JP7410513B2 - Functional materials using metal scavengers and their manufacturing method - Google Patents

Description

The present invention relates to a metal scavenger that is effective in preventing the outflow of metal components used in the manufacturing process of antibacterial and antifungal materials, antibacterial and antifungal materials that utilize the same, and methods for producing the same.

Conventionally, several patent documents have been published as prior art related to effective metal components (mainly silver, copper, zinc, etc.), carriers (organic materials and inorganic materials), and metal scavengers of antibacterial and antifungal agents. and non-patent literature have been reported. For example, as a modifying agent for raw vegetables, there have been reported modifying agents for raw vegetables that use alcohol alone or in combination with alcohol as a main ingredient and organic acids and organic acid salts as pH adjusters ( Patent Document 1).

In addition, as a fast-dissolving organic acid formulation that can instantly dissolve poorly soluble organic salts (fumaric acid, adipic acid, succinic acid, itaconic acid, sorbic acid, benzoic acid, etc.), for example, An organic compound containing 5 to 40% by weight of a poorly soluble organic acid, one or more of water or an acidic solution, and 0.01 to 5% by weight of xanthan gum with a proportion of acetic acid groups of 0.1 to 3% as a dispersant. A formulation has been reported (Patent Document 2).

In addition, as luminescent silver (I) complexes from the perspective of the ligand, we designed a complex that glows blue-white (or blue-green) with a maximum below 500 nm and a luminescent complex in which the silver center is strongly involved. It has been reported that compounds exhibiting various colors from white to red can be synthesized (Non-Patent Document 1).

In addition, we will discuss the antibacterial effects and application development of DF30, a new micronized fumaric acid preparation that improves solubility in water through micronization of fumaric acid and a special manufacturing method. It has been reported that it exhibits a bactericidal effect against Staphylococcus aureus and Bacillus subtilis in an extremely short period of time, and is useful for cleaning products that cannot be heat sterilized, such as cut vegetables (Non-Patent Document 2).

Additionally, 5 to 40% by weight of a poorly soluble organic acid with an average particle size of 0.01 to 5 μm obtained by dry grinding, an acidic solution such as water or malic acid, and a dispersion stabilizer such as polyglycerin fatty acid ester 0.1 to 40% by weight. An organic acid preparation containing 10% by weight has been reported (Patent Document 3).

Furthermore, a muscle protein denaturation inhibitor that contains citrate as an active ingredient and is effective in strongly inhibiting heat denaturation and freeze denaturation of muscle protein derived from fish meat has been reported (Patent Document 4).

Here, to explain in detail the manufacturing method of antibacterial and antifungal agents, antibacterial and antifungal agents support metal components (mainly silver, copper, zinc, etc.) on the surface of the carrier (organic material or inorganic material) or between layers.・Manufactured by bonding, ion exchange, etc. In order to uniformly support, bond, and exchange metal components on the carrier surface and between layers, a wet method in which the metal components are mixed in an aqueous solution is more efficient than a dry method in which they are physically mixed.

Among the effective metal components (mainly silver, copper, zinc, etc.) that exhibit antibacterial and antifungal functions, silver is considered to be particularly safe for the human body. Silver easily ionizes in aqueous solutions and is used as an antibacterial and antifungal ingredient. Commercially available antibacterial and antifungal agents are mainly manufactured using a wet method. The reason for this is that silver is uniformly dispersed and supported on the carrier surface and between layers.

In order to improve antibacterial and antifungal functions, it is known that if metal components effective for antibacterial and antifungal functions can be supported more uniformly, higher functions will be exhibited. However, in the wet method, the amount of metal components contained in the obtained antibacterial and antifungal materials is significantly reduced compared to the amount of added metal components (silver, zinc, copper, etc.), and the amount of expensive metal components is reduced. There was a need for an efficient manufacturing method that would prevent spills.

When producing antibacterial and antifungal materials using a wet method, it is necessary to separate solids and liquids, and solid-liquid separation is performed using suction filtration to obtain the desired antibacterial and antifungal materials. In that case, it was found that a large amount of silver components were contained in the filtrate, and when the solid was washed, further silver components were found to be contained in the filtrate. This is thought to be due to the fact that the silver component is easily ionized in an aqueous solution and easily repeats adsorption and desorption to the material, which causes the silver component to easily flow out after passing through the suction filtration process.

Japanese Patent Application Publication No. 2-5822 Patent No. 4127529 Patent No. 4324346 Patent No. 4621834

Bull. Jpn. Soc. Coord. Chem. , Vol. 56 (2010), pages 24-40 Booklet of Kyushu/Okinawa regional companies, public testing institutes, and AIST joint results presentation (November 16-17, 2018)

Under these circumstances, the present inventors have developed an efficient method that suppresses the outflow of metal components even when the above-mentioned metal components (mainly silver, copper, zinc, etc.) are subjected to suction filtration operations. As a result of intensive research and development with this goal in mind, we discovered that the intended purpose could be achieved and completed the present invention.
An object of the present invention is to provide a functional product composed of a composite of a metal scavenger, an antibacterial/antifungal component and/or a catalyst material, and a carrier material, and a method for producing the same.

A feature of the metal scavenger according to the present invention is that fumarate or the like is added as an active ingredient to capture metal components exhibiting antibacterial and antifungal functions. By adding an appropriate amount of inexpensive fumarate or the like, expensive metal components can be captured, thereby eliminating waste of valuable resources (expensive metal components). In addition, the amount of fumarates added is small and inexpensive compared to the amount of metal components that exhibit antibacterial and antifungal functions, so it is possible to capture the expensive metal components and improve functionality at the same time. It is possible to do so.

Further, since the metal trapping agent according to the present invention has a high solubility in water, there is an advantage that the manufacturing apparatus can be downsized. Even if metal components with antibacterial and antifungal properties are added as active ingredients, if the active ingredients are substances that are difficult to dissolve in water, a large amount of water and large equipment containing the water ( This is because a container) is required. Metal components that exhibit antibacterial and antifungal properties can be dissolved in alcohol, but dissolving them in water allows for cheaper and more environmentally friendly manufacturing. The fact that it can be produced using water with small equipment reduces production costs, reduces the burden on workers, and is also advantageous for the environment.

In order to improve antibacterial and antifungal performance, a carrier that retains a metal component exhibiting antibacterial and antifungal functions is required. The larger the specific surface area of this carrier, the higher the ability to retain metal components, so the specific surface area of the carrier material itself also affects the antibacterial and antifungal performance.

However, the antibacterial and antifungal materials produced by the production method of the present invention have antibacterial and antifungal functions despite the carrier having a small specific surface area of several m ² /g (a carrier made of commercially available ceramic raw materials). This makes it possible to retain and contain metal components that exhibit high antibacterial and antifungal functions.

By employing the above configuration, the present invention provides the following effects.
1) In the present invention, by adding fumarate, etc., it is possible to prevent the outflow of expensive silver components that contribute to antibacterial and antifungal performance, etc., and to obtain a material supported and contained in a carrier material. Materials exhibiting antibacterial and antifungal properties can be obtained.
2) Furthermore, by optimizing the amount of inexpensive fumarate added, it is possible to capture all the added expensive silver components, thereby preventing the leakage of expensive resources while achieving functionality. Manufacturing becomes possible.
3) In addition, since the silver component is particularly efficiently captured, it is possible to exhibit the same antibacterial performance even if the amount of the silver component added is halved.
4) Furthermore, it was found that high trapping performance was exhibited not only for silver components but also for other metal components (zinc, copper, etc.) that are difficult to trap.
5) It was also found that it can be used not only as an antibacterial and antifungal material, but also as a promoter to improve catalytic function.
6) By using fumarates, etc., materials that are easily soluble in water are used, making it possible to provide simple manufacturing methods with smaller equipment and safe and secure products.

FIG. 1 shows the manufacturing process of an embodiment of the present invention. FIG. 2 shows an XRD pattern of silica containing only cristobalite crystal phase obtained by oxidizing and firing amorphous silica. FIG. 3 shows the XRD pattern of the composite and support material using sodium orthosilicate as the metal scavenger for Example 5. FIG. 4 shows the XRD pattern of the composite and support material using tripotassium phosphate as the metal scavenger for Example 10. Figure 5 shows the XRD patterns of the solid synthesized in Example 10 under various conditions ((a) synthesis temperature = 60°C, (b) standard conditions, (c) carrier material = quartz, (d) carrier material = 10 g). show. FIG. 6 shows the results of Example 10 (proportions of production of each silver carbonate due to differences in synthesis conditions). FIG. 7 shows the results of Example 10 (minimum inhibitory concentration; MIC for the production rate of β-silver carbonate). FIG. 8 shows the XRD patterns of the composite and carrier material (composite: top, carrier material: bottom) when sodium sulfite was used as the metal trapping agent in Example 10. FIG. 9 shows photographs of the photocatalyst sample produced in Example 14 before and after the test (upper part: before the test, lower part: after the 28-day test). FIG. 10 shows resin samples coated with the processing liquid prepared in Example 15 (left: against Staphylococcus aureus, right: against Escherichia coli). FIG. 11 shows the appearance of the sample after oxidation firing in Example 17 [(numbers) correspond to sample names in Table 20]. FIG. 12 shows the photocatalyst powder produced in Example 19 (left figure) and its UV-Vis absorption spectrum (right figure). FIG. 13 shows the appearance of the photocatalyst filter produced in Example 19.

Next, the present invention will be specifically explained based on examples, but the present invention is not limited to the following examples.

Examples of antibacterial and antifungal materials using the metal scavenger according to the present invention will be described below. Note that the scope of the present invention is not limited to the features shown by these examples.

[Example 1]
Succinic acid was selected as a metal scavenger, and 0.5 mass% of the weight of each carrier material was dissolved in 90 ml of distilled water. The carrier materials were cristobalite (10000LW; silica containing a quartz crystal phase and a cristobalite crystal phase) manufactured by Omura Ceratec Co., Ltd., Omura white clay, Goto PC clay (waxite) manufactured by Goto Mining Co., Ltd., and Nagasaki Ceramics Co., Ltd. Tsushima pottery stone (SP-80) and quartz (FK-3F) manufactured by Nitchtsu High Silica Business Headquarters Co., Ltd. were used in an amount of 22 g each. The silver nitrate aqueous solution used was a solution in which 0.025 mol of silver nitrate was dissolved in 10 ml of distilled water.

The silver content contained in the solid obtained by the manufacturing method shown in FIG. 1 was determined using a fluorescent X-ray analyzer. For comparison, a powder sample was obtained using the same manufacturing method as in FIG. 1 without adding a metal scavenger. We requested the Kyoto Microbiology Research Institute to evaluate the minimum inhibitory concentration (MIC) (E. coli) of powders with and without succinic acid added. The results are shown in Table 1.

It was confirmed that in the sample to which succinic acid was not added, 83.2 to 95.7 mass% of silver was leaked out by suction filtration, etc. On the other hand, in all samples to which 0.5 mass% of succinic acid was added, the silver content increased, indicating that the outflow of silver was suppressed. Furthermore, as the amount of captured silver increased, the MIC (E. coli) value also tended to decrease (expressing high functionality). In other words, it was found that suppressing the outflow of silver and increasing the silver content in the sample leads to improving antibacterial performance while reducing waste of resources.

In addition to the above-mentioned silica, silica containing only a cristobalite crystal phase obtained by oxidizing and firing amorphous silica can be used as the carrier material. The XRD pattern is shown in FIG.

[Example 2]
Therefore, in this example, a metal scavenger capable of increasing the silver content was searched for. A metal scavenger (= various dicarboxylic acids <linear dibasic acids>) was fixed at 0.5 mass% based on the weight of the carrier material, and dissolved in 90 ml of distilled water or alcohol solution. As the carrier material, 22 g of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. was used. The silver nitrate aqueous solution used was a solution in which 0.025 mol of silver nitrate was dissolved in 10 ml of distilled water. The silver content contained in the solid obtained by the manufacturing method shown in FIG. 1 was determined using a fluorescent X-ray analyzer. The results are shown in Table 2.

When the number of carbons (straight chain) of various dicarboxylic acids increases, the silver content increases by a maximum of 2.7 times, but even when the number of carbons is too large, the silver content decreases. It was also found that as the number of carbon atoms increases, the solubility in water or alcohol solution decreases, and a large amount of water or alcohol solution is required. For these reasons, when preparing a large amount, a large amount of water or alcohol solution is required, resulting in an increase in the size of the container for preparation and an increase in manufacturing cost.

[Example 3]
A metal scavenger (= various organic acids <containing carboxyl group -COOH>) was fixed at 0.5 mass% based on the weight of the carrier material and dissolved in 90 ml of distilled water. As the carrier material, 22 g of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. was used. As the silver nitrate aqueous solution, a solution in which 0.025 mol of silver nitrate was dissolved in 10 ml of distilled water was used. The silver content contained in the solid obtained by the manufacturing method shown in FIG. 1 was determined using a fluorescent X-ray analyzer. The results are shown in Table 3.

When hydroxy acids, sugars, and unsaturated dibasic acids were added as metal scavengers, the use of fumaric acid contained the highest amount of silver, and silver increased by more than 3.6 times compared to when fumaric acid was not added. I understand. This has led to a reduction in the amount of added silver component flowing out, and it was expected that expensive metal components could be used more effectively. However, since fumaric acid is poorly soluble in water, when a large amount of fumaric acid is prepared, a large amount of water is required, and there is a concern that the container for preparing the fumaric acid will also be large. It was expected that these things would lead to an increase in manufacturing costs and a long suction filtration time, leading to a decrease in production efficiency.

[Example 4]
Furthermore, we investigated metal scavengers that are easily water-soluble and safe (= various organic acids and inorganic compounds (including Na salts and K salts)). The metal scavenger was dissolved in 90 ml of distilled water at a fixed concentration of 0.5 mass% based on the weight of the carrier material. As the carrier material, 22 g of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. was used. The silver nitrate aqueous solution used was a solution in which 0.025 mol of silver nitrate was dissolved in 10 ml of distilled water. The silver content contained in the solid obtained by the manufacturing method shown in FIG. 1 was determined using a fluorescent X-ray analyzer. The results are shown in Table 4.

It was found that when potassium dihydrogen phosphate, sodium hydrogen fumarate, or the like is added as a metal scavenger, silver is contained up to 6.2 times more than when no metal scavenger is added. This was expected to further suppress the outflow of the added silver component, effectively utilize the expensive metal component, and improve antibacterial properties. Furthermore, even when preparing a large amount, it can be prepared with a small amount of water, there is no need to increase the size of the preparation container, suction filtration time can be completed in a short time, and it is possible to manufacture without reducing productivity. became.

[Example 5]
By optimizing the amount of inexpensive metal trapping agents added, we aim to capture all the expensive silver components by selecting from among safe metal trapping agents designated as food additives and varying the loading amount. The silver content contained in the sample was confirmed. The metal scavengers were dissolved in 90 ml of distilled water in amounts of 0.5, 3.0, and 10 mass%, respectively, based on the weight of the carrier material. As the carrier material, 22 g of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. was used. The silver nitrate aqueous solution used was a solution in which 0.025 mol of silver nitrate was dissolved in 10 ml of distilled water.

The silver content in the solid obtained in the same manner as in the manufacturing method shown in FIG. 1 was determined using a fluorescent X-ray analyzer. The results are shown in Table 5-1. As the amount of metal scavenger added increased, the silver content also increased. It was found that 18.5 times more silver components were captured compared to a sample to which no metal scavenger was added. On the other hand, in some samples to which a metal scavenger such as succinic acid or phosphoric acid was added, it was not possible to recover all of the silver components added even if 10 mass% was added.

The difference in the amount of remaining silver components is due to differences in the molecular structure of the metal scavenger, differences in complex formation, differences in ionization energy, differences in the amount of physical adsorption with the surface of the support material, or differences in the amount of silanol on the surface of the support material. This is thought to be due to differences in the amount stabilized by ion exchange with groups and hydrogen ions. In order to effectively utilize expensive silver components and improve functionality, it is desirable that all added silver components be captured and highly dispersed.

Further, the silver content was measured in the same manner as above using potassium hydrogen carbonate, sodium hydrogen carbonate, sodium pyrosulfite, sodium metasilicate, and sodium orthosilicate as metal scavengers. The results are shown in Table 5-2.
Further, FIG. 3 shows the XRD pattern of the powder obtained by the manufacturing method of FIG. 1 using sodium orthosilicate as the metal scavenger. Formation of silver oxide was confirmed in the composite.

[Example 6]
In order to confirm whether changing the metal scavenger changes the content of silver components and changes the antibacterial performance, we selected succinic acid, fumaric acid, and sodium hydrogen fumarate as the metal scavengers, and used carriers for each. It was prepared by dissolving 0.5 mass% based on the weight of the substance in 90 ml of distilled water. As the carrier material, 22 g each of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. was used. The silver nitrate aqueous solution used was a solution in which 0.025 mol of silver nitrate was dissolved in 10 ml of distilled water.

The content of silver components contained in the solid obtained in the same manner as in the manufacturing method shown in FIG. 1 was determined using a fluorescent X-ray analyzer. The obtained powder was evaluated by the Kyoto Microbial Research Institute (General Incorporated Association) for Minimum Inhibitory Concentration (MIC) (E. coli). The results are shown in Table 6.

Silver content was increased by changing the metal scavenger to succinic acid, fumaric acid, and sodium hydrogen fumarate. It was confirmed that the MIC value also decreased accordingly. In other words, it was found that by using an inexpensive and safe metal scavenger that can retain a large amount of silver, the minimum inhibitory concentration against E. coli can be reduced and the effect of inhibiting the growth of E. coli can be increased.

[Example 7]
In order to confirm the trapping ability of sodium hydrogen fumarate due to differences in metal components and carrier materials, 10 mass% of sodium hydrogen fumarate based on the weight of the carrier material was dissolved in 90 ml of distilled water. As the carrier material, 22 g of Goto PC clay (Rouxite) manufactured by Goto Mining Co., Ltd. was used. The zinc nitrate aqueous solution used was a solution in which 0.025 mol of zinc nitrate hexahydrate was dissolved in 10 ml of distilled water. The copper nitrate aqueous solution used was a solution in which 0.025 mol of copper nitrate trihydrate was dissolved in 10 ml of distilled water.

The zinc and copper contents contained in the solid obtained by the same manufacturing method as in FIG. 1 were determined using a fluorescent X-ray analyzer, and the capture rate for the added metal components was determined. The results are shown in Table 7. For comparison, the silver capture rate when using an aqueous solution containing 0.025 mol of silver nitrate is also shown. Sodium hydrogen fumarate was found to be able to capture all the silver even if the carrier material was changed. Regarding the zinc and copper components, it was not possible to capture all of the added metal components (zinc, copper). From these results, it was also found that sodium hydrogen fumarate has a particularly high ability to capture silver components among metal components, even if the carrier material is changed.

[Example 8]
In order to confirm the antibacterial properties when adding a small amount of silver component, a metal scavenger was fixed in sodium hydrogen fumarate and dissolved in 90 ml of distilled water at 10 mass% based on the weight of the carrier material. As the carrier material, 22 g each of Goto PC clay (Rowite) manufactured by Goto Mining Co., Ltd. was used. The silver nitrate aqueous solution used was a solution in which 0.025 mol, 0.0125 mol, and 0.00625 mol of silver nitrate were dissolved in 10 ml of distilled water.

The obtained powder was produced in the same manner as the production method shown in FIG. 1, and the minimum inhibitory concentration (MIC) (E. coli) evaluation was requested to the Kyoto Microbial Research Institute. The results are shown in Table 8.

It was found that even if the amount of silver nitrate added was reduced to 1/2, the same minimum inhibitory concentration against E. coli was exhibited. This means that the amount of raw materials initially added as antibacterial and antifungal ingredients can be reduced by 50%, leading to cost reductions. Furthermore, it was also found that even if the amount of silver nitrate added was reduced to 1/4, it still exhibited antibacterial activity against E. coli, which grows rapidly.

[Example 9]
In order to confirm the content of silver components due to differences in the specific surface area of the carrier material, a metal scavenger was fixed in sodium hydrogen fumarate, and 0.5 mass% based on the weight of the carrier material was dissolved in 90 ml to 150 ml of distilled water. did. The carrier materials were cristobalite (10000LW: 3.8 m ² /g) manufactured by Omura Ceratec Co., Ltd., amorphous silica (380:380 m ² /g) manufactured by Nippon Aerosil Co., Ltd., and (P-1 manufactured by Shinagawa General Co., Ltd.). :301.5m ² /g) were used in an amount of 22g each. The silver nitrate aqueous solution used was a solution in which 0.025 mol of silver nitrate was dissolved in 10 ml of distilled water.

The silver content contained in the solid obtained in the same manner as in the manufacturing method shown in FIG. 1 was determined using a fluorescent X-ray analyzer. The results are shown in Table 9. It was found that the use of a carrier material with a high specific surface area increased the content of silver components. In other words, in order to retain silver, it is effective to select a carrier material with a high specific surface area. However, in the case of a bulky powder carrier material with a high specific surface area and ultrafine particles, a large amount of water is required to be added, and stirring, suction filtration, and drying time are also long, resulting in an extremely low workability. I also understood that.

[Example 10]
The metal scavenger was sodium hydrogen fumarate, which was dissolved in 90 ml of distilled water in an amount of 10 mass% based on the weight of the carrier material. As carrier materials, 22 g each of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. and Goto PC clay (waxite) manufactured by Goto Mining Co., Ltd. were used. The silver nitrate aqueous solution used was a solution in which 0.025 mol of silver nitrate was dissolved in 10 ml of distilled water. The silver content contained in the solid obtained in the same manner as in the manufacturing method shown in FIG. 1 was determined using a fluorescent X-ray analyzer. The obtained powder was evaluated by the Kyoto Microbial Research Institute, a general incorporated association, for minimum inhibitory concentration (MIC) (E. coli/black koji mold). The results are shown in Table 10-1.

Further, the silver content and MIC were measured in the same manner as above using tripotassium phosphate and potassium carbonate as the metal scavengers and using 22 g of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. as the carrier material. The results are shown in Table 10-2. The antibacterial activity against black koji mold was improved compared to when sodium hydrogen fumarate was added.
Further, FIG. 4 shows the XRD pattern of the powder obtained by the manufacturing method of FIG. 1 using tripotassium phosphate as the metal scavenger. Formation of silver phosphate was confirmed in the composite.

In addition, the silver content was determined in the same manner as above, except that potassium carbonate was used as the metal scavenger and the production method shown in Figure 1 was improved (the dropping speed of the silver nitrate aqueous solution was slowed, the stirring speed was increased, and the synthesis temperature was raised). and MIC were measured. The results are shown in Table 10-3. Further, FIG. 5 shows XRD patterns of solids synthesized under various conditions ((a) synthesis temperature = 60° C., (b) standard conditions, (c) carrier material = quartz, (d) carrier material = 10 g).
As shown in FIG. 6, the amount of β-silver carbonate (hereinafter referred to as β phase) increased compared to standard conditions (Table 10-2). It was also found that a higher synthesis temperature is more advantageous for the production of β-phase, and that by using cristobalite as the carrier material, the amount of β-phase produced increases. It was also confirmed that the β-phase will not be produced if cristobalite is not included during the synthesis, and that increasing the synthesis temperature will not have an advantageous effect on the production of the β-phase. Furthermore, as shown in FIG. 7, the antibacterial activity against Escherichia coli and black koji mold was improved by producing a large amount of β phase.

Furthermore, the silver content and MIC were measured in the same manner as above using sodium sulfite as the metal scavenger and using 22 g of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. as the carrier material. The results are shown in Table 10-4. Further, the results of identifying the crystal phase of the obtained powder using a powder X-ray diffraction apparatus are shown in FIG. Formation of silver sulfite was confirmed in the composite. In addition, antibacterial activity against E. coli was improved. Furthermore, compared to samples that did not use metal scavengers (cristobalite and silver nitrate) [MIC: E. coli 3,200 ppm, black koji mold 3,200 ppm], the MIC was 1/256 for E. coli and 1/256 for black koji mold. The antibacterial and antifungal effects were significantly improved.

For comparison, Table 11 also shows the antibacterial and antifungal properties of a sample prepared using the same manufacturing method as in FIG. 1, to which no metal scavenger was added, and to which a silver nitrate aqueous solution was not added. The carrier material was not a special material, but a ceramic raw material with a small specific surface area that is manufactured and sold by a company within the prefecture. From the results in Table 11, the sample to which 10 mass% sodium hydrogen fumarate was added and no silver component was added showed a value exceeding 3,200 against E. coli and a value exceeding 3,200 against black koji mold, indicating an antibacterial and antifungal effect. I also found out that it doesn't show up.

From these results, it is possible to use metal trapping agents on carrier materials with a surface area of several m ² /g, even if they do not have a high specific surface area (several tens of m ² /g to hundreds of m ² /g). It was easy to prepare, captured more silver components, and had high antibacterial activity against both Escherichia coli and Aspergillus aspergillus, which have different growth mechanisms.

[Example 11]
We investigated metal capture agents that can further capture metal components (zinc and copper) that had low capture rates. In addition, in order to confirm the capture ability of different carrier materials, the capture rates of each were determined. Various metal scavengers were dissolved in 90 ml of distilled water in an amount of 10 mass% based on the weight of the carrier material. As carrier materials, 22 g each of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. and Goto PC clay (waxite) manufactured by Goto Mining Co., Ltd. were used. The zinc nitrate aqueous solution used was a solution in which 0.025 mol of zinc nitrate hexahydrate was dissolved in 10 ml of distilled water. The copper nitrate aqueous solution used was a solution in which 0.025 mol of copper nitrate trihydrate was dissolved in 10 ml of distilled water.

The zinc and copper contents contained in the solid obtained by the same manufacturing method as in FIG. 1 were determined using a fluorescent X-ray analyzer, and the capture rate for each added metal component was determined. The results are shown in Table 12. It was also found that there is a metal trapping agent that can trap both zinc and copper components more efficiently than when sodium hydrogen fumarate is used. These composite materials are lower in cost (1/20 times the reagent price) than silver-composite materials, and if they show antibacterial and antifungal properties, they could lead to lower product costs. Be expected.

[Example 12-1]
We investigated whether it was possible to capture metal components (iron) other than silver, zinc, and copper components. Various metal scavengers were dissolved in 90 ml of distilled water in an amount of 10 mass% based on the weight of the carrier material. As the carrier material, 22 g of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. was used. Nitrate, chloride, and sulfate were used as iron components. Various aqueous solutions were used in which 0.025 mol of iron nitrate nonahydrate, iron chloride (anhydrous), and iron sulfate were dissolved in 10 ml of distilled water.

The iron content contained in the solids obtained by the same manufacturing method as in FIG. 1 was determined using a fluorescent X-ray analyzer, and the capture rate for the various iron salts added was determined. The results are shown in Table 13-1. As a result, when carbonate or the like was added as a metal trapping agent, the trapping rate was lower than that of zinc or copper components. However, by using succinate or fumarate as a metal capture agent, the capture rate for the metal component (iron) was improved.

[Example 12-2]
Other metal components (aluminum) were investigated. Various metal trapping agents were dissolved in 90 to 210 ml of distilled water in an amount of 10 to 40 mass% based on the weight of the carrier material. As the carrier material, 22 g of cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. was used. Nitrate (aluminum nitrate nonahydrate) was used as the aluminum component. The amount of nitrate added was 0.025 mol. Potassium sulfate, potassium acetate, tripotassium phosphate, disodium succinate, sodium hydrogen fumarate, trisodium citrate, tripotassium citrate, sodium sulfite, sodium pyrosulfite, and sodium hydrogen sulfite were selected as metal scavengers. The aluminum content contained in the solid obtained in the same manner as the manufacturing method shown in FIG. 1 was determined using a fluorescent X-ray analyzer. The results are shown in Table 13-2. A portion of the obtained powder was evaluated for minimum inhibitory concentration (MIC) (E. coli, black koji mold) at the Kyoto Microbial Research Institute. The results are shown in Table 13-3. The MIC evaluation showed 400 ppm relative to black koji mold. Aluminum nitrate is about 1/35th the price of silver nitrate and is not designated as a deleterious substance, so it can be used as an easy-to-handle and inexpensive metal component. A composite of aluminum nitrate, sodium hydrogen fumarate and cristobalite showed antibacterial activity against black koji mold.

[Example 13]
Ingredients such as silver and copper are not only used as antibacterial and antifungal materials, but are also expected to act as cocatalysts by supporting metals on the catalyst surface, so we verified their effectiveness. Contains fluororesin, dispersant, photocatalyst powder (photocatalyst (TiO ₂ -SiO ₂ ) made of titanium oxide supported silica containing titanium oxide supported on silica containing quartz crystal phase and cristobalite crystal phase: Patent No. 6561411), etc. An aqueous solution (hereinafter referred to as processing solution) is prepared, and composite powder supporting silver, iron, and copper components is added to the processing solution in an amount of 2.0 mass% based on the photocatalyst powder, and the silver component is mixed by rotation for one day and night. A machining fluid containing iron, a machining fluid containing an iron component, and a machining fluid containing a copper component were prepared.

The composite supporting iron, silver, and copper components uses cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. as a carrier material, and potassium carbonate is selected as a metal scavenger for iron and copper components. Sodium hydrogen fumarate was selected as the metal scavenger, and 10 mass% of each was used based on the weight of the carrier material. A composite containing 6.2 mass% of the carrier material in terms of metal (silver), 5.6 mass% of the carrier material in terms of metal (copper), and 0.7 mass% of the carrier material in terms of metal (iron). Powders were prepared respectively. Each processing solution containing silver, iron, and copper components was coated on a porous filter (50 mm x 50 mm x 9 mm thickness), and after drying at room temperature, a photocatalyst filter in which about 1 g of each was supported was obtained. For the photocatalytic activity, four types of photocatalytic filters (no metal component added, silver component added, copper component added, and iron component added) were prepared, and the active oxygen species generated from the photocatalyst surface was quantified.

The test method was to leave various photocatalyst filters in a circulating 500 ml of 10 ppm dimethyl sulfoxide (DMSO) aqueous solution. When ultraviolet rays (ultraviolet intensity: 1.47 mW/cm ² ) are irradiated from above the photocatalytic filter, methanesulfonic acid (hereinafter referred to as MSA) is generated from DMSO in an equimolar amount as active oxygen species due to a photocatalytic reaction. 10 ml of water was sampled 5 hours after UV irradiation, and MSA contained in the aqueous solution was quantified using an ion chromatography device. The results of the amount of MSA produced are shown in Table 14-1.

As a result, it was found that the machining fluids containing silver, copper, and iron components all produced an increased amount of MSA compared to the machining fluids containing no additives, thereby enhancing the catalytic action. From this result, it was found that the use of inexpensive (1/20 times the reagent price) iron nitrate, copper nitrate, etc. has the potential to improve the catalytic function and contribute to cost reduction. . Furthermore, Tables 15 and 16 show the dependence of the added amount of cristobalite (10000LW) powder retaining iron and copper components on the amount of MSA produced. As a result, it was found that the photocatalyst containing an iron component produced a large amount of MSA, that is, a large amount of active oxygen species, when the amount of the photocatalyst containing an iron component was 4.8 mass%, and the amount of photocatalyst containing a copper component was 4.2 mass%. Do you get it.

In addition, the composite powder supporting iron, copper, and silver components was prepared by using cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. as a carrier material, and by selecting disodium succinate as a metal scavenger for the iron component. Potassium carbonate was selected as the component metal scavenger, and tripotassium phosphate was selected as the silver component metal scavenger, and each was used in an amount of 10 mass% based on the weight of the carrier material. Composite powder containing 12 mass% of the carrier material in terms of metal (silver), 5.6 mass% of the carrier material in terms of metal (copper), and 4.0 mass% of the carrier material in terms of metal (iron). Each was created. The processing liquid containing photocatalyst powder (TiO ₂ -SiO ₂ : Patent No. 6561411) and silver, copper, iron components, etc. is a sheet made of 18/16 mesh reticulated aluminum alloy (50 mm x 50 mm x 0.55 mm thick). (manufactured by Takashi Yoshida Co., Ltd.). After drying at room temperature, a photocatalyst filter coated with a composite etc. was obtained. The photocatalytic activity was tested in accordance with JISR1704 using four types of photocatalytic filters (no metal added, silver added, copper added, iron added), and Sankyo Denki Black Light Blue Fluorescent as a light source. Irradiation was performed from above the photocatalyst filter using a lamp (352 nm FL20SBLB x 2). The ultraviolet light intensity was 1.43 mW/cm ² . Active oxygen species generated from the photocatalyst surface were quantified using ion chromatography. Photocatalytic filters with added metal components generate up to 2.25 times the amount of active oxygen species produced (up to 1.5 times in the case of the ceramic filter of patent application 2019-068594) compared to photocatalytic filters without added metal components. ) increased. In addition, the amount of active oxygen species produced, etc. of a commercially available photocatalyst filter and a photocatalyst filter of the present invention were compared. The results are shown in Tables 14-2 and 14-3. It was found that the photocatalyst filter of the present invention produces more than twice as much active oxygen species as commercially available photocatalyst filters, even though the filter thickness and weight are about 1/10. By coating an aluminum alloy sheet with a machining fluid containing the composite of the present invention, it can be deformed into any shape, and when incorporated into a device, it can also be made smaller and lighter. Furthermore, since the risk of damage is lower than that of ceramic photocatalyst filters, it can contribute to stable product manufacturing and the development of new products with high functionality.

[Example 14]
In connection with Example 13, a processing liquid was prepared by mixing the prepared composite with a fluororesin, a dispersant, and TiO ₂ -SiO ₂ (Japanese Patent No. 6561411). Among them, processing liquid containing silver components is coated on the surface of a reticulated aluminum alloy sheet (50 mm x 50 mm x 0.55 mm thick) and a PTFE (tetrafluoroethylene) porous film (50 mm x 50 mm x 0.08 mm thick). An aluminum alloy photocatalyst and a PTFE porous film photocatalyst were prepared, and JIS Z 2911 (mold resistance test) evaluation was performed at the Kyoto Microbial Research Institute. The sample was placed in a constant temperature and humidity chamber set at 29° C. and a relative humidity of 95% or higher. 0.1 ml of mold spore suspension was inoculated onto the surface of the sample, and the test was conducted for 28 days. The five types of molds used in the evaluation were Aspergillus niger (NBRC-105649), Penicillium pinophilum (NBRC-33285), P. chinensis (NBRC-6347), Trichoderma (NBRC-6355), and Pecilomyces (NBRC-33284). . The results are shown in Table 17 and FIG. In the aluminum alloy photocatalyst made of a reticulated aluminum alloy sheet, no mold growth was observed with the naked eye or under a microscope. The sample coated with the processing liquid containing the composite of the present invention suppressed the growth and proliferation of mycelium for a long period of time in the dark. When various samples receive light (particularly ultraviolet rays), they develop the ability to generate active oxygen species, which is expected to further enhance the antifungal effect.

[Example 15]
A plastic primer _is applied to the surface of the acrylic resin sample, and after drying _at room temperature, a composite containing the silver component of the present invention (in terms of metal (silver) A processing liquid containing 12 mass% of the carrier material, tripotassium phosphate (10 mass% of the weight of the carrier material) as a metal scavenger, and cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. as the carrier material was added. It was applied and dried at room temperature. The obtained sample was subjected to antibacterial activity evaluation (JIS L 1902 halo test) at the Kyoto Microbial Research Institute. The results are shown in Table 18 and FIG. Halos were observed against Staphylococcus aureus (NBRC-12732) and E. coli (NBRC-3972), and it was found to have antibacterial properties against Staphylococcus aureus and E. coli.

[Example 16]
Processing liquid containing photocatalyst powder (TiO ₂ -SiO ₂ : Patent No. 6561411), fluororesin, etc. and photocatalyst powder (TiO ₂ -SiO ₂ : Patent No. 6561411), but with the same amount of TiO ₂ -SiO ₂ Processing fluids containing SiO ₂ , fluororesin, etc. were prepared. Each processing liquid contained the composite of the present invention (12 mass% based on the carrier material in terms of metal (silver)) and tripotassium phosphate (by weight of the carrier material) as a metal scavenger so as to contain the same amount of silver component. cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. was used as a carrier material). Each processing liquid was coated on the surface of a PTFE (tetrafluoroethylene) porous film (50 mm long x 50 mm wide, 0.08 mm thick), fixed at room temperature, and after drying, the same amount (0.07 g) was applied to the surface. A sample was prepared in which a film containing antibacterial components was formed. The obtained sample was subjected to an antibacterial activity evaluation test (JIS Z 2801: film contact method) against Escherichia coli and Staphylococcus aureus at the Kyoto Microbial Research Institute. The results are shown in Table 19. E. coli and Staphylococcus aureus were not detected after 24 hours in the PTFE porous film coated with each of the processing fluids, demonstrating a high antibacterial effect. When a processing fluid containing photocatalyst powder (TiO ₂ -SiO ₂ : Patent No. 6561411) receives light such as ultraviolet rays, it is expected that active oxygen species will be generated. In an environment where it can receive light, it is also expected to be used for self-cleaning functions such as inhibiting the growth of bacteria or mold and antifouling through the production of silver components and active oxygen species.

[Example 17]
Succinic acid (0.5 mass% based on the weight of the carrier material) was selected as a metal scavenger, silver (4.95 mass% based on the carrier material in terms of metal (silver)) and cristobalite manufactured by Omura Ceratec Co., Ltd. A composite containing 10,000LW) (carrier material) and TiO ₂ -SiO ₂ (Patent No. 6561411) were prepared. 100 g of Kaolin Mat (dry powder) manufactured by Kailken Co., Ltd. was mixed with 50 g of the composite and 50 g of TiO ₂ -SiO ₂ [ratio of 1:1 (mass ratio)] (hereinafter referred to as photocatalyst-containing composite powder). '' and tap water (53.5%) was added thereto to prepare an aqueous solution (hereinafter referred to as photocatalyst-containing glaze). A tile (50 mm x 50 mm) made of low-fired china clay (matte glaze) was calcined at about 900°C, and then a glaze containing a photocatalyst etc. was applied to the surface of the tile to produce a tile. Thereafter, the tiles were dried at room temperature for one day and night, and then oxidized and fired at 1230° C. in an electric furnace to produce tiles. A photocatalyst-containing glaze was prepared by varying the amount of the photocatalyst-containing composite powder added, and a plurality of tiles were glazed with the photocatalyst-containing glaze. The dependence of the additive amount of composite powder containing photocatalyst etc. on Escherichia coli and Staphylococcus aureus was evaluated. Antibacterial activity evaluation tests (JIS Z 2801; film adhesion method) were conducted on various samples at the Kyoto Microbial Research Institute, a general incorporated association. The results are shown in Table 20 and FIG. 11. It has been found that adding 10% or more of a photocatalyst-containing composite powder to a photocatalyst-containing glaze exhibits a high antibacterial effect against E. coli and Staphylococcus aureus. If the metal scavenger is optimized, it is expected that the amount of composite powder containing photocatalyst etc. added can be further reduced.

[Example 18]
The processing fluid prepared in Example 15 was coated and fixed on the surface of the reticulated aluminum alloy sheet at room temperature. The prepared samples were subjected to a virus performance evaluation test (JIS R 1706; antiviral performance evaluation test using bacteriophage) at the Kanagawa Prefectural Institute of Industrial Science and Technology, a local independent administrative agency. The results are shown in Table 21. Both the antiviral activity value and the light irradiation effect were higher than the product judgment standard values of the Photocatalyst Industry Association (antiviral activity value: 2.0, light irradiation effect: 0.3).
BacterioQβ phage is used as an alternative to norovirus. This means that when the developed processing liquid was coated on a substrate and irradiated with light, more than 99.99% of the bacterioQβ phages were inactivated. This is expected to suppress not only the growth of bacteria and mold, but also viruses.

[Example 19]
A photocatalyst powder (TiO ₂ -SiO ₂ /Fe) was prepared by adding an iron component (iron nitrate nonahydrate) to an ultraviolet light-responsive photocatalyst powder (TiO ₂ -SiO ₂ : Patent No. 6561411). FIG. 12 shows each photocatalyst powder and its UV-Vis absorption spectrum. Compared to the ultraviolet light-responsive TiO ₂ -SiO ₂ powder (Patent No. 6561411), TiO ₂ -SiO ₂ /Fe powder absorbs visible light in the approximately 400 nm to 560 nm region, and absorbs light at longer wavelengths. I found out that it can be done.
Processing liquid A containing TiO ₂ -SiO ₂ powder (Patent No. 6561411) and the like and processing liquid B containing TiO ₂ -SiO ₂ /Fe powder and the like were prepared, respectively. In addition, in order to further activate the processing fluid, we added a composite containing the silver component of the present invention to the TiO ₂ -SiO ₂ /Fe powder (12 mass% based on the carrier material in terms of metal (silver), a metal scavenger). A composite powder (TiO ₂ -SiO ₂ /Fe-Ag) was added with tripotassium phosphate (10 mass% based on the weight of the carrier material) and cristobalite (10000LW) manufactured by Omura Ceratec Co., Ltd. was used as the carrier material. A processing liquid C containing the same was prepared in the same manner.
The three types of processing fluids were coated on two 18/16 mesh reticulated aluminum alloy sheets (100 mm x 100 mm x 0.55 mm thick) (manufactured by Takashi Yoshida Co., Ltd.). After drying at room temperature, three types of photocatalyst filters were obtained. The ability to generate active oxygen species was evaluated by testing in accordance with JISR1704. Irradiation was performed from above the photocatalyst filter using a Sankyo Denki black light blue fluorescent lamp (352 nm FL20SBLB x 1) and a Toshiba fluorescent lamp (white FL20S/W x 1) as light sources. The ultraviolet light intensity was 0.84 mW/cm ² . Active oxygen species (= methanesulfonic acid: hereinafter referred to as MSA) generated from the photocatalyst surface were quantified using an ion chromatograph. The results are shown in Table 22. The photocatalytic filter coated with processing fluid B had an increased amount of MSA produced (=active oxygen species produced) compared to the photocatalytic filter coated with processing fluid A. In addition, the photocatalytic filter coated with processing liquid C, which is made by adding a small amount of a composite containing a silver component to processing liquid B, produces approximately 2.1 times more MSA (=active oxygen species) than the photocatalyst filter coated with processing liquid B. production amount) increased.
The photocatalyst filter coated with processing fluid C that we created this time contributes to lower energy consumption of the light source by utilizing processing fluid B, which can also absorb light with longer wavelengths than ultraviolet rays, and by adding a composite containing a silver component. However, we were able to increase the amount of active oxygen species produced.

In addition, the appearance of photocatalyst filters produced using processing liquid A (ultraviolet light-responsive photocatalyst powder; TiO ₂ -SiO ₂ ) and processing liquid B (visible light-responsive photocatalyst powder; TiO ₂ -SiO ₂ /Fe) is shown below. It is shown in FIG. Since both photocatalytic filters exhibit white color, it is expected that the photocatalytic filter produced using processing liquid B in particular will have an expanded range of applications in the future.

As detailed above, the present invention relates to a functional material that utilizes a metal scavenger and a method for producing the same. , it is possible to provide a composite material that captures expensive silver components, etc., and a method for producing the same. Furthermore, since it can be used as a co-catalyst to enhance catalytic function, it will become possible to effectively utilize support materials that have been an unused resource, and its application to new fields is expected. Fumarate, etc., which is an important element of the present invention, specifically captures silver components, etc., so it is possible to suppress the amount of silver components added, and the cost of antibacterial and antifungal agents can be reduced. . Furthermore, since fumarates are food additives that can be safely used by the human body, they contribute to safe manufacturing in the field of manufacturing antibacterial and antifungal agents and the food industry that applies and processes them. It has high technical significance for people and the environment.

Claims (6)

A functional product consisting of a composite of a metal scavenger, an antibacterial/antifungal component and/or a catalyst material, and a carrier substance, wherein the metal scavenger is carbonate, sulfite, phosphate, or amber. containing an acid salt or a fumarate or an acetate or a thiosulfate or a citrate or a sulfate or a silicate as an active ingredient, the catalyst material being supported on silica containing a quartz crystal phase and a cristobalite crystal phase. Contains an antibacterial/antifungal material and/or a catalytic material characterized by being a photocatalyst made of titanium oxide-supported silica containing titanium oxide, or a photocatalyst that absorbs visible light by adding a metal component to the photocatalyst. Functional products. The carbonate of the metal trapping agent is potassium carbonate, potassium hydrogen carbonate, sodium carbonate, and sodium hydrogen carbonate, and the sulfite is potassium sulfite, sodium pyrosulfite, potassium pyrosulfite, sodium sulfite, and sodium hydrogen sulfite. The salt is tripotassium phosphate, potassium tripolyphosphate, sodium polyphosphate, trisodium phosphate, tetrasodium pyrophosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate. succinate is disodium succinate, monosodium succinate, fumarate is sodium hydrogen fumarate, acetate is potassium acetate, sodium acetate, thiosulfate is thiosulfate. The citrate is tripotassium citrate or trisodium citrate, the sulfate is potassium sulfate, and the silicate is sodium orthosilicate or sodium metasilicate (any metal scavenger). (including hydrates), the functional product according to claim 1. The functional product according to claim 1 or 2 , comprising one or more crystalline phases of β-silver carbonate, silver carbonate, silver sulfite, silver phosphate, or silver oxide. Functional product according to any one of claims 1 to 3 , wherein the carrier material is a cristobalite crystalline phase, or a silica comprising a quartz crystalline phase and a cristobalite crystalline phase. It is composed of a composite of a metal scavenger, an antibacterial/antifungal component and/or a catalyst material, and a carrier substance, and the metal scavenger is a carbonate, a sulfite, a phosphate, a succinate, a fumarate, or A method for producing a functional product containing an antibacterial/antifungal material and/or a catalytic material containing acetate or thiosulfate or citrate or sulfate or silicate as an active ingredient, the method comprising trapping metals in water. The antibacterial agent is characterized by the following steps: a step of dissolving the agent, a step of adding and mixing a carrier material thereto, a step of adding and mixing a functional metal component, a step of separating the aqueous solution and the solid, and a drying/classifying step. A method for producing a functional product containing an antifungal material and/or a catalytic material. A functional material characterized by using a composite material of any one of the metal trapping agents according to claims 1 to 4 , an antibacterial/antifungal component and/or a catalyst material, and a carrier substance as a functional material. How the product is manufactured.