WO2019058674A1 - Complex for decomposing and removing substance - Google Patents

Abstract

Provided is a complex for decomposing and removing a substance, the complex being capable of highly effectively and continuously decomposing and removing not only ammonia, acetic acid, isovaleric acid, and hydrogen sulfide, but also a wide variety of other substances. The complex for decomposing and removing a substance is characterized in that an air catalyst comprising a metal composition containing iron, aluminum, potassium, and tungsten is supported on the surface and/or the inside of a crosslinked acrylate-based moisture absorptive and desorptive polymer, wherein the metal content in the metal composition with respect to 100 ppm of iron is 1000-50000 ppm for aluminum, 50-1000 ppm for potassium, and 0.01-10 ppm for tungsten. A fibrous structure containing the complex for decomposing and removing a substance, and a product are also provided.

Description

Material decomposition removability complex

The present invention relates to a substance decomposable composite having a dramatically enhanced ability to decompose and remove a wide variety of substances by the synergetic effect of an air catalyst composed of a specific metal composition and a crosslinked acrylate-based moisture-absorbing polymer.

Development of materials having the function of decomposing or removing pollutants is strongly demanded from the recent increase in comfort and awareness of health, and the substance decomposition and removal agent having deodorizing property and antibacterial property based on these functions Many have been proposed.

Patent Document 1 proposes a photocatalyst-containing fiber which is formed of a polymer having a crosslinked structure and a carboxyl group and which contains metal oxide fine particles having photocatalytic activity. Such metal oxide fine particles have a function of adsorbing offensive odor substances, allergens, bacteria, viruses and the like to carboxyl groups and being decomposed by photocatalysts, but sufficient light irradiation is necessary to exhibit the functions. In addition, there is a problem that there is a substance which is not sufficiently decomposed and removed only by adsorption by the carboxyl group.

Patent Document 2 proposes a fiber structure in which an air catalyst that generates hydroxyl radicals, ozone or peroxide without light irradiation is fixed. Although air catalysts are excellent in the effect of decomposing and removing substances, in order to exert their functions effectively, it is necessary that a sufficient amount of water vapor be continuously present around them, and in the case of air catalysts alone, they are decomposed. There was a problem that there were substances that were not sufficiently 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. In this aqueous composition, since the moisture evaporates when it adheres to the object, there is a limit to the sustained performance of its function, and there is a problem that there is a substance which is not sufficiently decomposed and removed by the air catalyst alone. .

With respect to these problems, the applicant has proposed a substance decomposition removal agent containing an air catalyst and a crosslinked acrylate-based moisture absorbent / desorbent (Patent Document 4). Although the substance decomposition and removal agent of Patent Document 4 had the ability to decompose and remove many kinds of substances more effectively and continuously than before, it is not only ammonia, acetic acid, isovaleric acid, hydrogen sulfide, and further There is a need for the ability to more effectively degrade a wide variety of substances.

JP 2014-74243 A JP, 2005-60904, A Unexamined-Japanese-Patent No. 2007-215988 WO 2016/063873

The present invention has been made in view of the above-mentioned prior art, and its object is not only ammonia, acetic acid, isovaleric acid, hydrogen sulfide but also a wide variety of substances to be effectively and sustained at high levels. It is an object of the present invention to provide a material having the ability to decompose and remove substances which has the ability to be decomposed and removed.

As a result of intensive studies to achieve the above object, the inventor of the present invention has conventionally increased the amount of aluminum and potassium relative to iron and crosslinked an air catalyst comprising a metal composition to which a small amount of tungsten was added instead of titanium. In the air catalyst, the oxidation power of the iron ion catalyst is improved by the use of tungsten supported on the surface and / or the inside of the system moisture absorbing and releasing polymer, and the deodorizing of various odorous components by the increase of the amount of aluminum and potassium. It is found that the performance improvement and the material adsorption ability of the hygroscopic polymer are synergistically added to this, and the ability to decompose and remove a wide variety of organic substances and inorganic substances (except metals) is significantly enhanced than before. The present invention has been completed.

That is, the present invention has the following configurations (1) to (6).
(1) A material decomposition-removable composite in which an air catalyst comprising a metal composition containing iron, aluminum, potassium, and tungsten is supported on the surface and / or inside of a crosslinked acrylate-based moisture-absorbing polymer. A material decomposition-removable composite characterized in that the metal content ratio 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 according to (1), wherein the metal composition contains no titanium, or the titanium content in the metal composition is less than 0.1 ppm relative to 100 ppm of iron. body.
(3) The content of the metal composition is 0.01% by mass or more with respect to the crosslinked acrylate-based moisture absorbable polymer, and the substance decomposition and removability according to (1) or (2) is characterized. Complex.
(4) The metal composition is characterized in that 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 And 3.) the substance degradable complex according to any one of (3) to (3).
(5) A fiber structure comprising the substance decomposing / removing composition according to any one of (1) to (4).
(6) A product comprising the substance decomposable / removable complex according to any one of (1) to (4).

The substance decomposing / removing material of the present invention continuously increases the concentration of water vapor around the air catalyst by the presence of the crosslinked acrylate-based moisture-absorbing polymer, so that the organic substance and inorganic substance (metal Can sufficiently exhibit the decomposition / removal ability (excluded) and the adsorption effect of the substance by the crosslinkable acrylate type moisture absorbing and desorbing polymer also exists, so it can be applied to a wide variety of organic substances and inorganic substances (except metals). The ability to disassemble and remove is extremely excellent. In particular, the air catalyst used in the substance decomposing / removing composite of the present invention has a catalyst cycle with less energy due to the addition of tungsten, so the cross-linked acrylate-based polymer has odor components in equilibrium of adsorption and desorption. It breaks down more and faster. Moreover, the deodorizing performance of various odor components is also improved by the increase of the content of aluminum to the iron component in the air catalyst. Furthermore, the material decomposition and removability composite of the present invention is required to be deodorant, antibacterial, antiviral and antifungal, etc., a fiber structure such as batting, non-woven fabric, woven fabric, knitted fabric, yarn, and coating film It can be easily contained or attached to various products such as films, filters, etc. to exert its effect.

The substance decomposing / removing material of the present invention supports an air catalyst consisting of a specific metal composition on the surface and / or inside of a crosslinked acrylate-based moisture-absorbing polymer, and the air catalyst and the moisture-absorbing heavy polymer The synergetic effect of the combination dramatically enhances the decomposition and removal ability of the substance, and exerts a deodorizing property, an antibacterial property, an antiviral property, a mold resistance and the like at a sustained high level. In particular, the composition of the metal composition that constitutes the air catalyst has been reviewed, and its material decomposition and removal ability has been dramatically enhanced over the prior art.

The air catalyst used in the substance degradable complex of the present invention reacts with the moisture in the air by catalytic effect to generate hydroperoxyl radical and superoxide ion without using chemical agents, thereby producing harmful substances. It decomposes and exhibits superior effects such as antibacterial and deodorant.

The air catalyst of the present invention is composed of a metal composition containing iron, aluminum, potassium and tungsten, for example, an aqueous solution of iron (III) p-toluenesulfonate and a fine powder of aluminum and fine powder of aluminum oxide and fine powder of tungsten oxide (VI). It can be produced by uniformly mixing the powder. Alternatively, it can also be produced by selecting an appropriate soil whose component composition has been measured in advance, and blending iron, aluminum and potassium extracted therefrom with inorganic acid or sulfuric acid with tungsten from tungsten oxide. The air catalyst itself, including its mechanism of action, is conventionally and widely known, and there are commercially available products.

Potassium in the air catalyst is an energy source for the air catalyst to have the effect of decomposing and removing substances. An electron beam or the like emitted from potassium collides with surrounding water molecules to generate hydrated electrons, atomic hydrogen, hydrogen gas, hydroxyl radicals, hydrogen peroxide. Hydrated electrons and atomic hydrogen are oxidized to form hydroperoxyl radicals and superoxide ions, and hydroperoxyl radicals form hydrogen peroxide together with atomic hydrogen. Hydrogen peroxide is reduced by iron to form hydroxy radicals and hydroxide ions (Fenton reaction). Hydrogen peroxide is oxidized by iron to form hydroperoxyl radicals and hydrogen ions. Hydroxy radicals and superoxide ions have strong oxidizing power, and thereby have the effect of inhibiting the growth of microorganisms while decomposing and removing substances.

Iron promotes the formation reaction of hydroxy radical and hydroxide ion (Fenton reaction) as described above, and the formation reaction of hydroperoxyl radical and hydrogen ion. Aluminum functions as a bonding material for fixing and fixing to an object or carrier. Tungsten is a rare element that is particularly compatible with iron, and can always inject oxidizing power into the iron ion catalyst, thereby contributing to the maintenance and enhancement of the substance decomposition and removal effect. The contents of aluminum, potassium and tungsten are in proportions of 1000 to 50000 ppm, 50 to 1000 ppm and 0.01 to 10 ppm with respect to 100 ppm of iron, respectively. Preferably, it is a ratio of 5000 to 50000 ppm, 100 to 1000 ppm, and 0.1 to 5 ppm with respect to 100 ppm of iron, respectively. The content of aluminum and potassium of 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 with respect to the content of aluminum and potassium relative to iron. An increase in the aluminum content enhances the deodorizing effect of various odorous components, and an increase in the potassium content enhances the sustainability of the deodorizing effect. The metal composition constituting the air catalyst of the present invention preferably contains no titanium, or preferably contains less than 0.1 ppm with respect to 100 ppm of iron ions. The air catalyst of the present invention does not actively contain titanium, so the cost for synthesis and manufacture is low, and stable manufacture 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 polymer used in the substance decomposition-removable composite of the present invention is a conventionally known one having a crosslinked acrylate-based polymer having a crosslinked structure and a carboxyl group as a constituent, particularly a carboxyl group. The amount is preferably 0.1 to 10 mmol / g, more preferably 3 to 8 mmol / g. Further, as the form of the crosslinked acrylate-based moisture-absorbing polymer, for example, fiber type and particle type (powder or emulsion) can be used. As the fiber type, for example, as described in JP-A-2000-314082, it is possible to use a nitrogen content introduced by a crosslinking treatment of an acrylic fiber having an acrylonitrile content of 85 to 95% by weight with a hydrazine compound. A cross-linked acrylic fiber having an increase of 1.0 to 5.0% by weight, and a part of the remaining nitrile group is converted to an alkali metal salt type carboxyl group of 3.0 to 6.0 meq / g, In addition, moisture absorbing and desorbing fibers having a moisture absorption difference of 50% by weight or more and 150% by weight or less between the conditions of 20 ° C. × 50% RH and 20 ° C. × 95% RH are mentioned. The cross-linked acrylic fiber is an H-type carboxyl group which is not converted into a salt form other than those converted into alkali metal or alkaline earth metal salt type carboxyl groups such as Na salt, Mg salt and Ca salt as described above. There is a type of thing. Among the particle types, as powdery ones, for example, as described in JP-A-10-237126, it 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. A polymer can be used, and as an emulsion, for example, as described in the example of Japanese Patent No. 5203604, a fine particulate emulsion polyacrylonitrile-based polymer can be used.

The content of the metal composition of the air catalyst in the substance decomposing / removing composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass, relative to the crosslinked acrylate-based moisture absorbable polymer. The content is more preferably 0.1% by mass or more, and the upper limit is not particularly limited, but is 20% by mass from the economical viewpoint.

Further, in the present invention, the air catalyst is supported on the surface and / or inside of the crosslinked acrylate-based moisture-absorbent polymer. As a method of supporting, there can be mentioned a method of impregnating a dispersion containing an air catalyst with a crosslinked acrylate-based moisture-absorbing polymer and then drying it. At this time, when a liquid containing water is used as a dispersion medium, the crosslinked acrylate-based moisture-absorbing 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 on the inside of the crosslinked acrylate-based moisture-absorbing polymer, the air catalyst is prevented from coming off due to friction or the like, and the material decomposition and removal performance is less likely to deteriorate even in long-term use.

The degradable composite of the present invention can be used alone or in combination with other materials or combined with other materials to form a fibrous structure. In addition, the substance decomposition-removable composite of the present invention can be used by being mixed or attached to a film, a molded article, paper or the like. When used in combination with other materials, it is preferable to use 3 wt% or more, and more preferably 5 wt% or more of the material decomposition-removable composite of the present invention in terms of effect expression. The upper limit is not particularly limited, but is 80% by weight from an economic viewpoint.

In addition, as described above, when the substance decomposing / removing composition of the present invention is combined with other materials, binder components for fixing to other materials, solvents such as water and organic solvents for viscosity adjustment, etc. It can be used together. Here, as the binder component, a thermoplastic resin, a thermosetting resin, or the like is used. 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 batts, yarns, knitted fabrics, woven fabrics, nonwoven fabrics, non-woven fabrics, pile fabrics, paper-like materials, filters and the like. The form of inclusion of the substance degradable complex in the fiber structure of the present invention is substantially uniformly distributed, concentrated at a specific place, or distributed at a specific ratio for each place And so on.

The products containing the substance decomposition and removability composite of the present invention include duvets, skin care covers, general skin coverings, care pads, down jackets, absorber sheets, odor control sheets, antibacterial sheets, PM 2.5 measures Masks, bag filters, filters for adsorptive decomposition of environmental contaminants, covers for adsorptive decomposition of environmental contaminants, filters for washing machines, filters for vacuum cleaners, filters for futon cleaners, filters for air cleaners, air conditioner filters, sewing threads for names, hems, Neck cooler, muffler, table cloth, curtain, lace curtain, screen door, screen door filter, inner fabric, socks, film for touch panel, cleaned cover film, incontinence diaper, absorber, plaster, urethane film, environmental pollution Material adsorptive decomposition sheet, freshness holding sheet, silicone rubber Molding, nylon resin moldings, picture material, and the like freshness keeping agent.

The degradable complex of the present invention, and fiber structures containing them, products are 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 (except metals) can be continuously decomposed and removed at higher levels than before. It also has an antibacterial function to suppress the growth of bacteria, viruses and molds. Furthermore, the present invention is also applicable to polluting substances such as tobacco dust and pollen. On the other hand, decomposition of growth promoting hormone (ethylene gas) produced from fresh food such as fruits and vegetables is also possible, and it can be used as a freshness keeping agent for fresh food as well as antibacterial effect. Therefore, the substance decomposition and removal complex of the present invention can function as a deodorant, an antibacterial agent, an antiviral agent, an antifungal agent, an environmental pollutants adsorptive removal agent, a freshness maintenance agent, and an antifouling agent.

The effects of the substance degradable complex of the present invention will be shown below by way of examples, but the present invention is not limited thereto.

Examples 1 to 10, Comparative Examples 1 to 4
<Production of air catalysts (A) to (F)>
Alum (aluminum potassium sulfate dodecahydrate) 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 as described in Table 1 (Particle diameter: 1 μm or less), tungsten oxide (VI) fine powder (particle diameter: 1 μm or less), titanium oxide fine powder (particle size: 1 μm or less) are uniformly mixed to produce air catalysts (A) to (F) did.

<Production of Crosslinked Acrylate-Based Moisture Absorbing and Desorbable Polymer (a) to (d)>
As crosslinked acrylate-based moisture-absorbable polymers (a) to (d), crosslinked acrylate-based moisture-desorbable fibers having a COOH type, a COONa salt type, a COOMg salt type, and a COOCa salt type, respectively, were prepared.

The crosslinked acrylate-based moisture-absorbing polymer (a) having a COOH type carboxyl group was produced as follows.
A spinning solution prepared by dissolving 90 wt% acrylonitrile and 10 wt% methyl acrylate acrylonitrile polymer in a 48 wt% aqueous solution of rhodanate soda according to a conventional method is spun, washed with water, drawn, crimped and heat treated to obtain a single fiber denier 1 Raw material fiber of .5d was obtained. The raw material fiber was subjected to a hydrazine treatment and a hydrolysis treatment, and then acid treatment was performed, followed by dehydration, washing with water and drying to obtain a COOH type crosslinked acrylate moisture absorbing and desorbable fiber. It was 4.5 mmol / g when the carboxyl group amount of this fiber was determined by titration using sodium hydroxide aqueous solution.

A crosslinked acrylate-based moisture-absorbing polymer in which the carboxyl group is COONa salt type (b), COOMg salt type (c), or COOCa salt type (d) was also produced by the same method.

Each of the crosslinked acrylate-based moisture-absorbent fibers is immersed in the above-described air catalyst-containing solution according to the description in Table 2, centrifuged and then dried to obtain Examples 1-10 and Comparative Examples 2-4. A substance degradable complex was obtained. Further, with regard to Comparative Example 1, a substance decomposition and removal composite was obtained in the same manner as in Example 1 except that polyester fiber was used instead of the crosslinked acrylate moisture absorbing and desorbing fiber. In addition, about content (mass%) of the air catalyst contained in each crosslinked acrylate moisture absorbing and desorbing fiber or polyester fiber, the fiber was absorbed by subtracting the fiber weight before immersion from the fiber weight after centrifugal dewatering. The amount of air catalyst containing liquid was determined, this was multiplied by the concentration of the contained liquid, and it was calculated by dividing by the fiber weight before immersion. Moreover, adjustment of air catalyst content was performed by adjustment of the density | concentration of an air catalyst containing liquid.

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

As can be seen from the results in Table 3, Examples 1 to 10 in which the air catalyst of the metal composition within the scope of the present invention and the crosslinked acrylate moisture absorbing and desorbing fiber were used in combination decreased the concentration for all the tested substances with time. It is possible to achieve high substance decomposition and removal effects and deodorizing effects. On the other hand, in Comparative Example 1 of the single use of the air catalyst and Comparative Example 2 of the single use of the cross-linked acrylate moisture absorbing and desorbing fiber, the types of substances in which the substance removing effect is recognized are limited. Effects are considerably inferior to those of Examples 1 to 10. Further, in 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 moisture absorbing and desorbing fiber were used in combination, the effect of removing the substance was recognized for the specific substance. The effect over time is clearly inferior to Examples 1 to 10.

Since the decomposition / removal composite of the present invention is maintained at a high level of the effects of decomposition and removal of a wide variety of substances, it is used by being mixed or imparted to various fiber structures and products for which expression of this effect is required can do.

Claims (6)

1. An air catalyst comprising a metal composition containing iron, aluminum, potassium and tungsten is a substance decomposing / removing composite material supported on the surface and / or inside of a crosslinked acrylate-based moisture-absorbing polymer, wherein the metal composition A material decomposition-removable composite characterized in that a metal content ratio in the substance 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 decomposition-removable composite 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 relative to 100 ppm of iron.
3. The material decomposition and removal composite according to claim 1 or 2, wherein the content of the metal composition is 0.01% by mass or more with respect to the crosslinked acrylate-based moisture-absorbing polymer.
4. 4. The metal composition according to claim 1, wherein 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 degradable complex according to any one of the above.
5. A fiber structure comprising the substance decomposing / removing composite according to any one of claims 1 to 4.
6. An article comprising the substance degradable complex according to any one of claims 1 to 4.