zirconium phosphate particles as described in any one of [1] to [5].

[0024]

[10] A basic gas deodorizing resin composition comprising zirconium phosphate particles as described in any one of [1] to [5].

[0025]

[11] Basic gas deodorizing fiber containing zirconium phosphate particles as described in any one of [1]~[5].

[0026]

[12] Basic gas deodorizing fibers described in

[11] comprising at least one fiber selected from the group consisting of polyester, polyurethane, nylon, rayon, cotton, acrylic, aramid, vinylon, polyethylene and polypropylene.

[0027]

[13] A method for producing zirconium phosphate particles as described in any one of [1] to [5], comprising contacting the α-zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then further contacting them with an acidic liquid with a pH of 6 or lower.

[0028]

[14] A method for producing zirconium phosphate particles as described in

[13] , wherein the basic liquid contains an alkali metal and / or an alkaline earth metal.

[0029]

[15] A method for preparing a basic gas deodorizing resin composition comprising mixing zirconium phosphate particles and resin obtained by the manufacturing method described in

[13] or

[14] .

[0030]

[16] A method for preparing a basic gas deodorizing resin composition comprising contacting zirconium phosphate particles with a basic liquid with a pH of 9 or higher, then further contacting them with an acidic liquid with a pH of 6 or lower to obtain liquid-treated zirconium phosphate particles, and mixing the liquid-treated zirconium phosphate particles and the resin.

[0031]

[17] A method for manufacturing a basic gas deodorizing fiber comprising spinning a basic gas deodorizing resin composition obtained by the manufacturing method described in

[15] or

[16] .

[0032]

[18] A method for preparing a basic gas deodorizing resin composition comprising contacting a resin containing zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then contacting it with an acidic liquid with a pH of 6 or lower.

[0033]

[19] A method for preparing a basic gas deodorizing resin composition as described in

[18] , wherein the above zirconium phosphate particles are as described in any one of [1] to [5].

[0034]

[20] A method for manufacturing a basic gas deodorizing fiber comprising contacting a fiber containing zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then contacting it with an acidic liquid with a pH of 6 or lower.

[0035]

[21] A method for manufacturing basic gas deodorizing fibers as described in

[20] , wherein the above zirconium phosphate particles are as described in any one of [1] to [5]. Effects of the invention

[0036] According to one embodiment of the present invention, zirconium phosphate particles having high deodorizing performance against basic gases such as ammonia and trimethylamine, and particularly excellent deodorizing speed of ammonia, a deodorizing agent using the same, a composition for deodorizing processing, a deodorizing resin composition, and a deodorizing fiber, and a method for manufacturing the same are provided. Specific details for implementing the invention

[0037] The present disclosure will be described in detail below.

[0038] Additionally, in this specification, '%' means 'weight %' unless specifically stated otherwise, 'part' means 'weight part', and 'ppm' means 'volume ppm'.

[0039] Furthermore, in this specification, the description of a numerical range as 'lower limit to upper limit' indicates 'greater than or equal to the lower limit, less than or equal to the upper limit,' and the description of 'upper limit to lower limit' indicates 'less than or equal to the upper limit, greater than or equal to the lower limit.' That is, it indicates a numerical range that includes the upper limit and the lower limit.

[0040] In addition, in this specification, 'room temperature' means 25±5℃.

[0041] In addition, regarding the present disclosure, a combination of two or more preferred embodiments described below is also a preferred embodiment.

[0042] The zirconium phosphate particles in the present disclosure are particles having zirconium phosphate as the main component, and may include impurities and moisture introduced from raw materials and manufacturing processes, etc. The main component is a zirconium phosphate component contained in the particles that is 50% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and even more preferably 95% by weight or more.

[0043] 1. Zirconium phosphate particles

[0044] The zirconium phosphate particles related to the first aspect of the present disclosure are zirconium phosphate particles obtained by contacting α-zirconium phosphate particles with a basic liquid with a pH of 9 or higher (hereinafter also simply referred to as "basic liquid") and then further contacting them with an acidic liquid with a pH of 6 or lower (hereinafter also simply referred to as "acidic liquid").

[0045] The zirconium phosphate particles related to the second aspect of the present disclosure are zirconium phosphate particles in which 10 mg of zirconium phosphate particles and 3 L of air containing 1000 ppm of ammonia gas are placed in a test bag at room temperature and atmospheric pressure and left for 10 minutes, and the ammonia gas reduction rate (X; unit %) in the test bag containing the zirconium phosphate particles is 50% or more as shown by the following formula (1).

[0046] X={(A0-A1) / A0)}×100 (1)

[0047] [In Equation (1), A0 represents the ammonia gas concentration of a test bag without zirconium phosphate particles, and A1 represents the ammonia gas concentration of a test bag with zirconium phosphate particles.]

[0048] Additionally, in this specification, the term "zirconium phosphate particles of the present disclosure" includes zirconium phosphate particles related to the first aspect and zirconium phosphate particles related to the second aspect.

[0049] 1-1. Zirconium phosphate particles associated with the first sun

[0050] The zirconium phosphate particles associated with the first sun are zirconium phosphate particles obtained by contacting α-zirconium phosphate particles with a basic liquid and then further contacting them with an acidic liquid.

[0051] Below, a basic liquid, an acidic liquid, raw material α-zirconium phosphate particles, and a method for manufacturing zirconium phosphate are described.

[0052] 1-1-1. Basic Liquids

[0053] The base included in the basic liquid is not particularly limited, and well-known bases including, for example, alkali metals, alkaline earth metals, ammonia, amines, and ammonium salts may be used. Examples of alkali metals include lithium, sodium, and potassium, and examples of alkaline earth metals include magnesium and calcium. Examples of amines include alkyl amines such as methylamine, dimethylamine, and trimethylamine; aryl amines such as aniline and phenylmethylamine; and heterocyclic aromatic amines such as pyridine. Examples of ammonium salts include tetramethylammonium hydroxide. These may be used individually or in combination of two or more.

[0054] Among these, it is preferable to use a base containing an alkali metal and / or an alkaline earth metal, as it has strong basicity, allows for efficient contact treatment with a basic liquid, has almost no odor, and provides a good working environment. Examples of bases containing an alkali metal include lithium hydroxide, sodium hydroxide, and potassium hydroxide, and examples of bases containing an alkaline earth metal include magnesium hydroxide and calcium hydroxide.

[0055] The solvent used for the basic liquid with a pH of 9 or higher is not particularly limited, but is preferably water and lower alcohols such as methanol, and more preferably water. The method of preparing the basic liquid with a pH of 9 or higher is not particularly limited, and well-known methods may be applied. For example, it can be prepared by dissolving a base containing an alkali metal and / or alkaline earth metal, specifically lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc., or tetramethylammonium hydroxide, etc., in a solvent such as water.

[0056] The pH of the basic liquid is not particularly limited as long as it satisfies 9 or higher, but from the perspective of efficiency of the manufacturing process and resource conservation, it is preferably 12 or higher, and more preferably 13 or higher.

[0057] In addition, when α-zirconium phosphate particles are brought into contact with a basic liquid, the total amount of a base, such as an alkali metal and / or alkaline earth metal, is preferably 1 / 20 molar ratio or more with respect to the hydroxyl group (hereinafter also referred to as 'P-OH group') bonded to the phosphorus atom of the α-zirconium phosphate, more preferably 1 / 10 molar ratio or more, and even more preferably 1 / 5 molar ratio or more. If the molar ratio is 1 / 20 molar ratio or more, the effect of imparting high-speed deodorizing properties to the α-zirconium phosphate can be sufficiently obtained.

[0058] 1-1-2. Acidic liquid

[0059] The acid used in the acidic liquid is not particularly limited, but well-known acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid may be used, and an acid having a lower acid dissociation index (i.e., pKa) than the phosphate group of zirconium α-phosphate is preferred.

[0060] The solvent used for acidic liquids is not particularly limited, but is preferably water and lower alcohols such as methanol, and more preferably water.

[0061] The pH of the acidic liquid is not particularly limited as long as it satisfies 6 or less, but from the perspective of efficiency of the manufacturing process and resource conservation, it is preferably pH 2 or less, and more preferably pH 1 or less.

[0062] In addition, the total amount of acid when contacting zirconium phosphate particles with an acidic liquid is preferably 100 mol% or more, more preferably 300 mol% or more, and even more preferably 1000 mol% or more, with respect to the amount of P-OH groups of α-zirconium phosphate before contacting with a basic liquid of pH 9 or higher. If it is 100 mol% or more, the effect of imparting high-speed deodorizing properties to α-zirconium phosphate can be sufficiently obtained.

[0063] 1-1-3. Zirconium α-phosphate particles

[0064] As for the α-zirconium phosphate used as a raw material in the manufacture of zirconium phosphate related to the first sun, various compounds can be used, and conventionally known α-zirconium phosphate can be used.

[0065] As for α-zirconium phosphate, various compounds can be used, but a compound represented by the following formula (3) and having a cation exchange capacity of 6.7 meq / g per unit weight is preferred.

[0066] Zr 1-x Hf x H a (PO4) b ·nH2O (3)

[0067] In equation (3), a and b are integers satisfying 3b-a=4, b is 2.0<b≤2.1, x is an integer 0≤x≤0.2, and n is an integer 0≤n≤2.0.

[0068] In the above formula (3) of α-zirconium phosphate, hafnium (Hf) is derived from a raw zirconium compound. x in formula (3) is an integer such that 0 ≤ x ≤ 0.2. In the present disclosure, preferably 0 ≤ x ≤ 0.2, more preferably 0.005 ≤ x ≤ 0.1, and even more preferably 0.005 ≤ x < 0.03.

[0069] In formula (3), n is preferably 2.0 or less, and more preferably 1.0 or less. By making the value of n 2.0 or less, attached water or crystal water can be removed during resin melting when spinning, and foaming or breakage of the thread can be prevented.

[0070] The method for adjusting the diameter of the zirconium phosphate particles related to the first aspect is not particularly limited. For example, adjustment can be made at any stage before and after contact with a basic liquid with a pH of 9 or higher, and after contact with an acidic liquid with a pH of 6 or lower, but it is preferable to control it before contact with a basic liquid with a pH of 9 or higher, that is, at the stage of manufacturing the raw material α-zirconium phosphate particles.

[0071] The method for adjusting the diameter of the α-zirconium phosphate particles used in the present disclosure is not limited, but in order to obtain the desired particle size distribution, it is preferable to adjust the diameter by synthesizing the α-zirconium phosphate particles in an aqueous solution. When synthesized in an aqueous solution, it is easy to make the particle diameter uniform during synthesis and easy to obtain a sharp particle size distribution. On the other hand, if the particle diameter is adjusted by grinding, fine powder or large particles are mixed in, and the width of the particle size distribution widens, and when used as a deodorizing fiber by kneading it into a fiber, it is easy to cause yarn breakage during spinning.

[0072] The α-zirconium phosphate particles used in the present disclosure can be manufactured by well-known methods. The method for manufacturing α-zirconium phosphate can utilize conventional technology, and there are no restrictions on raw materials, equipment, etc. Examples include the methods described in Japanese Patent Publication No. 5545328 and Japanese Patent Publication No. 5821258.

[0073] As a method for manufacturing α-zirconium phosphate particles, a method of reacting raw material compounds in an aqueous solution is preferred because it is easy to obtain particles with a uniform particle diameter.

[0074] For example, a method may be used in which an aqueous solution of a zirconium compound is mixed with an aqueous solution containing phosphoric acid and / or its salt [hereinafter also referred to as 'phosphoric acid (salt)'] to produce a precipitate, and then aged to crystallize.

[0075] Examples of zirconium compounds used as raw materials for manufacturing α-zirconium phosphate particles include zirconium nitrate, zirconium acetate, zirconium sulfate, zirconium carbonate, basic zirconium sulfate, zirconium oxysulfate, and zirconium oxychloride. Zirconium nitrate, zirconium acetate, zirconium sulfate, zirconium carbonate, basic zirconium sulfate, zirconium oxysulfate, and zirconium oxychloride are preferred, and considering reactivity and economic feasibility, zirconium oxychloride is more preferably.

[0076] Examples of the phosphoric acid (salt) of the above-mentioned manufacturing raw material include phosphoric acid, sodium phosphate, potassium phosphate, and ammonium phosphate, and preferably phosphoric acid.

[0077] The reaction ratio of phosphoric acid (salt) is, as a molar ratio to the zirconium compound, 2 or more, preferably 2.05 or more, and more preferably 2.1 or more.

[0078] The reaction ratio of phosphoric acid (salt) may be in excess with respect to the zirconium compound, but considering the conductivity of the supernatant during washing after synthesis, from the perspective of improving the efficiency of the washing process, the above molar ratio is, for example, 3 or less, preferably 2.9 or less, and more preferably 2.6 or less.

[0079] In the production of α-zirconium phosphate particles, it is preferable to add a dicarboxylic acid (which may be in the form of a hydrate) or its salt into the reaction system, examples of which include oxalic acid, malonic acid, succinic acid, and their salts. Among these, adding oxalic acid or its salt is preferable because it accelerates the production of α-zirconium phosphate, reduces the waste of raw materials, and enables efficient production.

[0080] Examples of oxalic acid or its salts in this case include oxalic acid dihydrate, ammonium oxalate, and ammonium hydrogen oxalate, and oxalic acid dihydrate is preferred.

[0081] The reaction ratio of oxalic acid or its salt is a molar ratio to the zirconium compound, for example, 1.0 to 3.5, more preferably 1.5 to 3.2, and even more preferably 2.0 to 3.0. In the present disclosure, within the above range of ratios is desirable because it facilitates the production of α-zirconium phosphate.

[0082] In the preparation of α-zirconium phosphate particles, an aqueous solution of a zirconium compound is mixed with an aqueous solution containing phosphoric acid (salt), and then aged. This aging may be carried out at room temperature, but it is preferable to perform it at a wet atmospheric pressure of 90°C or higher to accelerate the aging process. Additionally, synthesis may be carried out under conditions exceeding 100°C, known as hydrothermal conditions, in an atmosphere of pressure higher than atmospheric pressure. When preparing α-zirconium phosphate particles under hydrothermal conditions, it is preferable to synthesize at 130°C or lower in terms of manufacturing costs.

[0083] The preparation time for α-zirconium phosphate particles can be any time that allows for the synthesis of α-zirconium phosphate particles. For example, α-zirconium phosphate particles can be obtained by mixing phosphoric acid (salt) and a zirconium compound to induce precipitation, and then aging the mixture. The aging time varies depending on the aging temperature and is appropriately selected.

[0084] For example, in aging at 90°C, the aging time is preferably 4 hours or more. In addition, even if aging is carried out for 24 hours or more, the content of α-zirconium phosphate particles tends to reach a limit point.

[0085] After synthesis, the α-zirconium phosphate particles can be separated by further filtration, thoroughly washed with water, and then dried to obtain α-zirconium phosphate particles.

[0086] 1-1-4. Method for manufacturing zirconium phosphate particles

[0087] A method for manufacturing zirconium phosphate particles related to the first sun includes contacting α-zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then further contacting them with an acidic liquid with a pH of 6 or lower.

[0088] The composition of the basic liquid, the acidic liquid, and the α-zirconium phosphate particles of the raw material is as described above, and the preferred range is as described above.

[0089] There are no particular limitations on the temperature at which α-zirconium phosphate particles are brought into contact with a basic liquid, or additionally with an acidic liquid, and are typically carried out in a range of, for example, 0 to 100°C, but preferably 10 to 90°C, and more preferably 15 to 85°C.

[0090] Depending on the purpose, the contact temperature with the basic liquid and the contact temperature with the acidic liquid may be performed at different temperatures.

[0091] There are no particular limitations on the method of contacting α-zirconium phosphate particles with a basic liquid, and the method of further contacting them with an acidic liquid after contacting them with a basic liquid, and all well-known methods can be applied.

[0092] For example, methods include immersing α-zirconium phosphate particles in each of these liquids, immersing α-zirconium phosphate particles in each of these liquids and stirring, and spraying, dropping, or coating each of these liquids onto α-zirconium phosphate particles. These methods can be carried out individually or in combination, but the method of immersing and stirring in each liquid is preferred in that it allows for sufficient contact treatment.

[0093] The contact time of the α-zirconium phosphate particles with a basic liquid should be appropriately set according to the type and pH of the basic liquid used, the contact temperature, and the intended use of the final zirconium phosphate particles. The contact time of the α-zirconium phosphate particles with the basic liquid is preferably 3 minutes to 10 hours, more preferably 15 minutes to 5 hours, and even more preferably 30 minutes to 3 hours. Depending on the type and pH of the basic liquid used, the contact temperature, and the intended use of the final zirconium phosphate particles, contact may be extended to more than 10 hours; however, contacting for 10 hours or less is economically preferable because it improves production efficiency. Furthermore, contact treatment of 3 minutes or more is desirable because it tends to allow the α-zirconium phosphate particles to come into uniform contact with the basic liquid.

[0094] In addition, the time for contacting the acidic liquid after contacting the basic liquid should be appropriately set according to the type and pH of the acidic liquid used, the contact temperature, and the intended use of the zirconium phosphate particles obtained at the end. The time for contacting the acidic liquid after contacting the basic liquid is preferably 3 minutes to 10 hours, more preferably 15 minutes to 5 hours, and even more preferably 30 minutes to 3 hours. Depending on the type and pH of the acidic liquid used, the contact temperature, and the intended use of the zirconium phosphate particles obtained at the end, contact may be extended to more than 10 hours; however, contacting for 10 hours or less is economically preferable because it improves production efficiency. Furthermore, contact treatment of 3 minutes or more is desirable because it tends to allow the α-zirconium phosphate particles to come into uniform contact with the acidic liquid.

[0095] 1-2. Zirconium phosphate particles related to the second sun

[0096] The zirconium phosphate particles related to the second sun are zirconium phosphate particles in which 10 mg of zirconium phosphate particles and 3 L of air containing 1000 ppm of ammonia gas are placed in a test bag at room temperature and pressure, and after being left for 10 minutes, the ammonia gas reduction rate (X; unit %) in the test bag containing the zirconium phosphate particles is 50% or more as indicated by the following formula (1).

[0097] X={(A0-A1) / A0)}×100 (1)

[0098] [In Equation (1), A0 represents the ammonia gas concentration of a test bag without zirconium phosphate particles, and A1 represents the ammonia gas concentration of a test bag with zirconium phosphate particles.]

[0099] It is preferable that the ammonia gas reduction rate represented by the above formula (1) after leaving the second zirconium phosphate particles related to the sun for 10 minutes is 55% or more, and more preferable that it is 60% or more.

[0100] The zirconium phosphate particles related to the second sun are preferably such that the ammonia gas reduction rate (X; unit %) represented by the above formula (1) is 40% or more, more preferably 50% or more, and even more preferably 55% or more, after placing 3L of air containing 10 mg of zirconium phosphate particles and 1000 ppm of ammonia gas into a test bag at room temperature and atmospheric pressure and leaving it for 5 minutes.

[0101] The material of the test bag used to determine the ammonia gas reduction rate in the present disclosure is not particularly limited and well-known materials may be used. Examples include polyvinyl alcohol, polyvinylidene fluoride, polyvinyl fluoride, tetrafluorinated ethylene-hexafluorinated propylene copolymer, and polyester.

[0102] The method for detecting the concentration of basic gases such as ammonia in the present disclosure may apply well-known methods and is not particularly limited. For example, the concentration of ammonia gas can be measured using a gas sampler and a detector tube. Specifically, a detector tube for detecting ammonia gas with a syringe needle set in it can be attached to a gas sampler and inserted into a test bag. Ammonia gas can be drawn in by the suction force of the gas sampler and adsorbed onto the detector tube, and the concentration can be measured by reading the value of the concentration from the color change of the detector tube.

[0103] 1-2-1. Method for manufacturing zirconium phosphate particles

[0104] The method for manufacturing the zirconium phosphate particles related to the second aspect is not particularly limited. For example, they may be manufactured using the method for manufacturing the zirconium phosphate particles related to the first aspect described above.

[0105] 1-3. Median Diameter

[0106] The median diameter of the primary particles of the zirconium phosphate particles of the present disclosure (hereinafter also simply referred to as "particle diameter") is preferably 0.1 to 10.0 μm, more preferably 0.2 to 3.0 μm, and even more preferably 0.2 to 1.5 μm. It is preferable that the median diameter of the primary particles be 0.2 to 1.5 μm because the number of particles is greater and the deodorizing effect is more likely to occur when kneaded into fibers. In addition, it is preferable that the median diameter of the primary particles be 0.1 μm or larger because aggregation becomes difficult and it is less likely to cause yarn breakage during spinning.

[0107] In this disclosure, particle diameter refers to a value measured by a laser diffraction particle size analyzer and interpreted on a volume basis.

[0108] The method for adjusting the diameter of the zirconium phosphate particles of the present disclosure is not particularly limited. For example, it can be adjusted in the method for manufacturing zirconium phosphate particles described above.

[0109] 1-4. Drying loss

[0110] The high-speed deodorizing zirconium phosphate particles of the present disclosure preferably have a drying loss (Y; unit weight%) represented by the following formula (2) after heating at 150°C for 2 hours under atmospheric pressure, which is 5.0 weight% or less, more preferably 3.0 weight% or less, and even more preferably 1.0 weight% or less.

[0111] It is desirable to reduce foaming and hydrolysis of the resin when producing a deodorizing resin composition or a deodorizing fiber masterbatch containing high-speed deodorizing zirconium phosphate particles by reducing the drying reduction amount to 5.0 weight% or less.

[0112] Y={(B0-B1) / B0}×100 (2)

[0113] [In Equation (2), B0 represents the weight of the zirconium phosphate particles before heating, and B1 represents the weight of the zirconium phosphate particles after heating.]

[0114] 2. Uses

[0115] The zirconium phosphate particles of the present disclosure can be used for various purposes.

[0116] In particular, the zirconium phosphate particles of the present disclosure can be preferably used as a basic gas adsorbent because they have a fast adsorption rate of basic gases.

[0117] In addition, the zirconium phosphate particles of the present disclosure can be preferably used as a deodorizer, and more preferably as a basic gas deodorizer.

[0118] Basic gases include ammonia, which causes bad odors, alkyl amines such as trimethylamine and dimethylamine, nitrogen-containing heterocyclic aromatic compounds such as pyridine, heterocyclic amines such as piperidine, aromatic amines such as aniline, and hydrazines.

[0119] In addition, as a basic gas deodorizer, it can be preferably used as a basic gas deodorizer for textiles and as a basic gas deodorizer for textile dough.

[0120] The specific method of use is described in detail below.

[0121] 3. Composition for deodorizing basic gases

[0122] The high-speed deodorizing zirconium phosphate particles of the present disclosure can be mixed with a suitable known binder, dispersant, emulsion, solvent, etc. to form a composition for deodorizing basic gases. Using these, a basic gas deodorizing agent can be electrodeposited on fibers, filters, fabrics, sheets, etc., and deodorizing properties can be imparted.

[0123] There are no particular restrictions on the binder, and any known binder may be used. For example, when manufacturing a deodorizing product, it is a component that adheres the deodorizing agent containing the zirconium phosphate particles of the present disclosure to a substrate such as a fiber. Preferably, it is a polymer compound, and it may be any one of a synthetic polymer compound, a semi-synthetic polymer compound, or a natural polymer compound.

[0124] Examples of polymer compounds include resins and polysaccharides, and preferably resins. In addition, the binder that can be included in the composition for processing basic gas deodorization of the present disclosure may be one or two or more types. The above resin may be either a water-soluble resin or a water-insoluble resin, and may be an ethylene-vinyl acetate copolymer or a modified product thereof (e.g., an acid modified product, etc.), an ethylene-vinyl chloride copolymer, a vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinyl chloride, a modified olefin resin (e.g., a chlorinated polyolefin, etc.), polyvinyl alcohol, alkyl cellulose, carboxyalkyl cellulose, carboxyalkyl hydroxyalkyl cellulose, polyacrylic acid, polyacrylate, acrylic resin, polyester resin, urethane resin, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, hydrogenation Examples include styrene-ethylene-butylene-styrene block copolymers, hydrogenated styrene-ethylene-propylene-styrene block copolymers, and styrene-maleic anhydride copolymers.

[0125] There are no particular restrictions on the dispersant, and well-known ones may be used. For example, any one of anionic surfactants, cationic surfactants, cationic surfactants, and nonionic surfactants may be used, or a combination of two or more may be used. Among these, anionic surfactants and nonionic surfactants are particularly preferred from the perspective of the dispersibility of zirconium phosphate particles. The preferred surfactant that may be contained in the composition for processing basic gas deodorization of the present disclosure may be either anionic surfactant or a nonionic surfactant, or both.

[0126] The composition for deodorizing basic gases disclosed herein may contain a medium. Although there are no particular limitations on the medium, examples include water alone or a mixture of water and a water-soluble organic solvent, and water is preferred.

[0127] Examples of organic solvents that are water-soluble include lower alcohols such as methanol, ethanol, and 2-propanol.

[0128] 4. Basic gas deodorizing resin composition

[0129] The high-speed deodorizing zirconium phosphate particles of the present disclosure can be mixed with a resin to form a basic gas deodorizing resin composition. Examples of resins include polypropylene, polyethylene, acrylonitrile-butadiene-styrene (ABS), polyester, polyurethane, nylon, polystyrene, polycarbonate, acrylic resin, and vinyl chloride resin, but are not limited to these resins.

[0130] The method for manufacturing a basic gas deodorizing resin composition is not particularly limited.

[0131] For example, it may be manufactured by a method comprising mixing zirconium phosphate particles obtained by the method for manufacturing zirconium phosphate particles described above with a resin.

[0132] In addition, it may be manufactured by a method including contacting zirconium phosphate particles with a basic liquid with a pH of 9 or higher, then further contacting them with an acidic liquid with a pH of 6 or lower to obtain liquid-treated zirconium phosphate particles, and mixing the liquid-treated zirconium phosphate particles and a resin.

[0133] Although the method of mixing zirconium phosphate particles and resin is not particularly limited, it is preferable to knead the zirconium phosphate particles into the resin to impart durability and wear resistance so that the zirconium phosphate does not detach from the resin, and to maintain deodorizing performance.

[0134] 5. Basic gas deodorizing fiber

[0135] The basic gas deodorizing fiber of the present disclosure is not particularly limited as long as it comprises the zirconium phosphate particles of the present disclosure or a basic gas deodorizing agent containing the same.

[0136] As a method for manufacturing the basic gas deodorizing fiber of the present disclosure, a conventional method may be followed.

[0137] For example, methods include a method of mixing the basic gas deodorizer of the present disclosure into a fiber and spinning it, and a method of coating the spun fiber with a basic gas deodorizing processing composition containing the basic gas deodorizer of the present disclosure.

[0138] There are no restrictions on the fiber resins that can be used for processing the basic gas deodorizer of the present disclosure, and all known chemical fibers may be used. Preferred specific examples include, for instance, polyester, polyurethane, nylon, rayon, acrylic resin, aramid, vinylon, polyethylene, and polypropylene. Among these, polyurethane, polyester, nylon, acrylic resin, and polyethylene are preferred. These resins may be homopolymers or copolymers. In the case of copolymers, there are no particular restrictions on the polymerization ratio of each copolymer component.

[0139] Polyurethane may be any material based on polymer diols and diisocyanates as starting materials, and is not particularly limited. Furthermore, the synthesis method is not particularly limited.

[0140] In addition, the polyester is not particularly limited, but, for example, polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polybutylene terephthalate are preferred.

[0141] The basic gas deodorizer of the present disclosure can be preferably used as a deodorizer for fiber dough.

[0142] Specific manufacturing methods for the basic gas deodorizing fiber in this case include a method of mixing and adding the deodorizing agent of the present disclosure into a molten liquid fiber resin or a fiber resin solution dissolved in a solvent and spinning it, or a method of processing a masterbatch resin containing a high concentration of the basic gas deodorizing agent, then mixing and melting it with the fiber resin and spinning it.

[0143] The ratio of the basic gas deodorizer of the present disclosure to be included in the fiber resin is not particularly limited. Generally, increasing the content allows for strong deodorizing properties to be sustained for a long period, but considering that there is no significant difference in the deodorizing effect even if the content is increased beyond a certain level, or that the resin strength decreases, and from the perspective of economic feasibility, it is preferably 0.1 to 5.0 parts by weight per 100 parts by weight of resin, and more preferably 0.5 to 2.0 parts by weight.

[0144] A method for preparing a basic gas deodorizing resin composition containing zirconium phosphate particles according to the present disclosure involves contacting a resin containing zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then contacting it with an acidic liquid with a pH of 6 or lower.

[0145] The method for manufacturing a basic gas deodorizing fiber containing zirconium phosphate particles of the present disclosure is to contact a fiber containing zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then contact it with an acidic liquid with a pH of 6 or lower.

[0146] In the present invention, contacting zirconium phosphate with a basic liquid with a pH of 9 or higher, and then further contacting it with an acidic liquid with a pH of 6 or lower, may be done by direct contact with the zirconium phosphate, or by contacting it with a mixture of zirconium phosphate and a resin or fiber, such that the liquid penetrates into the resin or fiber, and the basic liquid and the acidic liquid come into contact with the zirconium phosphate inside the resin or fiber; this falls within the same conceptual scope and exhibits the same effect.

[0147] Examples of the above zirconium phosphate particles include zirconium phosphate particles having basic gas adsorption capacity, such as α-zirconium phosphate particles, zirconium phosphate particles obtained by contacting α-zirconium phosphate particles with a basic liquid of pH 9 or higher and then further contacting them with an acidic liquid of pH 6 or lower, β-zirconium phosphate particles, γ-zirconium phosphate particles, and amorphous zirconium phosphate particles. Preferably, examples include α-zirconium phosphate particles and zirconium phosphate particles obtained by contacting α-zirconium phosphate particles with a basic liquid of pH 9 or higher and then further contacting them with an acidic liquid of pH 6 or lower. More preferably, examples include zirconium phosphate particles obtained by contacting α-zirconium phosphate particles with a basic liquid of pH 9 or higher and then further contacting them with an acidic liquid of pH 6 or lower. That is, when using the zirconium phosphate particles that are the liquid treated product of the above-mentioned α-zirconium phosphate particles, a second liquid treatment is performed on the resin or fiber containing them. The second liquid treatment may substantially include a dyeing treatment, etc.

[0148] Basic gas deodorizing resin compositions and basic gas deodorizing fibers containing zirconium phosphate particles may experience a deterioration in their deodorizing performance and subsequent disappearance after contact treatment with a basic liquid, for example, in a fiber manufacturing process such as dyeing. In response to this, as disclosed in the present disclosure, by additionally performing contact treatment with an acidic liquid after the contact treatment with the aforementioned basic liquid, a basic gas deodorizing resin composition and a basic gas deodorizing fiber are provided that not only exhibit deodorizing performance but also have an improved basic gas deodorizing rate compared to the basic gas deodorizing resin composition and basic gas deodorizing fiber prior to the additional contact treatment with the acidic liquid after the contact treatment with the basic liquid of the present disclosure.

[0149] 6. Additives

[0150] The basic gas deodorizer comprising the high-speed deodorizing type zirconium phosphate particles of the present disclosure, the basic gas deodorizer for textiles, the composition for basic gas deodorization processing, the basic gas deodorization resin composition, and the basic gas deodorization fiber may suitably include additives.

[0151] There are no particular restrictions on additives, and examples include thickeners, other well-known deodorizers, such as acidic gas deodorizers, basic gas deodorizers, sulfur-based gas deodorizers, aldehyde-based gas deodorizers, ketone-based gas deodorizers, antibacterial agents, antifungal agents, antiviral processing agents, anti-allergens, defoaming agents, coloring agents, preservatives, viscosity modifiers, and fragrances.

[0152] In addition, other well-known deodorizers do not include the basic gas deodorizer of the present disclosure.

[0153] There are no particular restrictions on the thickener, and known ones may be used. Examples include polysaccharides, and specific examples include xanthan gum, alginate, gum arabic, starch, tamarind seed gum, guar gum, and carboxymethyl cellulose.

[0154] Other deodorizing agents may be incorporated in types and proportions that do not reduce the deodorizing performance of basic gases in the resulting deodorizing product.

[0155] Compounds that cause bad odors include basic gases such as ammonia gas and trimethylamine; acidic gases such as acetic acid and isovaleric acid; aldehyde-based gases such as formaldehyde, acetaldehyde and nonenal; and sulfur-based gases such as hydrogen sulfide and methyl mercaptan, and may contain other deodorizing agents having deodorizing performance against these.

[0156] Examples of deodorizing agents for basic gases include amorphous complex oxides such as zeolite, Al2O3, SiO2, MgO, CaO, SrO, BaO, ZrO2, TiO2, WO2, CeO2, Li2O, Na2O, and K2O.

[0157] Examples of deodorizers for acidic gases include zirconium hydroxide, zirconium oxide, and hydrotalcite-based compounds such as magnesium-aluminum hydrotalcite.

[0158] Examples of deodorizers for aldehyde-based gases include hydrazine-based compounds such as adipic acid dihydrazide, carbohydrazide, succinic acid dihydrazide and oxalic acid dihydrazide, aminoguanidine salts such as aminoguanidine hydrochloride, aminoguanidine sulfate and aminoguanidine bicarbonate.

[0159] Examples of deodorizers for sulfur-based gases include copper silicate, zirconium copper phosphate hydrate, zinc oxide, zinc aluminum oxide, zinc silicate, zinc aluminum silicate, and layered aluminosilicate.

[0160] A deodorizing resin composition using the deodorizing agent of the present disclosure can be used in various fields requiring deodorizing properties, and can be used in many resin products such as daily necessities like trash cans, triangular corners, plastic wrap, and sponges; electrical products like refrigerators, air purifier filters, and air conditioner filters; housing and building materials such as wallpaper, toilets, toilet seats, kitchen counters, ventilation fan filters, and paints; textile products such as clothing, bedding, curtains, mats, shoes, stockings, and socks; pet products; and care products.

[0161] Deodorizing fibers using the deodorizing agent of the present disclosure can be used in various fields requiring deodorizing properties, and can be used in many textile products such as underwear, stockings, socks, bedding, duvet covers, cushions, blankets, carpets, curtains, sofas, car seats, air filters, and caregiving clothing.

[0162] Examples

[0163] Next, the present disclosure will be described in detail based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0164] <Preparation Example 1> (Preparation of α-zirconium phosphate)

[0165] 1345 mL of deionized water and 135 g of 35% hydrochloric acid were placed in a 2 L round-bottom flask, and 225 g of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18 wt% hafnium was added, followed by the addition of 93 g of oxalic acid dihydrate to dissolve it. While stirring the solution well, 101 g of 75% phosphoric acid was added. The temperature was raised to 98°C over 2 hours, and then refluxed while stirring for 12 hours. After cooling the reaction system, the resulting precipitate was filtered, thoroughly washed, and dried at 105°C under atmospheric pressure to obtain zirconium phosphate. This was then crushed using a rotor speed mill (16,000 rpm, sieve mesh size 80 μm). Powder X-ray diffraction and fluorescence X-ray analysis were performed on the obtained zirconium phosphate, confirming that it was α-zirconium phosphate.

[0166] Fluorescence X-ray analysis and thermogravimetric differential thermal coherence analysis (TG-DTA) were performed on this α-zirconium phosphate, and the compositional formula was Zr 0.99 Hf 0.01 H 2.03 (PO4) 2.01 ·0.05H2O and the median diameter was 0.89μm.

[0167] In addition, the measurement conditions and methods for powder X-ray diffraction, fluorescence X-ray analysis, TG-DTA, and particle diameter (median diameter) are described below.

[0168] <Powder X-ray Diffraction>

[0169] The BRUKER D8 ADVANCE X-ray diffraction apparatus was used. X-ray diffraction patterns were obtained using CuKα generated at an applied voltage of 40 kV and a current of 40 mA, utilizing a Cu-encapsulated X-ray source. The detailed measurement conditions are as follows.

[0170] X-ray source: Encapsulated X-ray source (Cu source), 0.4×12 mm 2 Long Fine Focus

[0171] Rated: 2.2kW

[0172] Output power: 40kV-40 mA (1.6 kW)

[0173] Goniometer radius: 280mm

[0174] Sample Stage: FlipStick_Twin_Twin-XE

[0175] Measurement range 2θ: 5°~55°

[0176] Step width: 0.02°

[0177] Step time: 0.05 seconds / step

[0178] Incident side solar slit: 2.5°

[0179] Anti-scattering slit: 10.5mm

[0180] Curvature: 1.00

[0181] Detector: LYNXEYE XE

[0182] Detector slit width: 5.758 mm

[0183] Detector window width: 2.9°

[0184] <Fluorescent X-ray Analysis>

[0185] Fluorescent X-ray analysis was measured under the following conditions.

[0186] Measuring instrument: Rigaku ZSX Primus II

[0187] Measurement conditions

[0188] Measured elements: C~U (Precise measurement on F, Cl, Br, I, BG 4 sec, peak 8 sec)

[0189] Analysis diameter: 20mm

[0190] Measurement count: Measured with n2

[0191] Sample processing: The sample was pressure-molded into a pellet shape using a tablet molding machine and provided for measurement.

[0192] analysis

[0193] Software: ZSX version 7.49

[0194] Model: Bulk

[0195] <TG-DTA>

[0196] TG-DTA measurements were performed under the following conditions.

[0197] Measuring instrument: TG / DTA 6300 manufactured by Hitachi High-Tech Science

[0198] Measurement method: 7 to 8 mg of sample was placed in an Al pan and set up, and the temperature was raised to 600°C at 20°C / min. The weight loss from room temperature to 100°C was defined as the moisture content (attached water), and the weight loss from 100°C to 250°C was evaluated as the crystal water.

[0199] <Measurement of Particle Diameter (Median Diameter)>

[0200] The particle diameter of the deodorant was measured using the Marban-manufactured laser diffraction particle size distribution measuring device "Master Sizer-2000," and the results were interpreted on a volume basis. The deodorant dispersion solution containing the deodorant was dispersed by ultrasound and measured with a refractive index of 2.4.

[0201] <Example 1>

[0202] [Sodium hydroxide usage: 1 / 4 molar ratio with respect to the P-OH groups of α-zirconium phosphate, Bath ratio: α-zirconium phosphate / NaOH aqueous solution = 1 / 20 weight ratio]

[0203] 3 g of the α-zirconium phosphate obtained in Preparation Example 1 and 3 g of pure water were placed in a 100 mL beaker and stirred with a stirrer. Then, 57 g of an aqueous sodium hydroxide solution (1 / 4 molar ratio with respect to the P-OH groups of α-zirconium phosphate) adjusted to a pH of 12.9 was added and stirred at 80°C for 1 hour, after which the mixture was filtered and taken. Subsequently, the filtrate was filtered and washed until the electrical conductivity of the filtrate was 100 μS / cm or less. The obtained zirconium phosphate was dried at 120°C for 2 hours under atmospheric pressure and ground in a mortar and pestle to obtain basic liquid-treated zirconium phosphate particles (A-1). Next, 200 g of a 1 N aqueous nitric acid solution (pH 1) was placed in a 200 mL beaker, and 1.8 g of basic liquid-treated zirconium phosphate was added thereto. After stirring at 80°C for 2 hours, the mixture was filtered and washed in the same manner as above until the electrical conductivity of the filtrate was 100 μS / cm or less. The obtained zirconium phosphate was dried at 120°C for 2 hours under atmospheric pressure and then ground in an agate mortar to obtain acidic liquid-treated zirconium phosphate particles (A-2). Additionally, a HORIBA-manufactured SD-51 pH meter was used to adjust the pH.

[0204] The median diameter of A-2 was measured according to the above method, and the drying loss fraction was measured according to the method shown in (1) below. The results are shown in Table 1.

[0205] In addition, the performance of A-2 as a deodorizer was measured according to the method shown in (2) below. The results are shown in Table 1.

[0206] (1) Measurement of drying reduction rate (%)

[0207] The drying loss fraction of the deodorizing agent particles was measured according to the first method of 4.1.1(1) of JIS K 0067:1992 (Method for testing weight loss and residue of chemical products). After leaving the deodorizing agent particles in a room at a temperature of 25°C and a humidity of 50% for 24 hours, they were heated at 150°C for 2 hours under atmospheric pressure, and the weight before and after heating was measured to calculate the drying loss fraction (Y; unit weight%) of the deodorizing agent from the following formula (2).

[0208] Y={(B0-B1) / B0}×100 (2)

[0209] [In Equation (2), B0 represents the weight of the zirconium phosphate particles (deodorizer) before heating, and B1 represents the weight of the zirconium phosphate particles (deodorizer) after heating.]

[0210] (2) Deodorizing test

[0211] As a deodorization test, the deodorizing ability of the odor components was evaluated by instrument testing as follows.

[0212] First, 10 mg of zirconium phosphate particles were placed in a test bag (Tedler bag), and ammonia gas and dry air were injected into it. After setting the ammonia gas concentration in the test bag to 1000 ppm and the gas volume to 3 L, the ammonia gas reduction rate (X; unit %) in the test bag was calculated by the following formula (1) after being left at room temperature and atmospheric pressure for 10 minutes. In addition, to calculate the ammonia gas reduction rate, a test bag without zirconium phosphate particles was also prepared, and the ammonia gas concentration after 10 minutes was measured.

[0213] X={(A0-A1) / A0)}×100 (1)

[0214] [In Equation (1), A0 represents the ammonia gas concentration of a test bag without zirconium phosphate particles, and A1 represents the ammonia gas concentration of a test bag with zirconium phosphate particles.]

[0215] <Example 2>

[0216] [Sodium hydroxide usage: 1 / 3 molar ratio with respect to the P-OH groups of α-zirconium phosphate, bath ratio: α-zirconium phosphate / NaOH aqueous solution = 1 / 20 weight ratio]

[0217] Basic liquid-treated zirconium phosphate particles (B-1) and acidic liquid-treated zirconium phosphate particles (B-2) were obtained by performing the same procedure as in Example 1, except that 57 g of an aqueous sodium hydroxide solution adjusted to pH 13.1 (1 / 3 molar ratio with respect to the P-OH group of α-zirconium phosphate) was used.

[0218] The median diameter, drying reduction fraction, and deodorizing performance of B-2 were measured and evaluated in the same manner as in Example 1. These results are shown in Table 1.

[0219] <Example 3>

[0220] [Sodium hydroxide usage: 1 / 2 molar ratio with respect to the P-OH groups of α-zirconium phosphate, Bath ratio: α-zirconium phosphate / NaOH aqueous solution = 1 / 20 weight ratio]

[0221] Basic liquid-treated zirconium phosphate particles (C-1) and acidic liquid-treated zirconium phosphate particles (C-2) were obtained by performing the same procedure as in Example 1, except that 57 g of an aqueous sodium hydroxide solution (1 / 2 molar ratio with respect to the P-OH group of α-zirconium phosphate) with the pH adjusted to 13.3 was used.

[0222] The median diameter, drying reduction fraction, and deodorizing performance of C-2 were measured and evaluated in the same manner as in Example 1. These results are shown in Table 1.

[0223] <Example 4>

[0224] [Sodium hydroxide usage: 1 / 1.5 molar ratio with respect to the P-OH groups of α-zirconium phosphate, bath ratio: α-zirconium phosphate / NaOH aqueous solution = 1 / 20 weight ratio]

[0225] Basic liquid-treated zirconium phosphate particles (D-1) and acidic liquid-treated zirconium phosphate particles (D-2) were obtained by performing the same procedure as in Example 1, except that 57 g of an aqueous sodium hydroxide solution adjusted to pH 13.4 (1 / 1.5 molar ratio with respect to the P-OH group of α-zirconium phosphate) was used.

[0226] The median diameter, drying reduction fraction, and deodorizing performance of D-2 were measured and evaluated in the same manner as in Example 1. These results are shown in Table 1.

[0227] <Example 5>

[0228] [Sodium hydroxide usage: 1 / 1 molar ratio with respect to the P-OH groups of α-zirconium phosphate, bath ratio: α-zirconium phosphate / NaOH aqueous solution = 1 / 20 weight ratio]

[0229] Basic liquid-treated zirconium phosphate particles (E-1) and acidic liquid-treated zirconium phosphate particles (E-2) were obtained by performing the same procedure as in Example 1, except that 57 g of an aqueous sodium hydroxide solution adjusted to pH 13.6 (1 / 1 molar ratio with respect to the P-OH group of α-zirconium phosphate) was used.

[0230] The median diameter, drying reduction fraction, and deodorizing performance of E-2 were measured and evaluated in the same manner as in Example 1. These results are shown in Table 1.

[0231] <Example 6>

[0232] [Sodium hydroxide usage: 1 / 3 molar ratio with respect to the P-OH groups of α-zirconium phosphate, bath ratio: α-zirconium phosphate / NaOH aqueous solution = 1 / 5 weight ratio]

[0233] Basic liquid-treated zirconium phosphate particles (F-1) and acidic liquid-treated zirconium phosphate particles (F-2) were obtained by the same method as in Example 1, except that 9 g of α-zirconium phosphate obtained in Preparation Example 1, 9 g of pure water, and 36 g of an aqueous sodium hydroxide solution adjusted to pH 13.8 (1 / 3 molar ratio with respect to the P-OH group of α-zirconium phosphate).

[0234] The median diameter, drying reduction fraction, and deodorizing performance of F-2 were measured and evaluated in the same manner as in Example 1. These results are shown in Table 1.

[0235] <Example 7>

[0236] [Sodium hydroxide usage: 1 / 2 molar ratio with respect to the P-OH groups of α-zirconium phosphate, Bath ratio: α-zirconium phosphate / NaOH aqueous solution = 1 / 5 weight ratio]

[0237] Basic liquid-treated zirconium phosphate particles (G-1) and acidic liquid-treated zirconium phosphate particles (G-2) were obtained by performing the same procedure as in Example 6, except that 36 g of an aqueous sodium hydroxide solution adjusted to pH 13.9 (1 / 2 molar ratio with respect to the P-OH group of α-zirconium phosphate) was used.

[0238] The median diameter, drying reduction fraction, and deodorizing performance of G-2 were measured and evaluated in the same manner as in Example 1. These results are shown in Table 1.

[0239] <Example 8>

[0240] [Sodium hydroxide usage: 1 / 1.5 molar ratio with respect to the P-OH groups of α-zirconium phosphate, bath ratio: α-zirconium phosphate / NaOH aqueous solution = 1 / 5 weight ratio]

[0241] Basic liquid-treated zirconium phosphate particles (H-1) and acidic liquid-treated zirconium phosphate particles (H-2) were obtained by performing the same procedure as in Example 6, except that 36 g of an aqueous sodium hydroxide solution adjusted to pH 14.0 (1 / 1.5 molar ratio with respect to the α-zirconium phosphate P-OH group) was used.

[0242] The median diameter, drying reduction fraction, and deodorizing performance of H-2 were measured and evaluated in the same manner as in Example 1. These results are shown in Table 1.

[0243] <Comparative Example 1>

[0244] [α-Zirconium Phosphate]

[0245] The median diameter, drying loss fraction, and deodorizing performance of the α-zirconium phosphate particles obtained in Preparation Example 1 were measured and evaluated in the same manner as in Example 1. These results are shown in Table 1.

[0246]

[0247] <Example 9>

[0248] 3 wt% of acid-treated zirconium phosphate (G-2) obtained in Example 7 and 97 wt% of polyester resin (manufactured by Unitika Co., Ltd., MA-2101M) dried at 150°C for 12 hours were mixed and fed into an automatic injection molding machine (manufactured by Meiki Seisakusho, model: M-50A II-DM) set to 270°C to produce an injection molding plate of 11 cm × 11 cm × 1 mm. Afterward, this plate was ground using a Wonder Blender (manufactured by Osaka Chemical Co., Ltd., model: WB-1) to obtain a resin composition A containing zirconium phosphate paste. The deodorizing performance was evaluated according to the method shown in (3) Deodorizing Performance Test-2 described below. The results are shown in Table 2.

[0249] <Comparative Example 2>

[0250] 3 wt% of the α-zirconium phosphate used in Comparative Example 1 and 97 wt% of a polyester resin (manufactured by Unitika Co., Ltd., MA-2101M) dried at 150°C for 12 hours were mixed, and a resin composition B containing zirconium phosphate paste was obtained in the same manner as in Example 9. The deodorizing performance was evaluated according to the method shown in (3) Deodorizing Performance Test-2 described below. The results are shown in Table 2.

[0251] (3) Deodorizing Test-2

[0252] 2.4 g of a resin composition containing zirconium phosphate paste was placed in a test bag (Tedler bag), and dry air and ammonia gas were injected therein to set the ammonia gas concentration in the test bag to 100 ppm and the gas volume to 3 L, and then left at room temperature and atmospheric pressure for 1 hour. The ammonia gas reduction rate in the test bag after leaving was calculated according to the above-described formula (1). In addition, A0 in formula (1) refers to the ammonia gas concentration of a test bag without the resin composition containing zirconium phosphate paste, and A1 refers to the ammonia gas concentration of a test bag containing the resin composition containing zirconium phosphate paste.

[0253]

[0254] The disclosure of Japanese Patent Application No. 2020-044208, filed on March 13, 2020, is incorporated herein by reference in its entirety.

[0255] All documents, patent applications, and technical specifications described in this specification are incorporated by reference in this specification to the same extent that each document, patent application, and technical specification is specifically and recorded therein.

[0256] [Industrial Applicability]

[0257] The zirconium phosphate particles of the present disclosure can be preferably used in deodorizers, and since the deodorizer has a fast adsorption rate for basic gases such as ammonia and particularly excellent deodorizing performance for ammonia, it can be additionally used in deodorizing processing compositions, deodorizing resin compositions, and deodorizing fibers.

[0258] In addition, the method for manufacturing zirconium phosphate particles of the present disclosure can provide a method for manufacturing that can improve the deodorizing performance.

Claims

Claim 1 Zirconium phosphate particles, wherein the zirconium phosphate particles have a drying loss fraction (Y; unit weight%) represented by the following formula (2) after heating at 150°C for 2 hours of 5.0 weight% or less, and the zirconium phosphate particles are obtained by contacting α-zirconium phosphate particles represented by the following formula (3) with a basic liquid with a pH of 9 or higher, and then further contacting them with an acidic liquid with a pH of 6 or lower. Y={(B0-B1) / B0}×100 (2)[In formula (2), B0 represents the weight of the zirconium phosphate particles before heating, and B1 represents the weight of the zirconium phosphate particles after heating.]Zr 1-x Hf x H a (PO4) b ·nH2O (3) [In Equation (3), a and b are integers satisfying 3b-a=4, b is 2.0<b≤2.1, x is an integer 0≤x≤0.2, and n is an integer 0≤n≤2.0.] Claim 2 Zirconium phosphate particles according to claim 1, wherein the basic liquid comprises at least one of an alkali metal and an alkaline earth metal. Claim 3 Zirconium phosphate particles, wherein 10 mg of the zirconium phosphate particles and 3 L of air containing 1000 ppm of ammonia gas are placed in a test bag at room temperature and atmospheric pressure and left for 10 minutes, and the ammonia gas reduction rate (X; unit %) represented by the following formula (1) in the test bag containing the zirconium phosphate particles is 50% or more, and the drying reduction fraction (Y; unit weight %) represented by the following formula (2) after heating at 150°C for 2 hours is 5.0 weight% or less. X = {(A0 - A1) / A0} × 100 (1) [In formula (1), A0 represents the ammonia gas concentration of a test bag without zirconium phosphate particles, and A1 represents the ammonia gas concentration of a test bag containing zirconium phosphate particles [Meaning.] Y={(B0-B1) / B0}×100 (2)[In Equation (2), B0 represents the weight of zirconium phosphate particles before heating, and B1 represents the weight of zirconium phosphate particles after heating.] Claim 4 Zirconium phosphate particles according to claim 1, wherein the median diameter of the primary particles is 0.1 to 10 μm. Claim 5 delete Claim 6 A basic gas deodorizer comprising zirconium phosphate particles as described in paragraph 1 or 3. Claim 7 A basic gas deodorizer for fibers comprising zirconium phosphate particles as described in paragraph 1 or 3. Claim 8 A basic gas deodorizer for fiber dough comprising zirconium phosphate particles as described in paragraph 1 or 3. Claim 9 A composition for processing basic gas deodorization comprising zirconium phosphate particles as described in claim 1 or 3. Claim 10 A basic gas deodorizing resin composition comprising zirconium phosphate particles as described in claim 1 or 3. Claim 11 Basic gas deodorizing fiber comprising zirconium phosphate particles as described in paragraph 1 or 3. Claim 12 A basic gas deodorizing fiber according to claim 11, comprising at least one fiber selected from the group consisting of polyester, polyurethane, nylon, rayon, cotton, acrylic, aramid, vinylon, polyethylene, and polypropylene. Claim 13 A method for manufacturing zirconium phosphate particles as described in claim 1, comprising contacting zirconium α-phosphate particles with a basic liquid with a pH of 9 or higher, and then further contacting them with an acidic liquid with a pH of 6 or lower. Claim 14 A method for manufacturing zirconium phosphate particles according to claim 13, wherein the basic liquid comprises at least one of an alkali metal and an alkaline earth metal. Claim 15 A method for manufacturing a basic gas deodorizing resin composition comprising mixing zirconium phosphate particles and a resin obtained by the manufacturing method described in paragraph 13. Claim 16 A method for preparing a basic gas deodorizing resin composition, comprising contacting zirconium phosphate particles with a basic liquid with a pH of 9 or higher, then further contacting them with an acidic liquid with a pH of 6 or lower to obtain liquid-treated zirconium phosphate particles, and mixing the liquid-treated zirconium phosphate particles and the resin. Claim 17 A method for manufacturing a basic gas deodorizing fiber, comprising spinning a basic gas deodorizing resin composition obtained by the manufacturing method described in paragraph 16. Claim 18 A method for preparing a basic gas deodorizing resin composition, comprising contacting a resin containing zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then contacting it with an acidic liquid with a pH of 6 or lower. Claim 19 A method for manufacturing a basic gas deodorizing resin composition, wherein, in claim 18, the zirconium phosphate particles are those described in claim 1 or 3. Claim 20 A method for manufacturing a basic gas deodorizing fiber comprising contacting a fiber containing zirconium phosphate particles with a basic liquid with a pH of 9 or higher, and then contacting it with an acidic liquid with a pH of 6 or lower. Claim 21 A method for manufacturing a basic gas deodorizing fiber, wherein, in claim 20, the zirconium phosphate particles are those described in claim 1 or 3.

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