Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/16—Oxyacids of phosphorus; Salts thereof
  • C01B25/26—Phosphates
  • C01B25/37—Phosphates of heavy metals
  • C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L9/00—Disinfection, sterilisation or deodorisation of air
  • A61L9/01—Deodorant compositions
  • A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
  • B01J20/0211—Compounds of Ti, Zr, Hf
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
  • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
  • B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/24—Chromium, molybdenum or tungsten
  • B01J23/30—Tungsten
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/16—Oxyacids of phosphorus; Salts thereof
  • C01B25/26—Phosphates
  • C01B25/37—Phosphates of heavy metals
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
  • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
  • D06M11/71—Salts of phosphoric acids
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
  • A61L2101/02—Inorganic materials
  • A61L2101/16—Inorganic materials containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
  • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

• the present disclosure includes a method for producing zirconium phosphate particles, zirconium phosphate particles, a deodorant, a deodorant for fibers, a deodorant for kneading fibers, a composition for deodorant processing, a deodorant resin composition, and a deodorant.
• odorous gases compounds that adsorb odorous gases
• Compounds that adsorb odorous gases include, for example, zirconium phosphate.
• Patent Document 1 describes "an adsorption filter that adsorbs ammonia gas, wherein the adsorption filter contains 0.5 to 4 weights of ⁇ -type zirconium phosphate with respect to 1 weight part of fibrillated fibers. and a propylene glycol monomethyl ether acetate (PGMEA) decomposition rate of less than 4%”.
• ⁇ -zirconium phosphate having a median diameter of 0.2 to 0.7 ⁇ m, a maximum particle diameter of 5.0 ⁇ m or less, and a D10 diameter of 0.1 ⁇ m or more, and/or A fiber deodorant containing ⁇ -titanium phosphate.” has been proposed.
• Patent Document 3 "(i) a mixture of a zirconium compound and a carboxylic acid having two or more carboxyl groups or a salt thereof and a phosphoric acid compound added to a liquid containing (ii) a zirconium compound (as Zr) , a carboxylic acid compound (as C 2 O 4 ) and a phosphoric acid compound (as PO 4 ) in the weight ratio triangular component diagram shown in FIG. 10), C (33, 10, 57) and D (2, 3, 95), and (iii) reacting the mixture in the region surrounded by the straight line connecting each point at pH 10 or less.
• Patent Document 4 proposes "zirconium phosphate particles obtained by contacting ⁇ -zirconium phosphate particles with a basic liquid having a pH of 9 or higher and then further contacting them with an acidic liquid having a pH of 6 or lower.”
• Patent Document 1 when zirconium phosphate is supported on fibers to form deodorant fibers, a large amount of zirconium phosphate must be supported on the fibers. Moreover, Patent Documents 2 and 3 do not describe or suggest a method for improving the odor gas adsorption speed of zirconium phosphate. Accordingly, an object of the present disclosure is to provide a method for producing zirconium phosphate particles with excellent deodorant performance.
• the zirconium phosphate particles described in Patent Document 4 have a high absorption rate of odorous gases.
• the ⁇ -zirconium phosphate particles used as a raw material for the zirconium phosphate particles described in Patent Document 4 are generally obtained by filtering, washing, and drying the precipitate obtained by mixing and aging the raw materials. can get.
• the production of zirconium phosphate particles described in Patent Document 4 is carried out by contacting raw material ⁇ -zirconium phosphate particles with a basic liquid and an acidic liquid under predetermined conditions, followed by filtering, washing with water, drying, and pulverization.
• an object of the present disclosure is to provide a method for producing zirconium phosphate particles that can obtain zirconium phosphate particles that adsorb odorous gases in a short process.
• ⁇ 1> a first step of mixing a zirconium compound, a phosphorus compound, a basic compound, and a solvent to obtain a solution containing zirconium phosphate; and a second step of heating and aging the solution containing the zirconium phosphate,
• the basic compound contains at least one selected from the group consisting of alkali metals and alkaline earth metals.
• X ⁇ (A 0 ⁇ A 1 )/A 0 ) ⁇ 100 (1)
• a 0 Ammonia gas concentration in a test bag containing no zirconium phosphate particles
• a 1 Ammonia gas concentration in a test bag containing zirconium phosphate particles.
• ⁇ 5> A deodorant containing the zirconium phosphate particles according to ⁇ 3> or ⁇ 4>.
• ⁇ 6> A fiber deodorant containing the zirconium phosphate particles according to ⁇ 3> or ⁇ 4>.
• ⁇ 7> A fiber-kneaded deodorant containing the zirconium phosphate particles according to ⁇ 3> or ⁇ 4>.
• ⁇ 8> A deodorizing composition comprising the zirconium phosphate particles according to ⁇ 3> or ⁇ 4>.
• ⁇ 9> A deodorizing resin composition containing the zirconium phosphate particles according to ⁇ 3> or ⁇ 4>.
• a method for producing zirconium phosphate particles with excellent deodorant performance is provided. Further, according to the present disclosure, there is provided a method for producing zirconium phosphate particles that can obtain zirconium phosphate particles that adsorb odorous gases in a short process.
• Each component may contain a plurality of applicable substances.
• the total amount of the multiple types of substances present in the composition means quantity.
• the term "step" includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
• a method for producing zirconium phosphate particles according to the present disclosure includes a first step of obtaining a solution containing zirconium phosphate by mixing a zirconium compound, a phosphorus compound, a basic compound, and a solvent, and heating the solution containing zirconium phosphate. and a second step of aging.
• the acid concentration of the solution containing zirconium phosphate after the second step (hereinafter also simply referred to as “acid concentration”) is 0.5 mol/kg or more and 1.55 mol or more. / kg or less.
• zirconium phosphate particles that adsorb odorous gases can be obtained in a short process with the above configuration. The reason is presumed as follows.
• an amorphous zirconium phosphate gel is produced when the zirconium compound and the phosphorus compound are mixed, and the crystallization of the amorphous zirconium phosphate gel proceeds in the heat aging in the second step, resulting in a layered structure. become particles.
• the added basic compound dissolves gels and crystals without being incorporated between the layers of zirconium phosphate, forming crystal defects.
• Contact with the odorous gas adsorbed between the layers is also possible from the formed crystal defect part, so the contact area with the odorous gas increases compared to the case where the crystal defect is not included, so the adsorption speed is improved.
• the method for producing zirconium phosphate particles according to the present disclosure can obtain zirconium phosphate particles that adsorb odorous gases in a short process with the above configuration. Details of each step of the method for producing zirconium phosphate particles according to the present disclosure will be described below.
• the first step is to obtain a solution containing zirconium phosphate by mixing a zirconium compound, a phosphorus compound, a basic compound, and a solvent.
• a zirconium compound is a compound containing zirconium. From the viewpoint of reactivity and availability, the zirconium compound is preferably a salt containing zirconium. Salts containing zirconium include zirconium nitrate, zirconium acetate, zirconium sulfate, zirconium carbonate, basic zirconium sulfate, zirconium oxysulfate, and zirconium oxychloride.
• the zirconium-containing salt is selected from the group consisting of zirconium nitrate, zirconium acetate, zirconium sulfate, zirconium carbonate, basic zirconium sulfate, zirconium oxysulfate, and zirconium oxychloride. At least one is preferable, and zirconium oxychloride is more preferable.
• a phosphorus compound is a compound containing phosphorus.
• the phosphorus compound is preferably at least one selected from the group consisting of phosphoric acid and phosphates.
• Phosphates include sodium phosphate, potassium phosphate, ammonium phosphate and the like.
• phosphoric acid is more preferable from the viewpoint of reactivity and availability.
• a basic compound is a compound that, when dissolved in water, generates hydroxide ions (OH ⁇ ) in an aqueous solution.
• Examples of basic compounds include, but are not limited to, ammonia, amines, quaternary ammonium hydroxides, alkali metal hydroxides, alkaline earth metal hydroxides, and the like.
• alkali metals refer to lithium, sodium, potassium, rubidium, cesium, and francium.
• alkaline earth metals refer to beryllium, magnesium, calcium, strontium, barium, and radium.
• Amines include primary amines, secondary amines, and tertiary amines.
• primary amines include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine and the like.
• secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine and the like.
• Tertiary amines include, for example, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine and the like.
• the quaternary ammonium hydroxide include tetramethylammonium hydroxide.
• Alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and francium hydroxide.
• Alkaline earth metal hydroxides include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and radium hydroxide.
• the basic compound is preferably at least one selected from the group consisting of alkali metals and alkaline earth metals. It is more preferably at least one selected from the group consisting of magnesium and calcium hydroxide, and more preferably sodium hydroxide.
• the solvent is not particularly limited, and includes water and organic solvents, which can be used alone or in combination.
• water include distilled water, ion-exchanged water, ultrafiltered water, and pure water.
• organic solvents include ester solvents such as methyl acetate and ethyl acetate; ketone solvents such as methyl ethyl ketone and methyl isopropyl ketone; aliphatic hydrocarbon solvents such as hexane and cyclohexane; and alcohol solvents such as methanol and ethanol. mentioned. From the viewpoint of ease of handling and reactivity, water is preferred as the solvent.
• the oxalic acid compound In the first step, it is preferable to mix the oxalic acid compound together with the zirconium compound, the phosphorus compound, the basic compound, and the solvent. Addition of the oxalic acid compound facilitates the acceleration of the reaction between the zirconium compound and the phosphoric acid compound.
• the oxalic acid compound includes oxalic anhydride, oxalic acid hydrate, oxalate and the like.
• oxalic acid hydrates include oxalic acid dihydrate.
• oxalates include alkali metal salts of oxalic acid, alkaline earth metal salts of oxalic acid, and ammonium oxalate. From the viewpoint of improving reactivity, the oxalic acid compound is preferably oxalic acid hydrate.
• the first step preferably mixes the acidic compound together with the zirconium compound, the phosphorus compound, the basic compound, and the solvent.
• An acidic compound is a compound that generates hydrogen ions (H + ) in an aqueous solution when dissolved in water.
• the acidic compound is preferably an inorganic acid.
• Inorganic acids are acids that do not contain carbon atoms. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, hydroiodic acid, hydrobromic acid, chloric acid, bromic acid, iodic acid, perchloric acid, perbromic acid, tetrafluoroboric acid, hexafluorophosphoric acid, and the like. be done.
• the inorganic acid is preferably at least one selected from the group consisting of hydrochloric acid having an acid dissociation index (pKa) of 0 or less, sulfuric acid, and nitric acid, and is hydrochloric acid. is more preferred.
• the order of adding the zirconium compound, the phosphorus compound, the basic compound and the solvent in the first step is not particularly limited, but from the viewpoint of controlling the particle size of the zirconium phosphate particles, the basic compound should be added last while stirring. is preferred.
• the solvent is added, and the phosphorus compound and the zirconium compound are added under stirring, and then the basic compound is added.
• the solvent is added and the phosphorus compound, the zirconium compound, the oxalic acid compound, the phosphorus compound, the zirconium compound, the oxalic acid compound, and the And it is preferable to add the basic compound after adding the acidic compound.
• the solvent is added and the oxalic acid compound, the acidic It is more preferable to add the compound, the phosphorus compound, the zirconium compound, and the basic compound in this order.
• the solution containing zirconium phosphate is excellently stirred, and it is possible to increase the solid content concentration (hereinafter also simply referred to as “solid content concentration”) in the reaction solution before the addition of the basic compound described later. is. Therefore, it is possible to increase the amount of zirconium phosphate particles obtained per unit charge (for example, unit volume or unit weight of the charged reaction liquid) (hereinafter also referred to as the acquisition rate), thereby improving productivity. can.
• the first step after adding raw materials other than basic compounds (referring to zirconium compounds, phosphorus compounds, solvents, oxalate compounds, and acidic compounds in this paragraph) to before adding basic compounds Time (hereinafter also referred to as "interval before addition of basic compound") may affect the particle size of the resulting zirconium phosphate particles.
• a gel containing amorphous zirconium phosphate results upon the addition of materials other than the basic compound. If the interval until the addition of the basic compound is long, the gel containing amorphous zirconium phosphate is sheared by stirring, and the particle size of the gel becomes smaller. As the particle size of the gel becomes smaller, the particle size of the resulting zirconium phosphate particles also becomes smaller. In other words, when the interval until the addition of the basic compound is long, the particle size of the obtained zirconium phosphate particles tends to be small.
• the interval before addition of the basic compound is preferably 0 minutes or more and 150 minutes or less. minutes or more and 130 minutes or less, and more preferably 2 minutes or more and 125 minutes or less.
• the order of addition of the solvent and raw materials other than the basic compound is not particularly limited, and can be added in any order. It is possible to obtain zirconium phosphate particles that are excellent in the rate of adsorption of odorous gases.
• the zirconium compound is added last in the order of adding the raw materials other than the solvent and the basic compound.
• the reaction liquid at the time of thickening that is, at least the zirconium compound, the phosphorus compound, the basic compound, and a solvent (the same shall apply hereinafter)
• the temperature of the reaction solution tends to become non-uniform.
• part of the reaction liquid is locally heated, and the solvent in the reaction liquid may bump.
• the solvent bumps the reaction liquid splatters, and along with this, the solid content in the reaction liquid may adhere to the lid of the reaction vessel, etc., which may cause a decrease in the yield. Therefore, it becomes difficult to increase the solid content concentration.
• the reaction solution can be easily stirred and the temperature uniformity of the reaction solution can be improved. easier. Therefore, local heating of the reaction liquid is suppressed, the solvent in the reaction liquid is less likely to boil, the solid content concentration can be increased, and the yield can be increased.
• the method of adding the zirconium compound, the phosphorus compound, the basic compound and the solvent in the first step is not particularly limited. From the viewpoint of controlling the particle size of the zirconium phosphate particles obtained by improving the uniformity of the reaction solution, the zirconium compound, the phosphorus compound, and the basic compound are selected from a solution containing a zirconium compound, a solution containing a phosphorus compound, and a solution containing a basic compound. Moreover, when adding an acidic compound in the first step, it is preferable to add the acidic compound as a solution containing the acidic compound from the viewpoint of availability.
• zirconium compound added in terms of zirconium oxychloride octahydrate is based on the mass of the entire raw material (in this paragraph, zirconium compound (in terms of zirconium oxychloride octahydrate), phosphorus compound, basic compound, oxalic acid compound (oxalic It is preferably 20% by mass or more and 45% by mass or less, more preferably 23% by mass or more and 42% by mass or less, based on the acid dihydrate) and the total mass of the acidic compound). It is preferably 26% by mass or more and 39% by mass or less, more preferably.
• zirconium oxychloride octahydrate means that the zirconium compound is assumed to be zirconium oxychloride octahydrate.
• "Calculated as oxalic acid dihydrate” means that the oxalic acid compound is assumed to be oxalic acid dihydrate.
• the ratio of the amount of the phosphorus compound added to the amount of the zirconium compound added is more than 1.9 and 3.0 or less on a molar basis. , more preferably 1.95 or more and 2.9 or less, and even more preferably 2.0 or more and 2.6 or less.
• the amount of the basic compound added is preferably such that the acid concentration of the solution containing zirconium phosphate after the second step is 0.5 mol/kg or more and 1.55 mol/kg or less, and is preferably 0.6 mol/kg or more. More preferably, the amount is 1.5 mol/kg or less, and particularly preferably 0.9 mol/kg or more and 1.3 mol/kg or less.
• zirconium phosphate particles with few aggregates can be easily obtained.
• the particle size of the zirconium phosphate particles does not become too large, and when the zirconium phosphate particles are used as a fiber deodorant, for example, fiber breakage caused by containing the zirconium phosphate particles is easily suppressed.
• the crystal structure of the resulting zirconium phosphate particles is less likely to be excessively disturbed.
• the amount of the solvent to be added is not particularly limited as long as the amount is such that the reaction solution can be stirred. It is preferably 3% by mass or more, and more preferably 5% by mass or more and 12% by mass or less in consideration of efficiency such as economy.
• the ratio of the added amount of the oxalic acid compound converted to oxalic acid dihydrate to the added amount of the zirconium compound converted to zirconium oxychloride octahydrate is preferably 0.1 or more and 10.0 or less, more preferably 0.5 or more and 6.0 or less, and 1.0 or more and 3.5 or less on a molar basis. More preferred.
• the ratio of the added amount of the acidic compound to the added amount of the zirconium compound in terms of zirconium oxychloride octahydrate is 0 on a molar basis. .1 or more and 20.0 or less, more preferably 0.5 or more and 10.0 or less, and even more preferably 1.0 or more and 5.0 or less.
• the temperature of the reaction solution in the first step is not particularly limited. It is more preferable to set the temperature to 70°C or less.
• the temperature control of the reaction solution can be performed by connecting a thermocouple inserted in the baffle to a temperature controller.
• a thermocouple for example, a K-sheath type can be used, and as the temperature controller, for example, a digital multi-temperature controller (TXN-700B) manufactured by AS ONE can be used.
• the raw materials when adding raw materials (referring to zirconium compounds, phosphorus compounds, basic compounds, solvents, oxalic acid compounds, and acidic compounds in this paragraph) to the reactor, the raw materials are added in a predetermined order. is preferred. From the viewpoint of improving the uniformity of the raw materials in the reaction liquid, it is preferable to add the raw materials while the stirring device is activated.
• the second step is a step of heating and aging a solution containing zirconium phosphate.
• Heat aging means holding the solution containing zirconium phosphate obtained in the first step at a temperature of 25° C. or higher for a certain period of time.
• the temperature of the solution containing zirconium phosphate is preferably 90°C or higher, more preferably 95°C or higher. Hydrothermal conditions may be used, and in that case, the temperature of the solution containing zirconium phosphate is preferably 130° C. or lower from the viewpoint of suppressing production costs.
• temperature control of the solution containing zirconium phosphate can be performed by connecting a thermocouple inserted in the baffle to a temperature controller.
• a thermocouple for example, a K-sheath type can be used
• the temperature controller for example, a digital multi-temperature controller (TXN-700B) manufactured by AS ONE can be used.
• the time for the second step is preferably 1 hour or more and 24 hours, and preferably 4 hours or more and 18 hours or less.
• the second step is preferably performed while stirring the solution containing zirconium phosphate.
• a reactor equipped with the above-described stirrer and baffle can be used.
• the acid concentration of the solution containing zirconium phosphate after the second step is 0.5 mol/kg or more and 1.55 mol/kg or less.
• the acid concentration is preferably 0.6 mol/kg or more and 1.5 mol/kg or less from the viewpoint of improving the isolation yield and odorous gas adsorption rate.
• the "acid concentration" as used herein can be obtained by neutralizing and titrating the filtrate obtained by filtering the solution containing zirconium phosphate after the second step, for example, with a 1.0 mol/L sodium hydroxide solution. It can be expressed as titratable acidity (mol/kg) per unit weight of the filtrate. Procedures for measuring the acid concentration are described in Examples below.
• the method for producing zirconium phosphate particles according to the present disclosure may include a washing step in addition to the first step and the second step.
• the washing step includes, for example, a step of washing the zirconium phosphate particles with water.
• a method for washing the zirconium phosphate particles with water for example, there is a method of contacting the zirconium phosphate particles with water and then filtering. At this time, it is preferable to wash the zirconium phosphate particles with water until the electric conductivity of the filtrate becomes 100 ⁇ S/cm or less.
• the electrical conductivity of the filtrate is a value measured using an electrical conductivity measuring device.
• a portable electrical conductivity meter manufactured by Horiba Advanced Techno can be used.
• the method for producing zirconium phosphate particles according to the present disclosure may include other steps in addition to the first step, second step, and washing step.
• Other processes include, for example, a drying process and a crushing process.
• the drying step is a step of drying the zirconium phosphate particles.
• the drying step includes, for example, a step of drying the zirconium phosphate particles by heating the zirconium phosphate particles.
• the heating temperature of the zirconium phosphate particles is, for example, preferably 50° C. or higher and 300° C. or lower, more preferably 80° C. or higher and 200° C. or lower, and particularly preferably 100° C. or higher and 150° C. or lower.
• the temperature in the heating method using a non-contact heating device represents the ambient temperature.
• the temperature in the heating method using a contact heating device represents the temperature of the article in direct contact with the zirconium phosphate particles.
• the crushing step is a step of crushing the zirconium phosphate particles.
• the crushing step includes, for example, a step of crushing zirconium phosphate particles with a device such as a jet mill, ball mill, hammer mill, rod mill, or rotor speed mill.
• the zirconium phosphate particles of the present disclosure are preferably produced by the method for producing zirconium phosphate particles of the present disclosure.
• the zirconium phosphate particles of the present disclosure have an ammonia gas reduction rate (X; unit %) represented by the following formula (1) of 50% or more, and a proportion of particles having a particle size of 5 ⁇ m or more is 20% or less.
• X ⁇ (A 0 ⁇ A 1 )/A 0 ) ⁇ 100 (1)
• a 0 Ammonia gas concentration in a test bag containing no zirconium phosphate particles
• a 1 Ammonia gas concentration in a test bag containing zirconium phosphate particles.
• the zirconium phosphate particles of the present disclosure preferably contain zirconium phosphate represented by general formula A below.
• the zirconium phosphate particles of the present disclosure are obtained by putting 10 mg of zirconium phosphate particles and 3 L of air containing 1000 ppm of ammonia gas into a test bag, , 101 kPa) for 10 minutes, 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.
• the zirconium phosphate particles are preferred, and zirconium phosphate particles with a content of 55% or more are more preferred.
• the material of the test bag used for determining the ammonia gas reduction rate in the present disclosure is not particularly limited, and known materials can be used.
• Examples of the material of the test bag include polyvinyl alcohol, polyvinylidene fluoride, polyvinyl fluoride, ethylene tetrafluoride/propylene hexafluoride copolymer, and polyester.
• a well-known method can be applied to the detection method of the concentration of ammonia in the present disclosure, and there is no particular limitation.
• a gas sampler and a sensing tube can be used to measure the concentration of ammonia gas.
• a gas sampler is fitted with a detection tube for ammonia detection with a syringe needle set, inserted into a test bag, and ammonia gas is sucked by the suction force of the gas sampler and adsorbed to the detection tube. It can be measured by reading the density value from the color change.
• the ammonia gas reduction rate represented by the above formula (1) of the zirconium phosphate particles of the present disclosure is more preferably 50% or more, and is 55% or more. is more preferred.
• the zirconium phosphate particles of the present disclosure preferably have an average particle size of 0.2 ⁇ m or more and 20 ⁇ m or less, more preferably 0.4 ⁇ m or more and 10 ⁇ m or less. More preferably, it is 0.6 ⁇ m or more and 5 ⁇ m or less.
• the average particle size of the zirconium phosphate particles is measured by laser diffraction particle size distribution measurement.
• a laser diffraction particle size distribution measuring device for example, a laser diffraction particle size distribution measuring device “Mastersizer 2000” manufactured by Malvern can be used. In the measurement, 120 ml of water, which is a dispersion medium, is placed in a circulation unit attached to the apparatus, and while stirring and circulating at 2450 rpm, zirconium phosphate particles are added so that the laser transmittance is in the range of 9% or more and 12% or less. Measurement is performed under the conditions of 2.4 to obtain a volume-based particle size distribution. Based on the measured particle size distribution, draw a volume-based cumulative undersize distribution from the smaller diameter side. The average particle size is defined as the particle size at which 50% of the integrated undersize distribution is obtained.
• the proportion of zirconium phosphate particles having a particle size of 5 ⁇ m or more is preferably 0% or more and 30% or less, more preferably 0% or more and 20% or less. More preferably, it is 0% or more and 10% or less.
• the content is particularly preferably 0% or more and 5% or less from the viewpoint of suppressing yarn breakage during spinning.
• the ratio of zirconium phosphate particles having a particle size of 5 ⁇ m or more is calculated as follows.
• the cumulative undersize distribution is drawn in the same manner as the procedure for measuring the average particle size of the zirconium phosphate particles described above. Then, the ratio of zirconium phosphate particles having a particle size of 5 ⁇ m or more is calculated in the cumulative distribution of undersize.
• the zirconium phosphate particles of the present disclosure preferably have a primary particle diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, more preferably 0.2 ⁇ m or more and 3 ⁇ m or less. More preferably, it is 0.2 ⁇ m or more and 1.5 ⁇ m or less.
• the zirconium phosphate particles of the present disclosure are kneaded into fibers, the number of zirconium phosphate particles contained in the fibers increases, and the deodorizing effect tends to increase. It is preferably 0.2 ⁇ m or more and 1.5 ⁇ m or less.
• the primary particle size of the zirconium phosphate particles is obtained by measuring the zirconium phosphate particles by laser diffraction particle size distribution measurement.
• the laser diffraction particle size distribution measuring device for example, a laser diffraction particle size distribution measuring device “Mastersizer 2000” manufactured by Malvern can be used. In the measurement, 120 ml of water, which is a dispersion medium, is placed in the circulation unit attached to the apparatus, and while stirring and circulating at 2450 rpm, zirconium phosphate particles are added so that the laser transmittance is in the range of 9% or more and 12% or less.
• the dispersion is performed under conditions of a refractive index of 2.4 to obtain a volume-based particle size distribution. Based on the measured particle size distribution, draw a volume-based cumulative undersize distribution from the smaller diameter side.
• the primary particle size is defined as the particle size at which 50% of the integrated undersize distribution is obtained.
• the zirconium phosphate particles according to the present disclosure are preferably used to adsorb odorous gases.
• the odorous gas is preferably a basic gas.
• a basic gas refers to a gas of a volatile basic substance at normal temperature and normal pressure, that is, at 25° C. and 1 atm.
• a basic substance is one whose aqueous solution has a pH of 7 or more.
• Examples of basic gases include alkylamines such as ammonia, trimethylamine and dimethylamine; nitrogen-containing heteroaromatic compounds such as pyridine; heterocyclic amines such as piperidine; aromatic amines such as aniline; mentioned.
• the zirconium phosphate particles according to the present disclosure are preferably used as a raw material for deodorants.
• the deodorant according to the present disclosure contains the zirconium phosphate particles according to the present disclosure, and preferably contains the zirconium phosphate particles according to the present disclosure as a main component.
• the main component refers to a content of 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, relative to the entire deodorant.
• the deodorant according to the present disclosure may contain an additive (hereinafter also referred to as "deodorant additive") in addition to the zirconium phosphate according to the present disclosure.
• deodorant additives include solvents, pH adjusters, preservatives, antibacterial agents, bactericides, antioxidants, ultraviolet absorbers, pigments, fragrances, and deodorant components other than zirconium phosphate according to the present disclosure. , surfactants, thickeners and the like.
• the form of the deodorant according to the present disclosure is not particularly limited, and includes any form such as powder, paste, solid, gel, and liquid at room temperature (25°C).
• the method for producing the deodorant according to the present disclosure is not particularly limited, and includes a method of adding deodorant additives as necessary to the zirconium phosphate particles according to the present disclosure.
• the deodorant according to the present disclosure is preferably added to materials (for example, resins, fibers, solutions, etc.) for the purpose of imparting a function of adsorbing odorous gases to the materials.
• the deodorant for fibers according to the present disclosure is a deodorant that imparts a function of adsorbing odorous gases to the fibers by being added to the fibers.
• composition of the fiber deodorant according to the present disclosure, the content, form, and production method of the zirconium phosphate particles are the composition of the deodorant, the content, form, and production method of the zirconium phosphate particles, according to the present disclosure. is preferably the same as
• a method for imparting a function of adsorbing odorous gases to fibers using the fiber deodorant according to the present disclosure is, for example, as follows.
• a method of applying the fiber deodorant according to the present disclosure to the spun fiber (hereinafter also referred to as a coating method), adding the fiber deodorant according to the present disclosure to the resin, and spinning it. and a method of making a fiber (hereinafter also referred to as a kneading method).
• the fiber deodorant used in the kneading method is referred to as the fiber kneading deodorant.
• the deodorant fibers produced by the kneading method have high adhesion between the fibers and the deodorant, detachment of the deodorant from the deodorant fibers is easily suppressed. Therefore, the deodorizing fiber produced by the kneading method is more likely to maintain the function of adsorbing odorous gases compared to the deodorizing fiber produced by the coating method.
• the deodorant fiber produced by the kneading method contains the deodorant inside the fiber. The deodorant contained inside the fibers does not easily come into contact with air, and therefore does not readily adsorb odorous gases.
• the deodorant fiber produced by the kneading method has a slower adsorption speed of odorous gases than the deodorant fiber produced by the coating method. Prone.
• the zirconium phosphate particles according to the present disclosure have a high adsorption speed of odorous gases, deodorant fibers having a practically acceptable adsorption speed of odorous gases can be obtained even with deodorant fibers produced by the kneading method. be able to.
• the deodorant for kneading fibers of the present disclosure is kneaded into a resin that has been melted by heating or a solution obtained by dissolving the resin in a solvent, A method of spinning this; a method of preparing a masterbatch resin containing a high concentration of the deodorant for kneading fibers of the present disclosure, followed by mixing and melting with the resin, and spinning;
• the resin used in the kneading method is not particularly limited, and resins contained in known fibers are applied.
• resins used in the kneading method include polyester, polyurethane, nylon, rayon, acrylic resin, aramid, vinylon, polyethylene, and polypropylene.
• Polyurethane, polyester, nylon, acrylic resin and polyethylene are preferred.
• a deodorizing fiber according to the present disclosure comprises zirconium phosphate particles according to the present disclosure.
• the deodorant fiber according to the present disclosure preferably contains at least one fiber selected from the group consisting of polyester, polyurethane, nylon, rayon, cotton, acrylic, aramid, vinylon, polyethylene, and polypropylene.
• the content of zirconium phosphate particles in the deodorant fiber according to the present disclosure is not particularly limited. In general, if the content of zirconium phosphate particles is increased, the adsorption speed of odorous gases can be improved and the ability to adsorb odorous gases can be maintained.
• the content of the zirconium phosphate particles is 0.1% by mass or more with respect to the mass of the entire deodorant fiber, from the viewpoints of economic efficiency and the fact that the strength of the resin decreases when it is contained in a certain amount or more. 0 mass % or less, more preferably 0.3 mass % or more and 3.0 mass % or less, and even more preferably 0.5 mass % or more and 2.0 mass % or less.
• a method of imparting a function of adsorbing odorous gases to the fiber using the fiber deodorant according to the present disclosure described above can be applied.
• a method of applying a deodorizing composition to the fiber can be applied.
• the deodorant fiber according to the present disclosure can be used in various fields that require deodorant properties, such as underwear, stockings, socks, futons, duvet covers, floor cushions, blankets, carpets, curtains, sofas, car seats, It can be used in many textile products such as air filters and nursing care clothing.
• a deodorant processing composition according to the present disclosure includes zirconium phosphate particles according to the present disclosure.
• the deodorant processing composition according to the present disclosure contains at least one selected from the group consisting of resins, dispersants, and solvents.
• resins applied to the deodorant processing composition according to the present disclosure include ethylene/vinyl acetate copolymer, ethylene/vinyl chloride copolymer, vinyl chloride/vinyl acetate copolymer, polyvinyl acetate, polyvinyl Vinyl chloride, 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
• Dispersants applied to the deodorant processing composition according to the present disclosure include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like.
• the solvent applied to the deodorant processing composition according to the present disclosure is not particularly limited, and includes water and organic solvents.
• the solvent is preferably at least one selected from the group consisting of water and lower alcohols (methanol, ethanol, 2-propanol, etc.).
• the deodorizing composition according to the present disclosure may contain additives (hereinafter also referred to as "additives for deodorizing composition") in addition to zirconium phosphate particles, resins, dispersants, and solvents. good.
• additives in the deodorant processing composition include pH adjusters, preservatives, antibacterial agents, bactericides, antioxidants, ultraviolet absorbers, dyes, fragrances, and deodorants other than zirconium phosphate according to the present disclosure. Ingredients, thickeners, and the like.
• the content of the zirconium phosphate particles in the deodorizing composition according to the present disclosure is preferably less than 90% by mass, and 0.5% by mass or more, relative to the total mass of the deodorizing composition. It is more preferably 85% by mass or less.
• the form of the deodorant processing composition according to the present disclosure is not particularly limited, and includes any form such as powder, paste, solid, gel, and liquid at room temperature (25°C).
• the method for producing the deodorant processing composition according to the present disclosure is not particularly limited, and at least one selected from the group consisting of a resin, a dispersant, and a solvent is added to the zirconium phosphate particles according to the present disclosure.
• a method of adding and mixing can be mentioned.
• the deodorant processing composition according to the present disclosure is spread on fibers, moldings (e.g., filters, films, etc.) that require deodorant properties, or products that require deodorant properties, It is preferably used for the purpose of imparting a function of adsorbing odorous gases to fibers, moldings or products.
• Molded articles requiring deodorizing properties include, for example, filters and films.
• products that require deodorizing properties include household appliances such as air purifiers, refrigerators, and air conditioners; general household items such as trash cans, drainers, wraps, and sponges; various nursing care products such as portable toilets, wallpaper, toilet bowls, House building materials such as toilet seats, kitchen counters, ventilation fan filters, paints; vehicle interiors, pet products, and daily necessities.
• a deodorant resin composition according to the present disclosure includes zirconium phosphate particles according to the present disclosure. Moreover, the deodorant resin composition according to the present disclosure contains a resin.
• resins applicable to the deodorant resin composition according to the present disclosure include polypropylene, polyethylene, acrylonitrile-butadiene-styrene (ABS), polyester, polyurethane, nylon, polystyrene, polycarbonate, acrylic resin, vinyl chloride resin, and the like. mentioned.
• the deodorant resin composition may contain additives (hereinafter also referred to as "additives of the deodorant resin composition") in addition to the zirconium phosphate particles according to the present disclosure and the resin.
• additives for the deodorant resin composition additives generally used for resins can be used.
• additives for the deodorant resin composition include antioxidants, ultraviolet absorbers, flame retardants, flame retardant aids, lubricants, fillers, antistatic agents, pigments, dyes, and the like.
• the content of the zirconium phosphate particles in the deodorant resin composition according to the present disclosure is appropriately adjusted according to the use of the deodorant resin composition.
• the content of the zirconium phosphate particles in the deodorant resin composition according to the present disclosure is preferably, for example, 0.1% by mass or more and 50% by mass or less with respect to the mass of the entire deodorant processing composition. .
• the shape of the deodorant resin composition according to the present disclosure is not particularly limited, and includes any shape such as sheet-like, block-like, plate-like, and spherical.
• a method for producing the deodorant resin composition according to the present disclosure includes, for example, a method of mixing the zirconium phosphate particles of the present disclosure and a resin.
• the deodorant resin composition according to the present disclosure can be applied to various products that require deodorant properties, such as air cleaners, refrigerators, home appliances such as air conditioners; trash cans, drainers, wraps, sponges, etc. general household goods; various nursing care goods such as portable toilets; wallpaper, toilet bowls, toilet seats, kitchen counters, ventilation fan filters, paints;
• the total amount charged excluding basic compounds is deionized water, 35% hydrochloric acid, 20% aqueous solution of zirconium oxychloride octahydrate (converted to ZrO2 ), oxalic acid dihydrate added in the first step. and the total mass of the 75% phosphoric acid aqueous solution.
• the acquisition rate is a value calculated by the following formula (8).
• Formula (8) L ⁇ (total amount charged (g)) ⁇ 100
• the "total amount charged” is deionized water, 35% hydrochloric acid, 20% aqueous solution of zirconium oxychloride octahydrate (converted to ZrO2 ), oxalic acid dihydrate, 75% phosphorus It is the total mass of the acid aqueous solution and the 20% or 25% sodium hydroxide aqueous solution.
• the acid concentration (titratable acidity) of the first filtrate recovered in the washing step was measured using an automatic potentiometric titrator manufactured by Kyoto Electronics Industry Co., Ltd.
• the acid concentration was calculated from the amount of base required to neutralize all of the acidic components (oxalic acid, hydrochloric acid, and phosphoric acid) contained in the first filtrate.
• a composite glass electrode (C-171) was used as the electrode, and a 1.0 mol/L sodium hydroxide aqueous solution manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. was used as the standard solution for titration.
• the titration parameters of the potentiometric automatic titrator were as follows. Method Type : Titration Titration mode: EP Stop (automatic endpoint stop) End point judgment method: Auto End Point No. : 3 Control speed mode: Slow
• ⁇ Measurement conditions for powder X-ray diffraction> The X-ray diffractometer used was D8 ADVANCE manufactured by BRUKER. An X-ray diffraction pattern was obtained using CuK ⁇ generated at an applied voltage of 40 kV and a current value of 40 mA using a Cu-filled X-ray source. Detailed measurement conditions are as follows.
• X-ray source Encapsulated X-ray source (Cu source), 0.4 ⁇ 12 mm 2 , Long Fine Focus Rating: 2.2kW Output used: 40kV-40mA (1.6kW) Goniometer radius: 280mm
• Example 1 ⁇ Production of Zirconium Phosphate Particles>> ⁇ Example 1> (First step) 984.6 g of deionized water as a solvent and 98.1 g of 35% hydrochloric acid as a solution containing an acidic compound were placed in a 2 L separable reactor and stirred at 220 rpm. After adding 162.9 g (equivalent to 0.26 mol of ZrO 2 ) of a 20% (ZrO 2 equivalent) aqueous solution of zirconium oxychloride octahydrate as a solution containing a zirconium compound, oxalic acid dihydrate as an oxalic acid compound. 68.4 g was added and dissolved.
• aqueous 75% phosphoric acid solution was added as a solution containing a phosphorus compound, and it was confirmed that a precipitate containing zirconium phosphate was formed.
• 210.3 g of a 20% aqueous sodium hydroxide solution as a solution containing the basic compound was added over 60 minutes.
• a 20% ( ZrO2 equivalent) aqueous solution of zirconium oxychloride octahydrate means that the content of ZrO2 is 20% with respect to the entire aqueous solution, assuming that the zirconium compound contained in the aqueous solution is ZrO2 .
• Example 2 The addition amount of the 20% sodium hydroxide aqueous solution in the first step was changed from 210.3 g to 262.9 g, and the addition time of the 20% sodium hydroxide aqueous solution in the first step was changed from 60 minutes to 80 minutes.
• Zirconium phosphate particles were obtained by the same procedure as in Example 1.
• Example 3 The addition amount of the 20% sodium hydroxide aqueous solution in the first step was changed from 210.3 g to 315.4 g, and the addition time of the 20% sodium hydroxide aqueous solution in the first step was changed from 60 minutes to 90 minutes.
• Zirconium phosphate particles were obtained by the same procedure as in Example 1.
• Example 4 (First step) 998.1 g of deionized water as a solvent and 74.3 g of oxalic acid dihydrate as an oxalic acid compound were placed in a 2 L separable reaction vessel and dissolved by stirring at 220 rpm. After adding 66.5 g of 35% hydrochloric acid as a solution containing an acidic compound, 118.2 g of an aqueous 75% phosphoric acid solution was added as a solution containing a phosphorus compound, and then zirconium oxychloride octahydrate was added as a solution containing a zirconium compound.
• Example 5 The addition amount of the 20% sodium hydroxide aqueous solution in the first step was changed from 256.8 g to 342.5 g, and the addition time of the 20% sodium hydroxide aqueous solution in the first step was changed from 50 minutes to 70 minutes.
• Zirconium phosphate particles were obtained by the same procedure as in Example 4.
• Example 6 (First step) 886.3 g of deionized water as a solvent and 88.1 g of oxalic acid dihydrate as an oxalic acid compound were placed in a 2 L separable reactor and stirred at 220 rpm for dissolution. After adding 78.8 g of 35% hydrochloric acid as a solution containing an acidic compound, 140.1 g of an aqueous 75% phosphoric acid solution was added as a solution containing a phosphorus compound, and then zirconium oxychloride octahydrate was added as a solution containing a zirconium compound.
• Example 7 (First step) 1116.5 g of deionized water as a solvent and 103.8 g of oxalic acid dihydrate as an oxalic acid compound were placed in a 2 L separable reactor and stirred at 220 rpm for dissolution. After adding 94.0 g of 35% hydrochloric acid as a solution containing an acidic compound, 165.0 g of an aqueous 75% phosphoric acid solution was added as a solution containing a phosphorus compound, and then zirconium oxychloride octahydrate was added as a solution containing a zirconium compound.
• Example 7 Phosphoric acid/ZrO 2 (molar ratio): 2.10, Oxalic acid/ZrO 2 (molar ratio): 1.37, Hydrochloric acid/ZrO 2 (molar ratio): 1.5, Sodium hydroxide load: 3, Base Solid content concentration in the reaction solution before adding the chemical compound: 9.8
• Example 8 Zirconium phosphate particles were obtained in the same manner as in Example 7, except that the interval until the addition of the basic compound was changed from 2 hours to 1 hour.
• Example 8 Phosphoric acid/ZrO 2 (molar ratio): 2.10, Oxalic acid/ZrO 2 (molar ratio): 1.37, Hydrochloric acid/ZrO 2 (molar ratio): 1.5, Sodium hydroxide load: 3, Base Solid content concentration in the reaction solution before adding the chemical compound: 9.8
• Example 9 Zirconium phosphate particles were obtained in the same manner as in Example 7, except that the interval until the addition of the basic compound was changed from 2 hours to 15 minutes.
• Example 9 Phosphoric acid/ZrO 2 (molar ratio): 2.10, Oxalic acid/ZrO 2 (molar ratio): 1.37, Hydrochloric acid/ZrO 2 (molar ratio): 1.5, Sodium hydroxide load: 3, Base Solid content concentration in the reaction solution before adding the chemical compound: 9.8
• Zirconium phosphate particles (C) were obtained by the method for producing zirconium phosphate particles described in Patent Document 4. The details of the fabrication procedure are described below.
• the obtained precipitate was washed with water until the electric conductivity of the filtrate became 100 ⁇ S/cm or less, and dried at 120° C. under normal pressure to obtain a dried precipitate. This was pulverized with a rotor speed mill (14000 rpm, sieve mesh size 80 ⁇ m). As a result of powder X-ray diffraction measurement of the obtained zirconium phosphate, it was confirmed to be ⁇ -zirconium phosphate.
• the obtained ⁇ -zirconium phosphate is referred to as “ ⁇ -zirconium phosphate (A) ” .
• the average particle size of the zirconium phosphate particles (C), the ratio of zirconium phosphate particles having a particle size of 5 ⁇ m or more, and the primary particle size were measured according to the methods described above.
• Deodorant test 1 Put 10 mg of zirconium phosphate particles into a test bag (Tedlar bag), inject ammonia gas and dry air into the test bag so that the ammonia gas concentration in the test bag is 1000 ppm and the gas volume is 3 L. , and left at normal pressure (101 kPa) for 10 minutes. After standing, the concentration of ammonia gas in the test bag was measured, and the obtained value was defined as A1 .
• a test bag containing no zirconium phosphate particles was also prepared, and the concentration of ammonia gas was measured after standing for 10 minutes, and the obtained value was defined as A0 . The obtained value was substituted into the above formula (1) to calculate the ammonia gas reduction rate.
• the "raw material addition order" in Table 1 includes a solution containing a zirconium compound, a solution containing a phosphorus compound, a solution containing a basic compound, a solvent, an oxalic acid compound, and an acidic compound in the first step.
• the order of addition of the solutions is indicated. In the case of "1", it indicates that the solvent, the solution containing the acidic compound, the solution containing the zirconium compound, the oxalic acid compound, the solution containing the phosphorus compound, and the solution containing the basic compound are added in this order. .
• the “percentage of particles of 5 ⁇ m or more” in Table 1 means the percentage of zirconium phosphate particles of 5 ⁇ m or more in diameter.
• “Concentration of solid content before addition of basic compound (wt%)” in Table 1 means the concentration of solid content (% by mass) in the reaction solution before addition of basic compound.
• Examples 1 to 9 do not require production of ⁇ -zirconium phosphate particles used as raw materials, and zirconium phosphate particles that adsorb odorous gases can be obtained directly using a zirconium compound, a phosphorus compound, and a basic compound as raw materials. can.
• Examples 1 to 9 have only one procedure of filtering, washing with water, and drying in (washing step) and (drying step).
• Reference Example 1 has procedures of filtering, washing, and drying zirconium phosphate in each of (production of raw material ⁇ -zirconium phosphate particles) and (production of zirconium phosphate particles).
• the zirconium phosphate particles obtained in Examples 1 to 9 have the same ammonia gas reduction rate as the zirconium phosphate particles (C) obtained in Reference Example 1, and the odor gas adsorption rate is the same. It turns out that
• zirconium phosphate particles of Examples 1 to 9 zirconium phosphate particles that adsorb odorous gases can be obtained in a short process.
• the zirconium phosphate particles obtained in Examples 1 to 9 have a higher ammonia gas reduction rate and a higher rate of adsorbing odorous gases than the zirconium phosphate particles obtained in Comparative Examples 1 to 5. . Therefore, the methods for producing zirconium phosphate particles of Examples 1 to 9 provide zirconium phosphate particles having a higher rate of adsorbing odorous gases than the methods for producing zirconium phosphate particles of Comparative Examples 1 to 5. It turns out that it is a manufacturing method.
• Example 101 3 parts of the zirconium phosphate particles obtained in Example 9 and 97 parts of a polyester resin (manufactured by Unitika Ltd., MA-2101M) dried at 150°C for 12 hours were mixed, and fully automatic injection was performed at 270°C. It was put into a molding machine (manufactured by Meiki Seisakusho Co., Ltd., model: M-50A 11-DM) to prepare a plate of 11 cm x 11 cm x 1 mm.
• a molding machine manufactured by Meiki Seisakusho Co., Ltd., model: M-50A 11-DM
• this plate was pulverized with a wonder blender (manufactured by Osaka Chemical Co., Ltd., type: WB-1) to a median diameter of 200 ⁇ m ⁇ 100 ⁇ m to obtain a deodorant resin composition A.
• the deodorant performance was evaluated according to the method shown below (Deodorant Test 2). Table 2 shows the results.
• Example 101 A deodorant resin composition B was obtained in the same manner as in Example 101 except that the zirconium phosphate particles obtained in Example 9 were replaced with the zirconium phosphate particles obtained in Comparative Example 1.
• the deodorant performance was evaluated according to the method shown below (Deodorant Test 2). Table 2 shows the results.
• Deodorant test 2 Put 2.4 g of the deodorant resin composition into a test bag (Tedlar bag), inject ammonia gas and dry air into the test bag so that the ammonia gas concentration in the test bag is 100 ppm, and the gas volume is 3 L. 25° C.) and normal pressure (101 kPa) for 1 hour. After standing, the concentration of ammonia gas in the test bag was measured, and the obtained value was defined as A1 .
• a test bag containing no zirconium phosphate particles was also prepared, and the ammonia gas concentration was measured after being left for 1 hour, and the obtained value was defined as A0 . The obtained value was substituted into the above formula (1) to calculate the ammonia gas reduction rate.
• the deodorant resin composition A containing the zirconium phosphate particles obtained in Example 9 was compared with the deodorant resin composition B containing the zirconium phosphate particles obtained in Comparative Example 1. It can be seen that the rate of reduction is high and the rate of adsorption of odorous gases is high.

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