JP6442120B1 - Substance-removable complex - Google Patents

Abstract

  Disclosed is a material having a substance decomposability that has the ability to effectively and continuously decompose and remove not only ammonia, acetic acid, isovaleric acid and hydrogen sulfide but also a wider variety of substances at a high level. An air catalyst comprising a metal composition containing iron, aluminum, potassium, and tungsten is a substance-decomposable / removable composite supported on the surface and / or inside of a crosslinked acrylate-based moisture-absorbing / releasing polymer, the metal composition The metal content ratio in the product is 1000 to 50000 ppm of aluminum, 50 to 1000 ppm of potassium, and 0.01 to 10 ppm of tungsten with respect to 100 ppm of iron. Also provided are fiber structures and products containing the material degradable composite.

Description

  The present invention relates to a substance-decomposable composite that dramatically increases the ability to decompose and remove a wide variety of substances by a synergistic effect of an air catalyst comprising a specific metal composition and a crosslinked acrylate-based moisture-absorbing / releasing polymer.

  With the recent increase in comfort and health awareness, there is a strong demand for the development of materials that have the function of decomposing or removing pollutants. Based on these functions, degrading and antibacterial substance decomposition and removal agents Many have been proposed.

  Patent Document 1 proposes a photocatalyst-containing fiber that is formed from a polymer having a crosslinked structure and a carboxyl group and contains metal oxide fine particles having photocatalytic activity. Such metal oxide fine particles have a function of adsorbing malodorous substances, allergens, fungi, viruses, etc. to carboxyl groups and decomposing with photocatalysts, but sufficient light irradiation is necessary to exert their functions. In addition, there is a problem that a substance that cannot be decomposed and removed only by adsorption with a carboxyl group exists.

  Patent Document 2 proposes a fiber structure in which an air catalyst that generates hydroxyl radicals, ozone, or peroxide without light irradiation is fixed. Air catalysts are excellent in decomposing and removing substances, but in order to perform their functions effectively, a sufficient amount of water vapor needs to be continuously present in the surroundings. There was a problem that there was a substance that was insufficiently removed.

  Patent Document 3 proposes a deodorant, an antibacterial agent, or an antifungal agent comprising a metal composition containing iron, aluminum and potassium, and an aqueous composition containing water. Since this water-based composition evaporates moisture when it adheres to an object, there is a limit to the continuous performance of the function, and there is a problem that there is a substance that is insufficiently decomposed and removed only by an air catalyst. .

  In response to these problems, the applicant has proposed a substance decomposition removal agent containing an air catalyst and a cross-linked acrylate type moisture absorbent (Patent Document 4). The substance decomposition / removal agent of Patent Document 4 had the ability to decompose and remove many types of substances more effectively and continuously than before, but not only ammonia, acetic acid, isovaleric acid, hydrogen sulfide, What has the ability to decompose more effectively to a wide variety of substances is required.

JP 2014-74243 A Japanese Patent Laying-Open No. 2005-60904 Japanese Patent Laid-Open No. 2007-215988 WO2016 / 063873

  The present invention was devised in view of the above-described conventional state of the art, and its purpose is not only ammonia, acetic acid, isovaleric acid, hydrogen sulfide, but also a wider variety of substances that are effective and sustained at a high level. It is an object of the present invention to provide a material having a material decomposing / removing property having an ability to be decomposed and removed.

  As a result of diligent studies to achieve the above object, the present inventors have increased the amount of aluminum and potassium relative to iron, and an air catalyst comprising a metal composition in which a small amount of tungsten is added in place of titanium, is used as a crosslinked acrylate. -Based moisture-absorbing / releasing polymer supported on the surface and / or inside, improving the oxidizing power of iron ion catalyst by tungsten in air catalyst and deodorizing various odor components by increasing the amount of aluminum and potassium It has been found that the ability to decompose and remove a wide variety of organic and inorganic substances (excluding metals) is dramatically improved by improving the performance and synergistically adding the substance adsorption ability of the hygroscopic polymer. The present invention has been completed.

That is, the present invention has the following configurations (1) to (6).
(1) An air catalyst composed of a metal composition containing iron, aluminum, potassium, and tungsten is a substance decomposition / removable composite supported on the surface and / or inside of a crosslinked acrylate moisture-absorbing / releasing polymer. A substance-decomposable composite, wherein the metal content in the metal composition is 1000 to 50000 ppm of aluminum, 50 to 1000 ppm of potassium, and 0.01 to 10 ppm of tungsten with respect to 100 ppm of iron.
(2) The material-decomposable composite as described in (1), wherein the metal composition does not contain titanium, or the titanium content in the metal composition is less than 0.1 ppm with respect to 100 ppm of iron. body.
(3) The material decomposition removability according to (1) or (2), wherein the content of the metal composition is 0.01% by mass or more with respect to the crosslinked acrylate-based hygroscopic polymer. Complex.
(4) The iron content in the metal composition is 5 to 100 ppm, the aluminum content is 500 to 5000 ppm, the potassium content is 10 to 100 ppm, and the tungsten content is 0.01 to 5 ppm (1 The substance-decomposable complex according to any one of (1) to (3).
(5) A fiber structure comprising the material decomposition-removable composite according to any one of (1) to (4).
(6) A product comprising the substance decomposition-removable complex according to any one of (1) to (4).

  The substance-decomposable composite of the present invention continuously increases the water vapor concentration around the air catalyst due to the presence of the crosslinked acrylate-based moisture-absorbing / releasing polymer. Except for the above), and the adsorption effect of the substance by the cross-linked acrylate type moisture-absorbing / releasing polymer exists, so it can be applied to a wide variety of organic and inorganic substances (excluding metals). Excellent decomposition and removal ability. In particular, the air catalyst used in the material decomposition-removable composite of the present invention has a catalyst cycle that rotates with less energy due to the addition of tungsten. Therefore, a cross-linked acrylate-based moisture-absorbing / releasing polymer has an odor component in an equilibrium state of adsorption / desorption. Decompose more and faster. Moreover, the deodorizing performance of various odor components is improved by increasing the aluminum content relative to the iron component in the air catalyst. Furthermore, the substance-decomposable / removable composite of the present invention is required to have deodorizing properties, antibacterial properties, antiviral properties, antifungal properties, etc., fiber structures such as batting, nonwoven fabrics, woven fabrics, knitted fabrics, yarns, etc. It can be easily contained in or attached to various products such as films and filters to exert its effect.

  The substance-decomposable / removable composite of the present invention carries an air catalyst comprising a specific metal composition on the surface and / or inside of a crosslinked acrylate-based moisture-absorbing / releasing polymer. Through the synergistic effect of coalescence, the ability to decompose and remove substances is dramatically improved, and deodorant, antibacterial, antiviral, and antifungal properties are continuously exhibited at a high level. In particular, the composition of the metal composition composing the air catalyst has been reviewed, and its ability to decompose and remove substances has been dramatically improved.

  The air catalyst used in the substance decomposition-removable complex of the present invention reacts with moisture in the air by a catalytic effect without using chemicals to generate hydroperoxyl radicals and superoxide ions, and removes harmful substances. Decomposes and exhibits excellent effects such as antibacterial and deodorant.

  The air catalyst of the present invention comprises a metal composition containing iron, aluminum, potassium, and tungsten. For example, alum, iron oxide (III) aqueous solution, alum, aluminum oxide fine powder, and tungsten oxide (VI) fine powder. It can be produced by mixing the powder uniformly. Or it can also manufacture by selecting the suitable soil which measured the component composition previously, and mix | blending the tungsten from tungsten oxide with iron, aluminum, and potassium extracted from there by an inorganic acid or a sulfuric acid. The air catalyst itself, including its mechanism of action, has been widely known and commercially available.

  Potassium in the air catalyst is an energy source for the air catalyst to have an effect of decomposing and removing substances. Electron beams emitted from potassium collide with surrounding water molecules, and hydrated electrons, atomic hydrogen, hydrogen gas, hydroxyl radicals, and hydrogen peroxide are generated. Hydrated electrons and atomic hydrogen are oxidized to produce hydroperoxyl radicals and superoxide ions, which together with atomic hydrogen produce hydrogen peroxide. Hydrogen peroxide is reduced by iron to generate hydroxy radicals and hydroxide ions (Fenton reaction). Hydrogen peroxide is oxidized by iron to produce hydroperoxyl radicals and hydrogen ions. Hydroxy radicals and superoxide ions have a strong oxidizing power, thereby decomposing / removing substances and inhibiting the growth of microorganisms.

  As described above, iron promotes the formation reaction of hydroxy radicals and hydroxide ions (Fenton reaction) and the formation reaction of hydroperoxyl radicals and hydrogen ions. Aluminum functions as a binding material for fixing and fixing to an object or a carrier. Tungsten is a rare element particularly compatible with iron, and can always inject oxidizing power into the iron ion catalyst, thereby contributing to the sustaining and strengthening of the substance decomposition / removal effect. Content of aluminum, potassium, and tungsten is the ratio of 1000-50000 ppm, 50-1000 ppm, and 0.01-10 ppm with respect to 100 ppm of iron, respectively. Preferably, the ratio is 5000 to 50000 ppm, 100 to 1000 ppm, and 0.1 to 5 ppm, respectively, with respect to 100 ppm of iron. The content of aluminum and potassium in the metal composition constituting the air catalyst of the present invention is much higher than that of the metal composition constituting the conventional air catalyst. The deodorizing effect of various odor components is enhanced by increasing the aluminum content, and the sustainability of the deodorizing effect is enhanced by increasing the potassium content. The metal composition constituting the air catalyst of the present invention preferably does not contain titanium or contains less than 0.1 ppm with respect to 100 ppm of iron ions even if it contains titanium. Since the air catalyst of the present invention does not actively contain titanium, the cost for synthesis and production is low, and stable production is possible.

  The iron content in the metal composition constituting the air catalyst of the present invention is 5 to 100 ppm, the aluminum content is 500 to 5000 ppm, the potassium content is 10 to 100 ppm, and the tungsten content is 0.01 to 5 ppm. preferable.

  The crosslinked acrylate-based moisture-absorbing / releasing polymer used in the substance-decomposable / removable composite of the present invention is a conventionally known polymer composed of a crosslinked acrylate-based polymer having a crosslinked structure and a carboxyl group. The thing whose amount is 0.1-10 mmol / g is preferable, and what is 3-8 mmol / g is more preferable. In addition, as the form of the crosslinked acrylate-based moisture-absorbing / releasing polymer, for example, a fiber type or a particle type (powder or emulsion) can be used. As the fiber type, for example, as described in JP-A-2000-314082, the nitrogen content introduced by a crosslinking treatment with a hydrazine compound on an acrylic fiber having an acrylonitrile content of 85 to 95% by weight The increase is 1.0 to 5.0% by weight of the crosslinked acrylic fiber, and a part of the residual nitrile group is converted to an alkali metal salt type carboxyl group of 3.0 to 6.0 meq / g. In addition, hygroscopic fibers having a difference in moisture absorption between 20 ° C. × 50% RH condition and 20 ° C. × 95% RH condition are 50 wt% or more and 150 wt% or less. The cross-linked acrylic fiber is an H-type carboxyl group that is not converted into a salt type other than those converted into an alkali metal or alkaline earth metal salt type carboxyl group such as Na salt, Mg salt, and Ca salt as described above. There are types. Among the particle types, the powder type has a polar group of any one of a sulfonic acid group, a carboxylic acid group, and a phosphoric acid group and a crosslinked acrylate structure, as described in, for example, JP-A-10-237126. A polymer can be used, and as an emulsion, for example, a fine particle emulsion polyacrylonitrile-based polymer can be used as described in Examples of Japanese Patent No. 5203604.

  The content of the metal composition of the air catalyst in the substance decomposition-removable composite of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass with respect to the crosslinked acrylate-based moisture-absorbing / releasing polymer. As mentioned above, More preferably, it is 0.1 mass% or more, and although an upper limit is not specifically limited, It is 20 mass% from an economical viewpoint.

  Moreover, in this invention, the air catalyst is carry | supported on the surface and / or inside of a crosslinked acrylate type moisture absorption / release polymer. Examples of the supporting method include a method in which a dispersion containing an air catalyst is impregnated with a crosslinked acrylate-based moisture-absorbing / releasing polymer and then dried. At this time, when a liquid containing water is used as a dispersion medium, the crosslinked acrylate-based moisture-absorbing / releasing polymer swells with the liquid, and therefore, an air catalyst can be supported not only on the surface of the polymer but also on the inside. It becomes possible. By supporting the air catalyst inside the cross-linked acrylate-based moisture-absorbing / releasing polymer, it is possible to suppress the air catalyst from falling off due to friction or the like, and it is difficult for the material decomposition and removal performance to deteriorate even during long-term use.

  The substance-decomposable / removable composite of the present invention can be formed alone or in combination with other materials or attached to other materials to form a fiber structure. Moreover, the substance decomposition-removable composite of the present invention can be used by being mixed or adhered to a film, a molded product, paper or the like. When used together with other materials, the substance decomposition / removable composite of the present invention is preferably used in an amount of 3% by weight or more, more preferably 5% by weight or more in terms of effect. The upper limit is not particularly limited, but is 80% by weight from an economic viewpoint.

  In addition, as described above, when combining the material decomposition-removable composite of the present invention with another material, a binder component for fixing to the other material, a solvent such as water or an organic solvent for viscosity adjustment, etc. Can be used together. Here, a thermoplastic resin or a thermosetting resin is used as the bainter component. When a solvent is used, a solvent in which the resin used can be dissolved or dispersed is preferable.

  Examples of the appearance of the fiber structure of the present invention include batting, yarn, knitted fabric, woven fabric, non-woven fabric, pile fabric, paper-like material, and filter. The inclusion form of the substance-decomposable / removable composite in the fiber structure of the present invention is substantially uniformly distributed, concentrated in a specific location, or distributed in a specific ratio at each location. And so on.

  Examples of products containing the substance-decomposable composite of the present invention include futons, nursing skins, general skins, nursing pads, down jackets, absorbent sheets, deodorant sheets, antibacterial sheets, PM2.5 measures Mask, bag filter, environmental pollutant adsorption / decomposition filter, environmental pollutant adsorption / decomposition cover, washing machine filter, vacuum cleaner filter, futon cleaner filter, air cleaner, air conditioner filter, name sewing thread, hem, Neck cooler, muffler, table cloth, curtain, lace curtain, screen door, screen door filter, table cloth, inner, socks, touch panel film, cleaned cover film, incontinence diaper, absorber, adhesive bandage, urethane film, environmental pollution Material adsorption decomposition sheet, freshness-keeping sheet, silicone rubber Type products, nylon resin moldings, picture material, and the like freshness keeping agent.

  The material decomposition-removable composite of the present invention, and the fiber structure and product containing them include a wide range of organic and inorganic substances such as ammonia, acetic acid, isovaleric acid, hydrogen sulfide, indole, toluene, formaldehyde, nitric oxide, nitrogen dioxide, etc. Substances (excluding metals) can be continuously decomposed and removed at a higher level than before. It also has an antibacterial function that suppresses the growth of bacteria, viruses, and molds. Furthermore, it can be applied to pollutants such as tobacco dust and pollen. On the other hand, growth-promoting hormone (ethylene gas) produced from fresh foods such as fruits and vegetables can be decomposed, and it can be used as a freshness-preserving agent for fresh foods together with antibacterial effects. Therefore, the substance decomposition-removable complex of the present invention can function as a deodorant, an antibacterial agent, an antiviral agent, a fungicide, an environmental pollutant adsorption decomposition remover, a freshness maintaining agent, and an antifouling agent.

  The effects of the substance-decomposable / removable complex of the present invention will be shown below by examples, but the present invention is not limited to these examples.

Examples 1-10, Comparative Examples 1-4
<Production of air catalysts (A) to (F)>
Alum (potassium aluminum sulfate twelve hydrate) and aluminum oxide fine powder in an aqueous solution of iron (III) paratoluenesulfonate so that the amounts of iron, aluminum, potassium, tungsten and titanium are in the proportions shown in Table 1. (Particle diameter 1 μm or less), tungsten oxide (VI) fine powder (particle diameter 1 μm or less), and titanium oxide fine powder (particle diameter 1 μm or less) are mixed uniformly to produce air catalysts (A) to (F). did.

<Production of Crosslinked Acrylate-Based Hygroscopic Polymers (a) to (d)>
As the crosslinked acrylate-based moisture-absorbing / releasing polymers (a) to (d), crosslinked acrylate-based moisture-absorbing / releasing fibers having carboxyl groups of COOH type, COONa salt type, COOMg salt type, and COOCa salt type were prepared.

The crosslinked acrylate-based moisture-absorbing / releasing polymer (a) having a carboxyl group of COOH type was produced as follows.
Spinning stock solution prepared by dissolving acrylonitrile polymer of 90% by weight of acrylonitrile and 10% by weight of methyl acrylate in 48% by weight of rhodium soda aqueous solution is spun, washed, drawn, crimped and heat-treated according to usual methods to obtain a single fiber fineness of 1 A 5d raw fiber was obtained. This raw fiber was subjected to hydrazine treatment and hydrolysis treatment, and then subjected to acid treatment, followed by dehydration, washing with water, and drying to obtain a COOH-type crosslinked acrylate moisture-absorbing and releasing fiber. It was 4.5 mmol / g when the amount of carboxyl groups of the fiber was determined by titration with an aqueous sodium hydroxide solution.

  Crosslinked acrylate-based moisture-absorbing / releasing polymers having carboxyl groups of COONa salt type (b), COOMg salt type (c), and COOCa salt type (d) were also produced in the same manner.

  According to the description in Table 2, each of the above-mentioned crosslinked acrylate-based moisture-absorbing / releasing fibers was immersed in the liquid containing each of the above-mentioned air catalysts, and after centrifugal dehydration, drying was carried out, so that Examples 1 to 10 and Comparative Examples 2 to 4 A substance-decomposable complex was obtained. Moreover, regarding Comparative Example 1, a substance-decomposable composite was obtained in the same manner as in Example 1 except that polyester fiber was used instead of the crosslinked acrylate-based moisture absorbing / releasing fiber. In addition, about content (mass%) of the air catalyst contained in each bridge | crosslinking acrylate type moisture absorption / release fiber or polyester fiber, the fiber absorbed by subtracting the fiber weight before immersion from the fiber weight after centrifugal dehydration. It calculated by calculating | requiring the air catalyst containing liquid amount, multiplying this by the density | concentration of a containing liquid, and remove | dividing by the fiber weight before immersion. The air catalyst content was adjusted by adjusting the concentration of the air catalyst containing liquid.

  After preparing 0.5 g (absolute dry weight) of each sample of the material decomposition removed bodies of Examples 1 to 10 and Comparative Examples 1 to 4 and adjusting the humidity under the condition of 20 ° C. × 65% RH for 24 hours, 5 liters were prepared. In a Tedora bag. In a Tedra bag containing the sample, 3 liters of 20 ° C. × 65% RH air and a predetermined substance (ammonia, acetic acid, isovaleric acid, hydrogen sulfide, indole, toluene, etc.) having an initial concentration shown in Table 3 Formaldehyde or nitric oxide) was added, and the concentration of the added substance was measured with a detector tube after 2 hours and 24 hours at 20 ° C. × 65% RH. Note that the same concentration measurement was performed on a blank in which no sample was sealed in the Tedora bag. The results are shown in Table 3.

  As can be seen from the results in Table 3, Examples 1-10, in which the air catalyst of the metal composition within the scope of the present invention and the crosslinked acrylate-based moisture-absorbing / desorbing fibers were used in combination, decreased the concentration for all the substances tested over time. Therefore, high substance decomposition / removal effect and deodorization effect can be achieved. On the other hand, Comparative Example 1 in which the air catalyst is used alone and Comparative Example 2 in which the crosslinked acrylate-based moisture-absorbing / releasing fiber is used are limited in the types of substances in which the substance-removing effect is recognized. The effective effect is considerably inferior to Examples 1-10. In addition, Comparative Examples 3 and 4 in which the air catalyst of the metal composition outside the scope of the present invention and the crosslinked acrylate-based moisture-absorbing / releasing fiber are used in combination have a substance removal effect for a specific substance, The effect over time is clearly inferior to Examples 1-10.

  The substance-decomposable composite of the present invention maintains a high level of decomposition / removal effect of a wide variety of substances. Therefore, the substance-decomposable complex is used by being mixed with or imparted to various fiber structures and products that are required to exhibit this effect. can do.

Claims (6)

  An air catalyst comprising a metal composition containing iron, aluminum, potassium, and tungsten is a substance-decomposable / removable composite supported on the surface and / or inside of a crosslinked acrylate-based moisture-absorbing / releasing polymer, the metal composition A substance-decomposable composite having a metal content ratio of 1000 to 50000 ppm of aluminum, 50 to 1000 ppm of potassium, and 0.01 to 10 ppm of tungsten with respect to 100 ppm of iron.   The metal composition according to claim 1, wherein the metal composition does not contain titanium, or the titanium content in the metal composition is less than 0.1 ppm with respect to 100 ppm of iron.   3. The substance-decomposable / removable composite according to claim 1, wherein the content of the metal composition is 0.01% by mass or more based on the crosslinked acrylate-based hygroscopic polymer.   The iron content in the metal composition is 5 to 100 ppm, the aluminum content is 500 to 5000 ppm, the potassium content is 10 to 100 ppm, and the tungsten content is 0.01 to 5 ppm. The substance-removable complex according to any one of the above.   A fiber structure comprising the substance-decomposable / removable composite according to claim 1.   A product comprising the substance decomposition-removable complex according to any one of claims 1 to 4.