Deodorizing materials

Abstract

To provide a simple deodorant excellent in deodorizing properties that can eliminate odorous components in a short period of time without receiving light on a wide range of various types of odorous components, capable of not only sustaining a deodorizing action for a long time and capable of repeatedly being used but also reused, by recovering the deodorant properties, having white color or pale color and not disturbing coloration of a base component, and containing deodorant components capable of deodorizing by using as it is or using by carrying on an aqueous solution, gel, a solid activator or fibers.SOLUTION: A deodorant material has a hydroxide layer containing one kind of metal element, and cations, anions, and / or water molecules are intercalated between the layers, and layered double hydroxide that intercalates, or adsorbs, or decomposes a deodorizing component is contained as a deodorant component.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention provides a layered deodorizing agent that can eliminate various odorous components (hereinafter, both are collectively referred to as deodorizing). of The present invention relates to a deodorizing material containing hydroxide as a deodorizing component. [Background technology]

[0002] Various deodorizers and deodorizing devices are used to remove or reduce body odors and household odors emitted by humans and pets, spatial odors such as the foul odors that linger in rooms, vehicles, work sites, factories, etc., and liquid or solid odors emitted from waste liquids, sewage, chemical substances, etc.

[0003] Various deodorizing methods are used. For example, adsorption methods, such as physical adsorption of odorous components using adsorbents with large surface areas, such as activated carbon, for various odorous components, and chemical adsorption of odorous components using adsorbents such as calcium carbonate for acidic odor components and aluminum sulfate for basic odor components, are commonly used in industrial and household deodorizing products. Other methods include photocatalytic deodorizers, such as highly active titanium dioxide (anatase type), and decomposition and removal methods that chemically decompose or change odorous components using ultraviolet light or ozone generation. Furthermore, masking methods, such as perfumes, fragrances, and air fresheners, mask unpleasant odors and prioritize pleasant scents, and pairing methods, which incorporate odorous components into aromatic compounds. Microbial deodorization methods, such as using bacteria, enzymes, or activated sludge to decompose organic matter in food waste and sewage, or antibacterial agents to inhibit the growth of putrefactive bacteria, are also commonly used. Most deodorization methods involve one or a combination of these methods.

[0004] Activated carbon, a physical adsorption deodorizer, is black in color and therefore blocks the color of the material, so it is used in applications that do not require coloring, such as in household deodorizers or deodorizers for industrial wastewater treatment and exhaust gas treatment.It can adsorb a wide range of odorous components, but it cannot be used on white or colored fabrics for clothing or fabric products for furniture and automobiles.

[0005] Chemical adsorption deodorizers such as calcium carbonate and aluminum sulfate utilize an acid-base reaction, and while they are specific to certain odorous components, the odorous components they can deodorize are limited.

[0006] Patent Document 1 discloses a pet urine treatment material containing water-absorbent granules and non-disintegrating humidity-regulating granules mainly composed of zeolite. This patent document also describes that the material may contain metal salts with deodorizing properties (e.g., zinc chloride, silver nitrate, aluminum sulfate, etc.) in addition to deodorizing additives such as water-soluble copper compounds. Furthermore, Patent Document 2 discloses a liquid oral composition containing a thickener and an abrasive. This patent document also describes that the material may contain deodorizing agents such as zinc chloride. Because the metal salts such as zinc chloride described in these patent documents are water-soluble, the pet urine treatment material of Patent Document 1 and the liquid oral composition of Patent Document 2 are disposable and are not reused to exhibit deodorizing properties.

[0007] Photocatalytic agents such as activated titanium oxide break down odorous components, bacteria, viruses, dirt, etc. when exposed to light energy, but because they require light, their range of use is limited.

[0008] Masking and pairing do not inherently remove odorous components. Furthermore, microbial deodorizing methods are used in large-scale facilities such as sewage treatment and industrial wastewater treatment, and are difficult to apply to general-purpose products such as everyday items.

[0009] Non-chemical deodorizing methods such as ultraviolet irradiation and ozone generation not only require large-scale equipment, but also cannot be directly exposed to the human body because exposure to large amounts of ultraviolet rays or ozone has adverse effects on the human body.

[0010] There was a need for a deodorizing material that could be used against a wide range of odorous components, that was durable, reusable, and reusable, that did not interfere with essential product properties such as coloring, and that could be used in liquid, gel, or solid form. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Patent Publication No. 2021-23163 [Patent Document 2] Japanese Patent Application Publication No. 2019-199466 [Patent Document 3] International Publication No. 2016 / 199905A1 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-38014 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made to solve the above problems, and has excellent deodorizing properties that can eliminate various types of wide-ranging odor components in a short time without exposure to light, and the deodorizing effect can be maintained for a long period of time and can be used repeatedly. R The present invention also aims to provide a simple deodorizing material containing a deodorizing component that can be reused by restoring its deodorizing properties, is white or light in color, does not interfere with the coloring of the base component, and can deodorize whether used as is or supported on an aqueous solution, gel, solid activator, fiber, etc. Another object of the present invention is to provide a simple method for preparing the deodorizing component that is efficient, has excellent reproducibility, and has a high yield. [Means for solving the problem]

[0013] The deodorizing material developed to achieve the above object has hydroxide layers containing one type of metal element, and cations, anions, and / or water molecules are intercalated between the layers, and the odorous components are intercalated, adsorbed, or decomposed. and the following chemical formula (1) [M 2+ x (OH) (2x-y) ][A n- y / n zH 2 O] ···(1) (In formula (1), M 2+ is a cation of a divalent metal element, A n- is an anion with a valence of n (n is 1 to 3), x is 1 to 5, y is 1 to 10, and z is 1 to 10), and is a hexagonal plate crystal with an aspect ratio L:H of 20:1 to 10:1, which is the ratio of the length L, which is the average diameter across the hexagonal faces, to the thickness H, which is the average height in the direction perpendicular to the hexagonal faces. Layered of It is characterized by containing hydroxide as a deodorizing ingredient. This is a deodorizing material for reuse that can be reused repeatedly by drying and releasing, releasing into water, and / or decomposing and absorbing the odorous components of ammonia, amine, mercaptan, acetaldehyde, isovaleric acid, and isobutanol.

[0014] In this deodorant material, the metal element is preferably divalent.

[0015] In this deodorant material, it is more preferable that the metal element is zinc.

[0016] This deodorizing material is Represented by chemical formula (1) Layered of Even more preferably, the hydroxide is simoncollite.

[0017] This deodorizing material is Represented by chemical formula (1) Layered of The hydroxide may be in the form of hexagonal plates, scales, flakes, or irregular shapes.

[0018] This deodorizing material is Represented by chemical formula (1) Layered of The hydroxide reduces the aspect ratio 10±2:1 It may be as follows.

[0019] This deodorizing material is, for example, a deodorizing agent in which the deodorizing component is either as is or contained in either a solid carrier or a liquid or gel-like fluid carrier; deodorizing fabrics, clothing, apparel, clothing items, or fibers thereof in which the deodorizing component is attached to or impregnated with the fabric; or building materials, industrial products, or daily necessities containing the deodorizing component. This deodorant may be one in which the layered hydroxide represented by the chemical formula (1) is kneaded into a resin carrier. This deodorant is formed into a film shape by using the resin, for example. In this deodorant, for example, the resin is polyethylene.

[0020] The method for preparing a deodorizing component of the present invention, which has been made to achieve the above object, comprises mixing an aqueous solution of a water-soluble salt of one kind of metal with an aqueous solution of an alkali metal hydroxide, At normal pressure After mixing, neutralize By leaving it at room temperature The compound has hydroxide layers containing one kind of metal element, and cations, anions, and / or water molecules are intercalated between the layers, and the compound intercalates, adsorbs, or decomposes odorous components. and the following chemical formula (1) [M 2+ x (OH) (2x-y) ][A n- y / n zH 2 O] ···(1) (In formula (1), M 2+ is a cation of a divalent metal element, A n- is an anion with a valence of n (n is 1 to 3), x is 1 to 5, y is 1 to 10, and z is 1 to 10), and is a hexagonal plate crystal with an aspect ratio L:H of 20:1 to 10:1, which is the ratio of the length L, which is the average diameter across the hexagonal faces, to the thickness H, which is the average height in the direction perpendicular to the hexagonal faces. Layered of The method is characterized by crystallizing the hydroxide. This is a method for preparing a deodorizing component for reuse that can be repeatedly reused by drying and releasing, releasing into water, and / or decomposing and absorbing the odorous components of ammonia, amine, mercaptan, acetaldehyde, isovaleric acid, and isobutanol. That is it. [Effects of the Invention]

[0021] The deodorizing material of the present invention can deodorize a wide variety of odorous components, including various household odors such as acidic, basic (e.g., amine), sulfuric, and neutral alcoholic or aldehyde odors, body odors, and industrial odors.

[0022] This deodorizing material has excellent deodorizing properties, being able to reduce or eliminate odorous components in a short period of time, such as a few minutes to a few hours, without the need for treatments such as exposure to light or heating to the temperature of human skin.

[0023] This deodorizing material has a long-lasting deodorizing effect against various odorous components and can be used repeatedly, making it economical and convenient. Moreover, because the deodorizing components are water-insoluble or poorly soluble, this deodorizing material can be reused repeatedly by cleaning, for example with water, to restore its deodorizing properties. Therefore, it does not need to be thrown away and does not cause environmental degradation, making it compatible with the Sustainable Development Goals (SDGs).

[0024] This deodorizing material does not interfere with the coloring of base components, such as fibers, that are used as needed because the deodorizing components are white or light in color, and therefore does not impair the desired designs of clothing, carpets, vehicle seats, various interiors, etc.

[0025] This deodorizing material is versatile because it exhibits excellent deodorizing effects whether the deodorizing ingredients are used as they are in powder or particle form, or whether they are supported on aqueous solutions, gels, solid activators, fibers, etc.

[0026] This deodorizing material exhibits a deodorizing function when the deodorizing component is contained, so it can be made into a simple structure and can be used in a variety of fields, such as daily products, industrial products, and deodorizing devices for plants.

[0027] Furthermore, the method for preparing the deodorizing component of the present invention is simple and short in steps, does not require any treatment such as heating, and can prepare the deodorizing component efficiently, with good reproducibility, and with high yield. Any amount can be prepared, from small to large amounts, and this contributes to the simple and inexpensive production of deodorizing materials. [Brief explanation of the drawings]

[0028] [Figure 1] 1 is a graph showing the deodorizing rate of each malodorous component by the deodorizing material of Example 1 to which the present invention is applied. [Figure 2] 1 is a graph showing the deodorizing rate of each malodorous component by the deodorizing materials of Example 2 to which the present invention is applied and Comparative Examples 2-1 and 2-2 to which the present invention is not applied. [Figure 3] 1 is a graph showing the deodorizing rate of each malodorous component by a deodorizing material which is a deodorizing gel of Example 3 to which the present invention is applied and a deodorizing material which is a deodorizing gel of Comparative Example 3 to which the present invention is not applied. [Figure 4] 1 is a graph showing the deodorizing rate of each malodorous component by a deodorizing material which is a deodorizing film of Example 4 to which the present invention is applied and a deodorizing material which is a deodorizing film of Comparative Example 4 to which the present invention is not applied. [Figure 5] 1 is a graph showing the re-release rate of each malodorous component for the deodorizing material of Example 5 to which the present invention is applied and the deodorizing material of Comparative Example 5 to which the present invention is not applied. [Figure 6] 10 is a graph showing the elution rate of malodorous components into an aqueous solution after deodorization of the malodorous components by the deodorizing material of Example 6 to which the present invention is applied. [Figure 7] 1 is a graph showing the elution rate of each malodorous component into an aqueous solution for each number of deodorization-water washing cycles by the deodorizing material of Example 7 to which the present invention is applied and the deodorizing material of Comparative Example 7 to which the present invention is not applied. [Figure 8] 1 is a graph showing the deodorizing rate of each malodorous component by the deodorizing materials for each thickness in Examples 8-1 and 8-2 to which the present invention is applied. [Figure 9] 1 is a graph showing the deodorizing rate of each malodorous component by the deodorizing materials of each shape in Examples 9-1 to 9-3 to which the present invention is applied, and electron microscope photographs of each shape. [Figure 10] 1 is a graph showing the change over time in deodorizing rate against each malodorous component by the deodorizing material of Example 10-1 to which the present invention is applied and the deodorizing materials of Comparative Examples 10-1 and 10-2 to which the present invention is not applied. DETAILED DESCRIPTION OF THE INVENTION

[0029] Hereinafter, embodiments for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to these embodiments.

[0030] The deodorant material of the present invention contains substantially only one type of metal element. Represented by chemical formula (1) Layered of It contains hydroxide as a deodorizing component.

[0031] Like this Represented by chemical formula (1) Layered of Each hydroxide particle has a plurality of hydroxide layers made up of hydroxide base layers.

[0032] Like this Represented by chemical formula (1) Layered of Hydroxides have a layered structure in which the hydroxide layers have a positive charge and are intercalated with negatively charged anions, water molecules, and / or cations in some cases between the layers.

[0033] Such a layered of The hydroxide is one in which the metal element is a divalent metal, preferably zinc. More specifically, it is represented by the following chemical formula (1): [M 2+ x (OH) (2x-y) ][A n- y / n ·zH2O] ···(1) (In formula (1), M 2+ is a cation of a divalent metal element, preferably a zinc ion, A n- is an n-valent anion (n is 1 to 3, preferably 1 or 2, more preferably 1), preferably a chloride ion, x=1 to 5, preferably 5, y=1 to 10, preferably 2, and z=1 to 10, preferably 1 to 8, more preferably 1). Represented by chemical formula (1) Layered of The hydroxide may be substantially represented by the chemical formula (1), Represented by chemical formula (1) Layered of M in hydroxide 2+ "Containing substantially only one type of metal element" means that it may contain impurity metal ions other than zinc, which are divalent and / or trivalent metal ions, on the order of ppm, for example, up to 10,000 ppm.

[0034] More specific and preferable Represented by the chemical formula (1) Layered ofThe hydroxide is simonkollite (or Simonkolleite). Simonkollite is also called basic zinc chloride (monohydroxide) or zinc hydroxychloride (monohydrate) and is represented by Zn5(OH)8Cl2·zH2O (z = 1 to 8), for example, Zn5(OH)8Cl2·H2O. For example, Patent Document 3 discloses a skin wound or rough skin treatment agent containing zinc chloride hydroxide hydrate such as simonkollite, and Patent Document 4 discloses an example of its use in cosmetics containing a flaky powder represented by Zn5(OH)8Cl2·nH2O (n = 1 to 8). However, it has not been previously known to have a deodorizing effect.

[0035] this The compound represented by the above chemical formula (1) Layered of The hydroxide may be in the form of a hexagonal plate, a scale, a flake, or an irregular shape, but the shape is not particularly limited.

[0036] this The compound represented by the above chemical formula (1) Layered of The hydroxide is preferably hexagonal plate-shaped, and when the aspect ratio L:H, which is the ratio of the average diameter across the hexagonal faces of the hexagonal plate crystals (length: L) to the average height perpendicular to the hexagonal faces (thickness: H), is 100:1 to 1:1, preferably 20:1 to 1:1, more preferably 20:1 to 10:1, even more preferably 10±2:1, and still more preferably 10:1, it can exhibit excellent deodorizing action against a wide range of odorous components, including acidic, basic (e.g., amine-based), sulfur-based, and neutral odorants.

[0037] this The compound represented by the above chemical formula (1) Layered of The hydroxide has an average particle size of several hundred to several μm, specifically 50 to 0.5 μm, more preferably 20 to 1 μm, and even more preferably 10 μm, as determined by randomly selecting 10 particles from among those measured by scanning electron microscope (SEM) observation. An average particle size within this range has the advantage of exhibiting a deodorizing effect against a wider range of odorous components (e.g., methyl mercaptan, trimethylamine, etc.).

[0038] this The compound represented by the above chemical formula (1) Layered of The mechanism by which hydroxide functions as a deodorizing component is not entirely clear, but is presumed to be as follows.

[0039] Represented by the chemical formula (1) Layered of Anion A originally intercalated between the hydroxide layers in the hydroxide n- It is thought that the mechanism by which water molecules such as HO and the like adsorb and deodorize acidic, basic, or neutral odor components, especially acidic ones such as fatty acids, amines or bases such as ammonia gas or alkylamines, alcohols such as aliphatic alcohols, or aldehydes such as aliphatic aldehydes, by intercalating them through substitution or electrostatic interaction, without being replaced or replaced. This is common to most odor components, Represented by the chemical formula (1) Layered of The odorous components intercalated in the hydroxide do not leave the gap between the layers in their original state, but when the deodorizing material is washed with water, they leave the gap between the layers, so it seems that they are held between the layers by a weak intermolecular force that allows for intercalation and deintercalation. However, not all odorous components are released and recovered by washing with water, so some Represented by the chemical formula (1) Layered of It is presumed that the metal elements in the hydroxide cause the decomposition.

[0040] On the other hand, among the odorous components, sulfur-based odorous components are Represented by the chemical formula (1) Layered of After deodorizing with hydroxide, it cannot be recovered even if washed with water. Represented by the chemical formula (1) Layered of Anion A originally intercalated between the hydroxide layers in the hydroxide n- It is presumed that the odor is eliminated by chemically reacting sulfur-based odorous components with ZnS-based compounds and intercalating them, with or without replacing them, or by decomposing the sulfur-based odorous components or oxidizing them into sulfonic acid components that do not emit a foul odor.

[0041] This deodorizing ingredient Represented by the chemical formula (1) Layered of The hydroxide can be prepared by mixing an aqueous solution of a water-soluble salt of one metal, such as an aqueous zinc chloride solution, and an aqueous solution of an alkali metal hydroxide, such as an aqueous sodium hydroxide solution, into the other, for example by adding dropwise or pouring the mixture, followed by neutralizing the mixture with an inorganic acid, such as hydrochloric acid, and then Represented by the chemical formula (1) Layered of The hydroxide is allowed to stand for 0 to 24 hours as needed to crystallize, and the crystals are grown to prepare the solution.

[0042] However, the preparation method differs from that of the zinc chloride hydroxide hydrate in Reference 3 in that it is produced by using an aqueous zinc salt solution and an aqueous alkali solution, using an inorganic acid as a pH adjuster, and aging for a certain period of time.

[0043] this The compound represented by the above chemical formula (1) Layered of Hexagonal plate-shaped hydroxides can be prepared by using a zinc chloride solution in an aqueous solution of a water-soluble salt of one metal, or a sodium hydroxide solution in an aqueous solution of an alkali metal hydroxide. Furthermore, by controlling the standing time, crystals of various thicknesses, such as 0.5 μm or 1.0 μm, can be prepared. By controlling the reaction temperature or changing the water-soluble aqueous solution of one metal from zinc chloride to zinc iodide, flake-shaped hydroxides can be prepared, and amorphous shapes can also be prepared.

[0044] The deodorizing material of the present invention may be used as a deodorizing agent either alone or in combination with or with an additive other than the carrier, such as polyethylene oxide or carboxymethyl cellulose, added internally or externally.

[0045] The deodorizing material of the present invention may be used as a solid deodorizing agent in the form of powder, beads, tablets, sticks, sheets, plates, or rectangles, contained in a solid carrier, for example, an excipient such as a resin, or as a liquid deodorizing agent such as a spray, contained in a liquid carrier, for example, water, alcohol, or a mixture thereof, to which the above-mentioned additives may be added as needed. Alternatively, the deodorizing material may be used as a gel-type deodorizing agent, in which the deodorizing component is mixed internally or externally with a gel-like fluid carrier such as κ-carrageenan, to which the above-mentioned additives may be added as needed. The deodorizing material may be used as a paste-type deodorizing agent, such as toothpaste, in which the deodorizing component and the semi-paste component are mixed internally or externally, to which the above-mentioned additives may be added as needed.

[0046] The deodorizing material of the present invention may be used as a deodorizing material such as deodorizing paper or deodorizing fabric, in which the deodorizing component and, if necessary, the additives, dyes, pigments, etc. are attached to the outside of or impregnated into fabric such as paper or woven fabric or nonwoven fabric, for example, fabric, cloth, clothing, sheets, blankets, curtains, covering materials for chairs or sofas, carpets, rugs, carpets, etc.

[0047] The deodorizing material of the present invention may be used as building materials containing the deodorizing component, such as wall materials, wallpaper, ceiling materials, floor materials, tatami mats, flooring, and filters for air conditioning equipment, by mixing the deodorizing component and, if necessary, the additives, into various base materials as internal or external additions; as industrial products containing the deodorizing component, such as filters or filter units for treating exhaust gases and waste liquids, water purification filters for water purification systems, and interior materials for automobiles and vehicles; as everyday items containing the deodorizing component, such as futons, cushions, cushions, clothing deodorizing sprays, room deodorizing sprays, toothpaste, bad breath preventatives, body odor preventative deodorants, and pet sheets; and as clothing products such as shirts, sweaters, underwear, and other clothing and apparel, or as fibers thereof. [Example]

[0048] Hereinafter, a deodorizing material of an example to which the present invention is applied and a deodorizing material of a comparative example to which the present invention is not applied will be specifically described.

[0049] (Preparation Example 1) 300 ml of 40% aqueous sodium hydroxide (NaOH) solution in a 1000 ml reaction vessel was set to 70°C, and 400 ml of 25% by weight aqueous zinc chloride (ZnCl) solution was added all at once. The temperature was set to 70°C and the mixture was stirred at normal pressure for 30 minutes. Then, 35 v / v% hydrochloric acid was added dropwise while stirring to adjust the pH to 7.0. Represented by chemical formula (1) Layered of hydroxide An example of Simoncollite was synthesized from Zn5(OH)8Cl2·zH2O (z = 1-8), and crystals were precipitated. The crystals were allowed to stand at room temperature for 6 hours to grow into hexagonal plate crystals. This hexagonal plate crystal Simoncollite, a deodorizing ingredient, was filtered, and the residue was dried in a 90°C dryer to obtain a powder of Simoncollite hexagonal plate crystals. This hexagonal plate crystal Simoncollite had an aspect ratio (L:H) of 10:1, which is the ratio of the average diameter across the hexagonal faces (length: L) to the average height perpendicular to the hexagonal faces (thickness: H). Scanning electron microscope (SEM) observation measured the average particle size (length L) of 10 randomly selected particles, and the average particle size was 10 μm. This was used as a test sample for Example 1, a deodorizing ingredient (or deodorant or odor-eliminating material) consisting solely of Simoncollite hexagonal plate crystals.

[0050] (Evaluation Test 1 of Deodorizing Effect on Various Malodorous Gases: Example 1 and Comparative Example 1 (Control Example)) The deodorizing test method 1 for evaluating the deodorizing effect on various malodorous gases as odor components is as follows. In Example 1, into separate 300 ml sealed containers, (1-i) a hydrogen sulfide solution prepared by heating solid hydrogen sulfide and dissolving the generated gas in distilled water was introduced to adjust the malodor concentration to 10 ppm, (1-ii) a methyl mercaptan solution prepared by diluting a methyl mercaptan standard solution was introduced to adjust the malodor concentration to 20 ppm, (1-iii) an ammonia solution prepared by diluting 25-30% ammonia water was introduced to adjust the malodor concentration to 150 ppm, (1-iv) a trimethylamine solution prepared by diluting a 30% trimethylamine solution was introduced to adjust the malodor concentration to 25 ppm, (1-v) a solution of isovaleric acid prepared by diluting a 99% isovaleric acid solution was introduced to adjust the malodor concentration to 40 ppm, and (1-vi) 99% isobutanol was introduced to adjust the malodor concentration to 80 ppm. 0.25 g of each test sample, which was a deodorizing material consisting only of the deodorizing component of hexagonal plate-shaped Simoncollite crystals prepared in Preparation Example 1, was placed in a 500 ml Erlenmeyer flask and sealed in an airtight container. 0.1 to 2.0 ml of each malodor solution was injected with a syringe through the gap in the rubber stopper to achieve a predetermined malodor concentration, and after a predetermined time (2 hours in Evaluation Test 1), each malodor concentration was measured. As Comparative Example 1 (control example), the malodor concentration was measured in the same manner as in Example 1, except that Simoncolite was not used and each malodor concentration was measured immediately after the malodorous gas was injected. For each Example 1 after 2 hours and Comparative Example 1 (control), odor concentration measurements were carried out using AS ONE Corporation's measurement detector tubes: (1-i) hydrogen sulfide 4LK, 4LT, (1-ii) methyl mercaptan 71, (1-iii, iv) amines 180, (1-v) acetic acid 81, and (1-vi) isobutyl alcohol 116. Each detector tube was used with a detector tube gas measuring instrument. For each malodorous gas, the reduction rate of the malodorous gas concentration after 2 hours in each Example 1 relative to the malodorous gas concentration in Comparative Example 1 (control) was calculated as the deodorization rate. The results are summarized in Figure 1.

[0051] As is clear from Figure 1, it was found that the deodorizing material containing Simoncolite, to which the present invention is applied, as a deodorizing component, has a wide range of deodorizing effects against sulfur-based odor components, nitrogen-based odor components, acidic odor components, and alcohol-based odor components.

[0052] (Comparative Preparation Example 2-1) Activated carbon manufactured by Kuraray Co., Ltd. under the trade name Kuraray Coal KW was used as the deodorizing component (deodorizer / deodorizing material) of Comparative Preparation Example 2-1 as Comparative Test Sample 1-1.

[0053] (Comparative Preparation Example 2-2) The deodorizing component (deodorizer / deodorizing material) of Comparative Preparation Example 2-2, which is a deodorizer manufactured by Toagosei Co., Ltd. and has a product name of Kesmon NS-10 (active ingredient: zirconium phosphate) that exhibits a deodorizing effect specifically on amine-based odor components, was used as Comparative Test Sample 2-2.

[0054] (Deodorizing Test 2 for Various Malodorous Gases: Example 2, Comparative Examples 2-1 and 2-2, and Control Example) A deodorizing material containing Simoncolite, to which the present invention is applied, as a deodorizing component was used, and hydrogen sulfide, methyl mercaptan, and isovaleric acid were used as the odor components in Example 1, to prepare Example 2, which was evaluated in the same manner as in Deodorizing Test 1. Meanwhile, a deodorizing material made of activated carbon, which is Comparative Test Sample 1-1 in Comparative Preparation Example 1-1, and a deodorizing material made of Kesmon, which is Comparative Test Sample 1-2 in Comparative Preparation Example 1-2, were used to prepare Comparative Examples 2-1 and 2-2, which were evaluated in the same manner as in Deodorizing Test 1. Note that a control example was tested in the same manner as used in Example 1. The deodorizing results are summarized in Figure 2.

[0055] As is clear from Figure 2, the deodorizing material of Example 2, which uses Simoncolite, to which the present invention is applied, as a deodorizing component, exhibited a deodorizing effect against sulfur-based odor components, nitrogen-based odor components, and acid-based odor components that was equal to or greater than that of the activated carbon of Comparative Example 2-1. On the other hand, Comparative Example 2-2, which uses Kesmon as test sample 2, had no effect at all against sulfur-based odor components, whereas Example 2 exhibited an almost complete deodorizing effect. Furthermore, Comparative Example 2-2 exhibited a considerable deodorizing effect against acid-based odor components, although it could not be said to be complete, whereas Example 2 exhibited a complete deodorizing effect.

[0056] (Preparation Example 3) The deodorizing component obtained in Example 1 was composed solely of hexagonal platelet simoncollite crystals. 0.25 g of the deodorizing component, 2.0 g of Adeka Tol LB (manufactured by ADEKA Corporation), and 2.5 ml of ethanol were added to a 50 ml beaker (i). 0.1 g of potassium chloride, 1.5 g of diethylene glycol, and 13.8 ml of distilled water were added to a 50 ml beaker (ii). 0.8 g of κ-carrageenan and 30 ml of distilled water were added to a 50 ml beaker (iii). Each was placed in a 70°C oven to dissolve the ingredients. While stirring the 50 ml beaker (iii) at 70°C and 400 rpm, the solutions from the 50 ml beakers (i) and (ii) were added to the 50 ml beaker (iii). The resulting deodorizing gel containing hexagonal platelet simoncollite crystals was used as the test sample for Example 3.

[0057] (Comparative Preparation Example 3) A deodorizing gel containing activated carbon was used as the test sample of Comparative Preparation Example 3 in the same manner as the deodorizing gel of Example Preparation Example 3, except that activated carbon manufactured by Kuraray Co., Ltd., product name Kuraray Coal KW, was used.

[0058] (For various odorous gases Ge Evaluation test 3 of deodorizing properties in the form of a capsule: Example 3, Comparative Example 3 and Control Example Example 3 was prepared using 50 g (0.25 g of deodorizing component) of a deodorizing gel containing Simoncolite, to which the present invention is applied, as a deodorizing component, and hydrogen sulfide, ammonia, trimethylamine, and isovaleric acid as the odor components in Example 1. This was evaluated in the same manner as in Deodorizing Test 1. On the other hand, Comparative Example 3 was prepared using a deodorizing gel containing activated carbon, which was Comparative Test Sample 3 of Comparative Preparation Example 3. A control example was also tested in the same manner as in Example 1. The deodorizing results are summarized in Figure 3.

[0059] As is clear from Figure 3, Example 3, a deodorizing gel containing hexagonal platelet simoncollite crystals to which the present invention is applied, had a higher deodorizing effect on hydrogen sulfide, ammonia, trimethylamine, and isovaleric acid than Comparative Example 3, a deodorizing gel containing activated carbon. This is because the activated carbon, which has a large surface area, is covered with gel and is unable to fully exert its deodorizing effect, whereas Example 3 has a large surface area rather than a large surface area. Represented by the chemical formula (1) Layered of It is presumed that the deodorizing effect was achieved by the odorous components intercalating between the hydroxide layers or becoming trapped as sulfides.

[0060] (Preparation Example 4) The deodorizing component used was composed solely of the simoncollite hexagonal plate crystals obtained in Preparation Example 1. 0.75 g of the deodorizing component, which is the simoncollite hexagonal plate crystals obtained in Preparation Example 1, was kneaded into 7.5 g of polyethylene resin and pressed with a press to form a 100 μm thick deodorizing film, which was used as the test sample for Preparation Example 4.

[0061] (Comparative Preparation Example 4) Except for using Kesmon NS-10, a deodorizer manufactured by Toagosei Co., Ltd., a deodorizing film containing Kesmon was used as the test sample of Comparative Preparation Example 4 in the same manner as the deodorizing film deodorizing material of Working Preparation Example 4. Note that activated carbon is black and cannot be colored, so there is little need for it to be used in deodorizing films, and therefore it was not used as a comparative example.

[0062] (Test 4 for evaluating the deodorizing properties of films against various malodorous gases: Example 4, Comparative Example 4, and Control Example) Example 4 was prepared by using 1.0 g (including 0.01 g of deodorizing component) of a deodorizing film containing Simoncolite, to which the present invention is applied, as a deodorizing component, and hydrogen sulfide and methyl mercaptan were used as the odor components in Example 1, and was evaluated in the same manner as in Deodorizing Test 1. On the other hand, Comparative Example 4 was prepared by using a deodorizing film containing Kesmon, which is Comparative Test Sample 4 of Comparative Preparation Example 4, and was evaluated in the same manner as in Deodorizing Test 1. Note that a control example was tested in the same manner as used in Example 1. The deodorizing results are summarized in Figure 4.

[0063] As is clear from Figure 4, Example 4, a deodorizing material that is a deodorizing film containing hexagonal platelet crystals of Simoncolite to which the present invention is applied, had a high deodorizing effect for both hydrogen sulfide and methyl mercaptan, whereas Comparative Example 3, a deodorizing material that is a deodorizing film containing Kesmon, had no deodorizing effect at all. Therefore, Example 4 had a much higher deodorizing effect than a deodorizing material that contains an inorganic deodorizing component such as Comparative Example 4.

[0064] (Preparation Example 5) The deodorizing material obtained in Preparation Example 1, which is a deodorizing component consisting only of simoncollite hexagonal plate crystals, was used as a test sample in Preparation Example 5.

[0065] (Comparative Preparation Example 5) A deodorizing material consisting solely of activated carbon (trade name: Kuraray Coal KW) manufactured by Kuraray Co., Ltd. was used as the test sample for Comparative Preparation Example 5.

[0066] (Evaluation Test 5 for Odor Component Re-release Properties for Various Malodorous Gases: Example 5, Comparative Example 5, and Control Example) Example 5 was prepared using 1.0 g of a deodorizing material containing only hexagonal platelet crystals of simoncollite as a deodorizing component of the present invention, with ammonia, trimethylamine, methyl mercaptan, acetaldehyde, and isobutanol substituted for the odorous components in Example 1. After deodorizing in the same manner as in Deodorizing Test 1, this deodorizing material was placed in a 500 ml container, stoppered, and placed in a dryer at 70°C. The gas concentration in the container was measured in the same manner as in Deodorizing Test 1, and the re-release rate of the odorous components was calculated. Meanwhile, Comparative Example 5 was prepared using the Kesmon deodorizing material, which was comparative test sample 5 of Comparative Preparation Example 5, and was evaluated in the same manner as in Example 5. A control example was also tested in the same manner as in Example 1. The deodorizing results are summarized in Figure 5.

[0067] As is clear from Figure 5, in Example 5, a deodorizing material made of a deodorizing component that is hexagonal plate-shaped Simoncollite crystals to which the present invention is applied, the re-release rate of odorous components was low for all of ammonia, trimethylamine, methyl mercaptan, acetaldehyde, and isobutanol, and therefore the deodorizing component that is hexagonal plate-shaped Simoncollite crystals hardly released any of the adsorbed odorous components or secondary odorous components formed by decomposition of the odorous components even when heated. On the other hand, it was found that the deodorizing component that is activated carbon as in Comparative Example 5 released a considerable amount of the adsorbed odorous components when heated.

[0068] (Preparation Example 6) The deodorizing material obtained in Preparation Example 1, which is a deodorizing component consisting only of simoncollite hexagonal plate crystals, was used as a test sample in Preparation Example 6.

[0069] (Test 6 for evaluating the water-washing release of odorous components from various malodorous gases: Example 6 and control example) Example 6 was prepared using 1.0 g of a deodorizing material composed solely of hexagonal plate-shaped simoncollite crystals of the present invention, with ammonia, trimethylamine, isovaleric acid, and isobutanol substituted for the odorous components in Example 1. After deodorizing in the same manner as in Deodorizing Test 1, the deodorizing material was stirred in 30 ml of water at 400 rpm for 24 hours. The solution was sampled using a Pack Test (model: WAK-NH4(C)-4, manufactured by Kyoritsu Scientific Research Institute) and colorimetrically measured 10 minutes later. The odor concentration was also measured using a liquid detector tube (detector tube: Dissolved Sulfide 211H, manufactured by GASTEC) with a detector tube-type gas analyzer to measure the elution concentration of the odorous components into the solution, and the elution rate into the aqueous solution was calculated. A control example was also tested, as in Example 1. The elution results are summarized in Figure 6.

[0070] As is clear from Figure 6, in Example 6 of the deodorizing material comprising the deodorizing component, which is hexagonal plate-shaped simoncollite crystals to which the present invention is applied, the odorous components, ammonia, trimethylamine, isovaleric acid, and isobutanol, were all eluted at a high elution rate when washed with water.

[0071] (Evaluation Test 7 of Repeated Washing and Deodorization of Odor Components of Various Malodorous Gases: Example 7 and Control Example) The test was carried out in the same manner as in Example 6, except that hydrogen sulfide and ammonia were used instead of the odorous components in Example 6, and the elution rate was measured after five cycles of deodorization and water washing. The results are shown in Figure 7.

[0072] As is clear from Figure 7, no decrease in deodorizing properties was observed even after repeated deodorizing and rinsing, indicating that repeated use is possible simply by rinsing with water.

[0073] (Preparation Example 8-1) 300 ml of 40% aqueous sodium hydroxide (NaOH) solution in a 1000 ml reaction vessel was set to 70°C, and 400 ml of 25 wt% aqueous zinc chloride (ZnCl2) solution was added all at once, and the temperature was set to 70°C and stirred at normal pressure for 30 minutes. After that, 35 v / v% hydrochloric acid was added dropwise while stirring to adjust the pH to 7.0, and the mixture was left to stand for 1 hour to mature, producing a deodorizing material consisting only of simoncollite hexagonal plate crystals (film thickness 0.5 μm; aspect ratio 20:1), which was used as the test sample for Example Preparation 8-1.

[0074] (Preparation Example 8-2) 300 ml of 40% aqueous sodium hydroxide (NaOH) solution in a 1000 ml reaction vessel was set to 70°C, and 400 ml of 25 wt% aqueous zinc chloride (ZnCl2) solution was added all at once, and the temperature was set to 70°C and stirred at normal pressure for 30 minutes. After that, 35 v / v% hydrochloric acid was added dropwise while stirring to adjust the pH to 7.0, and the mixture was left to stand for 6 hours to mature, producing a deodorizing material consisting only of simoncollite hexagonal plate crystals (film thickness 1 μm; aspect ratio 10:1), which was used as the test sample for Example Preparation 8-2.

[0075] (Test 8 to evaluate the deodorizing effect of the deodorizing component, simoncollite hexagonal plate crystals, on various odorous gases at different thicknesses (film thicknesses): Example 8 and Control Example) Using the test samples of Preparation Examples 8-1 and 8-2, ammonia, hydrogen sulfide, and isovaleric acid were used instead of the odorous components in Example 1 to form Example 8, and a deodorizing property evaluation test was carried out in the same manner as in Example 1. The results are shown in Figure 8.

[0076] As is clear from Figure 8, Example 8 of the deodorizing material, which is made of a deodorizing component that is a hexagonal plate-like simoncollite crystal according to the present invention, showed high deodorizing properties regardless of the thickness and aspect ratio of the hexagonal plate-like simoncollite crystal.

[0077] (Preparation Example 9-1) The deodorizing material, which is a deodorizing component consisting only of simoncollite hexagonal plate crystals (film thickness 1 μm; aspect ratio 10:1) obtained in Preparation Example 8-2, was used as the test sample in Preparation Example 9-1.

[0078] (Preparation Example 9-2) 300 ml of 40% aqueous sodium hydroxide (NaOH) solution in a 1000 ml reaction vessel was set to 25° C., and 400 ml of 25 wt % aqueous zinc iodide (ZnI2) solution was added all at once, and the temperature was set to 25° C. and stirred at normal pressure for 30 minutes. After that, 35 v / v % hydrochloric acid was added dropwise while stirring to adjust the pH to 7.0, and the mixture was left to stand for 6 hours to mature, producing a deodorizing material consisting only of simoncolite (amorphous crystals), which was used as the test sample for Example Preparation 9-2.

[0079] (Preparation Example 9-3) 300 ml of 40% aqueous sodium hydroxide (NaOH) solution in a 1000 ml reaction vessel was set to 25°C, and 400 ml of 25 wt% aqueous zinc chloride (ZnCl) solution was added all at once, and the temperature was set to 25°C and stirred at normal pressure for 30 minutes. After that, 35 v / v% hydrochloric acid was added dropwise while stirring to adjust the pH to 7.0, and the mixture was left to stand for 6 hours to mature, producing a deodorizing material consisting only of simoncolite (flaky crystals) as a deodorizing component, which was used as the test sample for Example Preparation 9-3.

[0080] (Test 9 to evaluate the deodorizing properties of the deodorizing component for each crystal shape against various malodorous gases: Example 9) Using the test samples of Preparation Examples 8-1, 8-2, and 8-3, ammonia, trimethylamine, hydrogen sulfide, methyl mercaptan, isovaleric acid, and isobutanol were used instead of the odorous components in Example 1 to form Example 9, and a deodorizing property evaluation test was conducted in the same manner as in Example 1. The results are shown in Figure 9. Electron microscope photographs of each crystal system are also shown in Figure 9.

[0081] As is clear from FIG. 9, Example 9 of the deodorizing material comprising the deodorizing component, which is simoncollite of various crystal forms to which the present invention is applied, exhibited similarly high deodorizing properties regardless of the crystal form of the simoncollite.

[0082] (Preparation Example 10) The deodorizing material obtained in Preparation Example 8-2, which is a deodorizing component consisting only of simoncollite hexagonal plate crystals (film thickness 1 μm; aspect ratio 10:1), was used as the test sample in Preparation Example 10.

[0083] (Comparative Preparation Example 10-1) A deodorizing material consisting solely of activated carbon (trade name: Kuraray Coal KW) manufactured by Kuraray Co., Ltd. was used as the test sample of Comparative Preparation Example 10-1.

[0084] (Comparative Preparation Example 10-2) A deodorizing material consisting solely of the deodorizing component Kesmon NS-10, a deodorizer manufactured by Toagosei Co., Ltd., was used as the test sample of Comparative Preparation Example 10-2.

[0085] (Test 10 for evaluating the deodorizing properties of deodorizing ingredients against various malodorous gases over time: Example 10 and Comparative Example 10) Using the test samples of Preparation Example 10 and Preparation Comparative Examples 10-1 and 10-2, and using hydrogen sulfide, methyl mercaptan, isovaleric acid, and isobutanol instead of the odorous components in Example 1, Example 10 and Comparative Example 10 were prepared, and a deodorizing property evaluation test was conducted in the same manner as in Example 1. The results are shown in Figure 10.

[0086] As is clear from Figure 10, Example 10, a deodorizing material made of the deodorizing component Simoncolite to which the present invention is applied, showed high deodorizing properties for hydrogen sulfide and isovaleric acid even in a short time, and for methyl mercaptan and isobutanol over time, and was substantially comparable to Comparative Example 10-1 of activated carbon. On the other hand, Comparative Example 10-1 of Kesmon was inferior to these. [Industrial Applicability]

[0087] The deodorizing material of the present invention is Represented by the chemical formula (1) Layered ofThe deodorizing component of the present invention is useful for producing a deodorizing agent containing a deodorizing component comprising a hydroxide, a deodorizing fabric in which the deodorizing component is applied to or impregnated with the fabric, and a building material, industrial product, or daily necessities containing the deodorizing component. The method for preparing the deodorizing component of the present invention is useful for producing the deodorizing component that is the raw material for these deodorizers.

Claims

1. It has hydroxide layers containing one type of metal element, and cations, anions, and / or water molecules are intercalated between the layers, and it intercalates, adsorbs, or decomposes odorous components, and is represented by the following chemical formula (1): [M 2+ x (OH) (2x-y) ][A ny / n ・zH 2 O] ... (1) A deodorizing material for reuse that can be repeatedly reused by drying and releasing, releasing into water, and / or decomposing, and absorbing odorous components, consisting of ammonia, amine, mercaptan, acetaldehyde, isovaleric acid, and isobutanol, characterized in that it contains, as a deodorizing component, a layered hydroxide represented by the formula (1): (in which M 2+ is a cation of a divalent metal element, A n- is an anion with a valence of n (n is 1 to 3), x = 1 to 5, y is 1 to 10, and z is 1 to 10), which is a hexagonal plate-like crystal and has an aspect ratio L:H, where L is the average diameter across the hexagonal faces and H is the average height perpendicular to the hexagonal faces, of 20:1 to 10:

1.

2. 2. The deodorizing material according to claim 1, wherein the metal element is zinc.

3. 3. The deodorizing material according to claim 1, wherein the layered hydroxide represented by the chemical formula (1) is simoncollite.

4. 4. The deodorizing material according to claim 1, wherein the layered hydroxide represented by the chemical formula (1) has an aspect ratio of 10 to 12:

1.

5. The deodorizing material according to any one of claims 1 to 4, characterized in that it is a deodorizing agent in which the deodorizing component is contained as is or in either a solid carrier or a liquid or gel-like fluid carrier, a deodorizing fabric, clothing, apparel, or clothing or fibers thereof in which the deodorizing component is attached to or impregnated in the fabric, or a building material, industrial product, or daily necessities containing the deodorizing component.

6. A deodorant according to any one of claims 1 to 5, characterized in that the layered hydroxide represented by the chemical formula (1) is kneaded into a resin carrier.

7. A deodorizer as described in claim 6, characterized in that the resin forms a film shape.

8. A deodorizer as described in Claim 6, characterized in that the resin is polyethylene.

9. An aqueous solution of a water-soluble salt of one kind of metal and an aqueous solution of an alkali metal hydroxide are mixed under normal pressure, neutralized, and then allowed to stand at room temperature to produce a hydroxide layer containing one kind of metal element, with cations, anions, and / or water molecules intercalated between the layers, which intercalates, adsorbs, or decomposes odorous components, and is represented by the following chemical formula (1): [M 2+ x (OH) (2x-y) ][A ny / n ・zH 2 O] ... (1) A method for preparing a deodorizing component for reuse, which can be repeatedly reused by drying and releasing, releasing into water, and / or decomposing, and absorbing odorous components, consisting of ammonia, amine, mercaptan, acetaldehyde, isovaleric acid, and isobutanol, characterized by crystallizing a layered hydroxide represented by the formula (1): (in which M 2+ is a divalent metal cation, A n- is an n-valent anion (n is 1 to 3), x = 1 to 5, y is 1 to 10, and z is 1 to 10), which is a hexagonal plate-like crystal having an aspect ratio L:H, where L is the average diameter across the hexagonal faces and H is the average height perpendicular to the hexagonal faces, of 20:1 to 10:1.

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