JP2016068543A - Base material-silica sol dried product complex having positive hole and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base material-silica sol dried product complex that exhibits a rapid antiviral action, a germicidal action, etc. under no light by treatment at the temperature containing ordinary temperature, and an applied article thereof.SOLUTION: Fibers, woven fabrics, nonwoven fabrics, papers, plastics, metals, glasses, refractories, bamboo charcoal, charcoal, or a composite thereof are used for a base material. A silica sol is applied on the base material and the resulting coated base material is dried in an atmosphere of 0 to 150°C to obtain a base material-silica sol dried product complex. Silica particles constituting the silica sol has 4 to 700 nm of a particle diameter. The adhesion amount of the silica sol based on the base material is 0.1 to 2.5 g/min a dry state.EFFECT: When a DMPO liquid drops down onto a nonwoven fabric that carries a dried silica sol under no light, a DMPO-OH radical is detected by an electron paramagnetic resonance (ESR) to verify the occurrence of a hydroxyl radical. A product is used as an air cleaning material in a wide range of fields, such as a hygienic mask, an air filter made into an element permeable to gas, medical and nursing clothing, and a partition.SELECTED DRAWING: Figure 2

Description

Detailed Description of the Invention

  The present invention relates to a substrate-silica sol dried composite having holes and having a virus inactivating action, and a method for producing the same. The present invention also relates to a product using the substrate-silica sol dried product composite, particularly a mask or an air filter.

  A photocatalyst is known as a technique for purifying viruses present in the air and water as living spaces, pathogenic bacteria such as Escherichia coli and volatile harmful organic substances in a short time without causing side effects.

It is said that such an action is to inactivate, sterilize and decompose viruses by generating reactive oxygen species when the photocatalyst is irradiated with ultraviolet rays. Active oxygen refers to superoxide anion, hydrogen peroxide solution, hydroxy radical, and singlet oxygen. Among them, after a semiconductor is irradiated with light such as ultraviolet rays, electrons in the valence band are excited and moved to the conduction band. Hydroxyl radicals (OH.) Generated by the generated holes (h ⁺ ) taking electrons from the hydrogen atoms of water are highly evaluated because they oxidize and decompose and sterilize various substances.

  However, it is necessary to irradiate the photocatalyst with ultraviolet rays in order to generate holes from the photocatalyst in a room where sunlight does not strike the holes that generate hydroxy radicals. For example, in an environment where light does not reach such as a sanitary mask, the catalytic function There is a problem that cannot be demonstrated. In addition, in the case of a catalyst that operates with visible light for illumination instead of the ultraviolet rays of sunlight, the generated holes are often lost by recombining with the electrons that have been excited and moved. There is also a problem that the cost is increased because it is necessary to blend a precious metal such as. Under these circumstances, a material carrying a catalyst that retains holes and functions in the absence of light is required.

  As such a catalyst body that retains holes in the absence of light, Patent Document 1 discloses that a non-stoichiometric oxide and / or non-stoichiometric nitride constitute a p-type semiconductor or a metal-deficient indefinite type of the alloy. Hydroxyl radicals generated in a coexistence environment with water molecules in a structure in which a specific oxide or metal-deficient non-stoichiometric nitride is supported on the surface of any structure composed of metals, ceramics, plastics and fibers A catalyst for decomposing organic and inorganic substances by an oxidation function has been proposed.

  In Patent Document 2, an aqueous solution containing one or more transition metal carboxylates such as titanium and a transition metal oxide carboxylate group and silica sol as an active ingredient was applied and dried. It has been shown that the substrate retains holes without being exposed to light. As evidence, DMPO-OH, which is recognized as having a hydroxyl radical in the ESR spectrum of an electron spin resonance test of a solution obtained by dropping a radical trapping agent DMPO (5,5-dimethyl-1-pyrroline-N-oxide) aqueous solution on the surface. It is described that holes are retained from the fact that the four peaks are detected.

  Patent Document 3 discloses a sanitary mask characterized in that a fiber base material and an activated carbon sheet on which fine particle antiviral agents that generate hydroxy radicals are laminated are laminated at a respiratory passage location of the mask body. ing. Patent Document 4 describes that a virus inactivating agent containing a monovalent copper compound as an active ingredient exerts a virus inactivating function in a dark place as well as in a bright place.

  Further, Patent Document 5 includes a face mask, which includes a plurality of layers including an outermost layer having a bactericidal agent, and the bactericidal agent-containing layer has a polyhexamethylene biguanide content of 0.01 to 20 wt. A face mask is disclosed having a percent, 0.01 to 10 percent by weight citric acid, and 0.01 to 10 percent by weight N-alkyl polyglycoside.

  Patent Document 6 selects from alkali metal oleate and alkali metal dioctylsulfosuccinate as a filter medium for the mask and air filter in order to ensure safety because viruses captured when the mask and air filter are replaced are scattered. There has been proposed a sheet carrying an antiviral agent containing the anionic surfactant as an active ingredient.

  On the other hand, in Patent Document 7, it is pointed out that when an organic solvent-dispersed silica sol is used by blending with a synthetic resin such as polyester, acrylic resin, or polycarbonate, it exhibits a solid acidic action on the surface of colloidal silica particles (specification). Calligraphy paragraph 0003).

  JP 2006-43574 A   JP 2013-126623 A   JP 2012-152327 A   JP 2011-153163 A   Japanese Patent No. 4823314   JP 2010-24587 A   JP 2007-63117 A

  However, according to the embodiment, the catalyst body disclosed in Patent Document 1 is inserted into a sealed container with the target metal Ti powder, heated, and the surface is activated under a reducing atmosphere. The sample was heated to a temperature of, and oxygen at a predetermined partial pressure was introduced, and the partial pressure of oxygen decreased due to the oxidation of the sample over time. After the treatment is completed, the sample is cooled as quickly as possible, and the resulting powder collides with the surface of metal, alloy, ceramics, or plastic with a carrier gas mainly composed of air or nitrogen gas having a flow rate of 100 m / s or more. As a result, the metal-deficient non-stoichiometric oxide powder is fixed to the surface layer of these structures, and there is a problem that the manufacturing cost is very high.

  On the other hand, the base material-catalyst film disclosed in Patent Document 2 uses a transition metal carboxylate or a transition metal oxide carboxylate as its main component in its production. There is a problem that the manufacturing process of the hole catalyst is high because the manufacturing process is complicated and troublesome and the manufacturing cost is very high.

  Patent Document 3 discloses a mask in which a fiber base material and an activated carbon sheet on which a fine particle antiviral agent that generates hydroxy radicals adheres to a respiratory passage portion of the mask body are laminated. The disclosed antiviral agent is, for example, baked and pulverized dolomite, etc., neutralized, and then pulverized into fine particles, which can be adhered to the fiber substrate by, for example, an adhesive component It is. For this reason, the fine particles as the active ingredient may be covered with an adhesive to reduce the effect, and the production cost may increase.

The means proposed in Patent Document 4 is a highly toxic substance having a limit concentration of 1 mg / m ^{3 in} the atmosphere of cuprous oxide which is an active ingredient. Since copper oxide itself has no adhesion to the substrate, there is a problem that a binder is required to fix the substrate to the substrate. Further, in the face mask disclosed in Patent Document 5, the bactericidal agent exhibiting the bactericidal action is mainly a chemical agent, and it takes about 30 minutes for the effect to be manifested, so that the virus is inactivated while passing through the mask. There is a problem that cannot be expected.

  In addition, there is a problem that the safety of the antiviral agent proposed in Patent Document 6 is unknown. In addition to this, many antiviral agents have been proposed, but those that have antiviral properties are also toxic to the human body as they are, and the fact is that no masks have been put to practical use.

  The description of Patent Document 7 suggests the action of the solid acidic catalyst on the surface of the colloidal silica particles, but does not lead to the purification action of the living space.

  The present invention solves the problems described in the above-mentioned prior art documents, and its production cost is extremely low, and when used in a space, it exhibits an antiviral action and the like, and is harmless to the human body. It is an object of the present invention to propose a substrate-silica sol dried composite, a production method thereof, and a product using the same, particularly a mask and an air treatment apparatus.

  The present inventor has further conducted detailed studies on the means disclosed in Patent Document 2 including the existence of holes by means of electron spin resonance and antiviral properties. As a result, the substrate-silica sol dried product composite obtained by applying silica sol to the substrate and drying it at an ambient temperature of 0 ° C. to 400 ° C., preferably 2 ° C. to 120 ° C., retains holes in the absence of light. The inventors have found that when they come into contact with moisture, a hydroxy radical is generated, and the present invention has been completed.

  The substrate-silica sol dried product composite according to the present invention is characterized by having a hole formed by drying after applying a silica sol on the substrate and the substrate.

  In the above invention, the silica sol as the raw material desirably has a silica particle size of 4 nm to 0.7 μm, particularly 8 to 20 nm.

  In each of the above inventions, the drying atmosphere temperature after application of the silica sol to the substrate is preferably 0 to 150 ° C, particularly 2 to 50 ° C.

  In each of the above inventions, the substrate can be any one of fiber, woven fabric, nonwoven fabric, paper, refractory, metal, wood, plastic, glass charcoal, bamboo charcoal, or a composite thereof.

When selecting a fiber, a woven fabric, or a nonwoven fabric as the substrate, the amount of silica attached to the substrate is 0.1 per mass (g · m ² ) per unit surface area of the substrate in a dry state. It is desirable to be in the range of ~ 2.1 g. In the above case, it is desirable that the drying atmosphere temperature after application of the silica sol is 2 to 50 ° C.

  Each of the above inventions is characterized by generating hydroxy radicals when contacted with water, and further exhibiting a virus inactivating action in the absence of light.

  Each of the above inventions is characterized by generating hydroxy radicals when contacted with water, and further exhibiting a virus inactivating action in the absence of light.

The base material-silica sol dried product composite is a mass per unit mass (g / m) per unit surface area of the base material in a dry state of a treatment liquid containing 1% to 40% silica. ² ) It can be manufactured by coating at 0.1 to 2.1 g per unit, and then drying at an atmospheric temperature of 0 to 150 ° C.
The base material-silica sol dried product composite is a mass per unit mass (g / m) per unit surface area of the base material in a dry state of a treatment liquid containing 1% to 40% silica. ² ) It can be manufactured by coating at 0.1 to 2.1 g per unit, and then drying at an atmospheric temperature of 0 to 150 ° C.

  The substrate-silica sol dried product composite is preferably applied to a mask. In this case, first, the mask has the base-silica sol dry matter composite according to any one of the inventions described above at least for the breath permeable portion of the members constituting the mask. In addition, a base material-silica sol dried composite produced by using a gauze mask as a mask, the base material being a cotton-based non-woven fabric, and a dry atmosphere temperature of 0 to 150 ° C. with respect to the breath transmitting portion. It can be attached.

  The base material-silica sol dried product composite is made of fiber, woven fabric or non-woven fabric as a base material, and is incorporated into at least one of or both the exhaust side and the intake side of the members constituting the air processing device to constitute the air processing device. can do.

  According to the present invention, it is possible to provide a substrate-silica sol dried product composite that exhibits rapid antiviral action and bactericidal action in the absence of light, at an extremely low manufacturing cost. In addition, by applying the substrate-silica sol dried product complex according to the present invention to a member that is required to have a function such as rapid virus inactivation under no light, such as a filter material of a face mask or an air filter, it is effective in living space Thus, it is possible to contribute to the maintenance of citizens' health, such as virus inactivation, sterilization of pathogenic bacteria, and removal of VOC that causes sick house syndrome.

  FIG. 1 is a chart showing thermal analysis results in the drying / dehydration process of silica sol used in the present invention.   FIG. 2 is a graph showing time-series changes in virus titer due to the dried substrate-silica sol composite according to one example (Example 2) of the present invention.

  The substrate-silica sol dried composite according to the present invention is basically a substrate-silica sol dried composite containing holes obtained by drying after applying the silica sol on the substrate. Characterized as a dried silica sol.

  Here, as a base material in the case of applying to the base material-silica sol dried product composite, there is no particular limitation, and for example, natural fibers and synthetic fibers that decompose at a relatively low temperature can be used. There is no restriction | limiting in particular also in the shape of a base material, A plate-like or granular thing can be used besides a fibrous thing. Specifically, natural or synthetic fibers, woven fabrics, non-woven fabrics, paper, refractories, plate-like or fibrous metals, wood, plastic, glass, charcoal, bamboo charcoal and their composites may be used. it can.

A solution containing silica sol as an active ingredient is applied onto the substrate and dried to form a dried substrate-silica sol. In the present invention, it is preferable that the silica sol dried product is obtained by gradually dehydrating and drying the silica sol solution at a low temperature including room temperature. The details of the produced dry matter are not necessarily clear, but when the OH ^- group such as (Si (OH) ₆ ) ^-2 etc. present in the silica sol water is gradually dried at a low temperature and free water evaporates, it is detached. It is presumed that dehydration is delayed and holes corresponding to negative charges are generated after drying.

  The silica sol solution used in the present invention includes those using water as a dispersion medium and those using an organic solvent as a dispersion medium, both of which can be used. The concentration is preferably about 1 to 40% by mass ratio. If the concentration is too low, the amount of silica sol solution required to obtain the necessary dry product or substrate-silica sol dry product increases, leading to a decrease in production efficiency. On the other hand, when the concentration is too high, the amount of adhesion cannot be controlled within an appropriate range, and problems such as difficulty in ensuring the air permeability of the base material-dried material complex occur. In the case of using a substrate that repels an aqueous silica sol such as plastic, organic coated metal, and stainless steel plate, an organic solvent silica sol such as methanol or isopropyl alcohol may be used.

  The drying temperature is also important. When the drying atmosphere temperature is higher than 150 ° C., the characteristic effect of the present invention is hardly expressed. Conversely, when the temperature is lower than 0 ° C., the silica sol is likely to be frozen or gelled, so that the object of the present invention cannot be achieved. The appropriate drying atmosphere temperature is affected by the concentration of the silica sol and the ventilation conditions during drying, but is generally 0 ° C. or higher and 150 ° C. or lower, preferably 2 ° C. or higher and 50 ° C. or lower.

  FIG. 1 shows the heat of powder obtained by dripping an aqueous solution of silica sol (Snowtex O (trademark), manufactured by Nissan Chemical Industries, Ltd.) containing 20% by mass of silica onto a glass plate and naturally drying. It is a graph which shows the result of having conducted the analytical test. As a tester, Seiko Epson Co., Ltd. EXSTAR6000 (registered trademark) was used. In a test room at a room temperature of 20 ° C., the thermal analysis conditions were a heating rate of 5 ° C./min. Therefore, air was flowed at a rate of 300 mL / min (flow rate: 1 m / min).

  From FIG. 1, the silica sol powder obtained by natural drying has already started to lose weight in the ventilation state before heating, and during the heating process, the sudden weight loss with an endothermic peak at about 46 ° C. becomes moderate from 100 ° C. It can be seen that the exotherm is moderate and reaches a peak at 400 ° C. In FIG. 1, the weight loss up to 57.6 ° C. is calculated as 11.2%. In addition, it is estimated that most of the silica sol has been modified into a partially dehydrated product during the drying process up to about 150 ° C.

When such a partially dehydrated product is produced on a substrate, as will be apparent from the following examples and the like, holes (h ⁺ ) are present and take electrons from the contacted partner. That is, it is presumed that the effect of oxidizing causes various effects as will be described later.

  Hereinafter, embodiments of the present invention will be further clarified by examples.

(Example 1: Confirmation and evaluation of appropriate value of drying temperature)
The effect of silica sol drying temperature on hole formation is investigated using electron spin resonance (ESR) spectroscopy. Hydroxyl radical OH. Produced by reaction of holes with water is highly reactive and has a short lifetime, so that it reacts with spin trap agent DMPO (5,5-dimethyl-1-pyrroline-N-oxide) and is stable radical DMPO. It is converted into —OH. And quantified by the peak size from the spectrum of the ESR.

(Sample preparation)
A cotton spunlace nonwoven fabric (Cot Ace C060S / A18 (trademark) manufactured by Unitika Ltd., basis weight: 60 g / m ² ) was prepared as a base material. This is cut into a size of 25 × 40 mm and placed on a stainless steel wire mesh. Silica sol (Snowtex O (trademark) manufactured by Nissan Chemical Industries, Ltd.) using water as a dispersion medium is doubled in water. Dilute to a concentration of 6.7% by mass, drop 0.35 mL per substrate, and dry in an atmosphere of 4 ° C., 28 ° C., 50 ° C., 80 ° C. and 150 ° C. to prepare a sample for ESR measurement . Three samples were prepared for each drying temperature.

(Preparation of DMPO reaction solution)
The measurement sample was reacted with a DMPO aqueous solution as follows to obtain a DMPO reaction solution (a solution containing DMPO-OH).
(1) Each of the three sheets prepared as described above is placed on a 26 × 75 mm slide glass.
(2) From above, 1.1 mL of a DMPO aqueous solution having a concentration of 5% by mass is dropped and permeated.
(3) Further, another slide glass is placed on a silica sol-coated cotton nonwoven fabric into which a DMPO aqueous solution is dropped and permeated, and held for 5 minutes.
(4) The slide glasses on the upper and lower surfaces are squeezed down, and the DMPO reaction solution reacted with the measurement sample is squeezed out (about 0.4 ml) to obtain a DMPO reaction solution for ESR measurement.

(Measurement of ESR)
About the obtained DMSR reaction liquid for ESR measurement, JEOL Ltd. JES-RE3X, resonance frequency: 9.4 GHz, sweep width: 334.5 ± 7.5 mT, magnetic field modulation width: 0.2 mT, time constant : ESR was measured under the condition of 0.03 sec. Since the spectrum obtained showed a four-line signal with DMPO-OH · specific intensity ratio of 1: 2: 2: 1, its peak value was measured.

  For comparison, the DMPO reaction solution was adjusted and ESR was measured using the substrate (untreated non-woven fabric) to obtain a control value.

  The evaluation was performed by the difference in control (cotton without silica sol coating) value from the left peak value of the two central peaks having the large peak. The results are shown in Table 1.

From Table 1, it can be seen that within the range of the drying conditions of Example 1, a peak difference is recognized with respect to the case of no treatment (control) regardless of the drying temperature and the drying conditions. This indicates that a base material-silica sol dry matter composite having holes (h ⁺ ) is obtained within the range of the experiment. In particular, when the drying conditions are temperature: 28 ° C., natural drying for 4 hours, and hot air drying at 50 ° C. for 30 minutes, the hole (h ⁺ ) retention amount is particularly high. By repeating such an experiment, it can be seen that adopting a drying temperature of 2 to 50 ° C. is particularly preferable for obtaining a base-silica sol dried product composite having holes (h ⁺ ).

(Example 2: Influence of silica particle size of silica sol)
Various silica sols that can be obtained on the market are coated and dried on the substrate, and the resulting base material-silica sol dried product is subjected to the following methylene blue test to investigate the effect on the generation of holes caused by the difference in the type of silica sol. did. In the investigation, a 55% Al—Zn plated steel plate was used as a substrate, 30 μL of the silica sol solution shown in Table 2 was dropped on the surface of a 3 cm × 3 cm square specimen, and then naturally dried in an atmosphere at a temperature of 26 ° C. for 4 hours. did. On the surface of the obtained 55% Al—Zn-plated steel sheet-silica sol dried product (silica sol coating production side), 50 μL of 0.3 mMole / L methylene blue aqueous solution was dropped and immediately covered with polypropylene film and held for 1 minute. Thereafter, the polypropylene film was peeled off, the surface was washed with 2 ml of purified water, and the concentration of the washing solution was measured by a methylene blue test using a spectrophotometer. In addition, the investigation was conducted for each of three 55% Al—Zn plated steel sheet specimens, and the results were shown as average values. The results are shown in Table 2.

  Table 2 shows the types, particle sizes, shapes, and concentrations of silica sols used in the investigation. Here, the particle size of the silica sol means the value of the catalog of the silica sol manufacturer, and the concentration means the mass ratio (%) of the silica content contained in the silica sol solution. The shape means the shape of the silica particles obtained when the silica sol solution is observed under an electron microscope. The spherical shape means that the silica particles appearing in the visual field are almost spherical. It means a spherical particle having a diameter of 300 to 700 nm in which many pores of ˜15 nm are present on the particle surface.

From the obtained results: (1) For silica sols with a spherical silica shape, when the silica sol concentration is the same, the smaller the particle size, the lower the methylene blue concentration, that is, more hole generation, If the concentration of silica sol is low, the amount of holes generated is reduced accordingly.
(2) Even when the silica sol has a coarse silica particle size and a porous shape, as the silica shape is spherical, the smaller the particle size, the more holes are generated. Is not much different from that of spherical silica having a particle size of 1/10 or less, and it can be seen that the specific surface area contributes greatly due to the presence of many fine pores on the particle surface.
(3) Adhesive force to the base material increases as the particle size decreases, and adhesion to the base material is an important factor as a characteristic of the base material-silica sol dried product composite. Therefore, a silica sol having a high concentration and a small particle size is desirable including the main hole generation function.

(Example 3: Confirmation and evaluation of antiviral properties)
(Sample adjustment)
For each material shown in Table 3, a small piece having a size of 30 mm × 30 mm was prepared, and a silica sol having a particle diameter of 10-15 nm with water as a dispersion medium (Snow manufactured by Nissan Chemical Industries, Ltd.) was prepared in the same procedure as in Example 1. 100 μL of a silica sol solution having a concentration of 6.7% by mass obtained by diluting Tex O (trademark) with purified water was dropped on a glass cloth piece and 350 μL on a cotton piece, and the solution was added in a 50 ° C. atmosphere. The sample was dried for 5 minutes to obtain a sample of the substrate-silica sol dried product composite.

(Antiviral evaluation)
The antiviral property was evaluated by the effect of the antiviral property against influenza virus on the virus titer (HA value) by the following method.
(1) Add 0.5 ml of A / Philippine / 2/82 (H3N2) influenza virus solution cultured in chicken embryos with a titer of 128 HA or more to each 30 mm × 30 mm sample piece of the substrate-silica sol dried product complex. .
(2) Each piece after addition of the obtained influenza virus solution is incubated at 37 ° C. for 1 hour.
(3) Each of the small pieces after the incubation is washed with 2 ml of PBS (phosphate buffer solution) three times, and the titer measurement solution after the reaction between the substrate-silica sol dried product complex and the influenza virus solution is performed. did.
(4) The titer (HA titer) was measured by the “erythrocyte agglutination (HA) test” using a 96-well microplate. The results are shown in Table 4.

  The antiviral activity value (L) represents the antiviral properties of the cloth itself including the catalytic function, and the virus reduction value (N) represents the catalytic antiviral properties. When the antiviral activity value (L) is 0, it is judged that there is no antiviral property and when it takes a positive value, it is judged that there is antiviral property. There is no increase in antiviral activity, and it is judged that there is an increase in antiviral activity when taking a positive value. The antiviral activity value (L) is considered to be the sum of antiviral properties of both the catalyst and the substrate. As shown in Table 3, it can be seen that the substrate-silica sol dried product composite according to the present invention exhibits a virus inactivating action on various fiber materials used as the substrate.

(Example 4: Confirmation / evaluation of substrate-silica sol dried product composite)
(Sample adjustment)
Silica sol (Nissan Chemical Industry Co., Ltd.) using a soft type cotton non-woven fabric (Cot Ace manufactured by Unitika Co., Ltd., C080S / Z09 (trademark), basis weight: 80 g / m ² ) as a base material and cut into 10 × 10 mm Snowtex C (trademark) manufactured by Co., Ltd. was diluted with pure water and naturally dried for a long time to obtain a dried substrate-silica sol composite, which was a 100 mm × 100 mm sample for measuring air permeability. The amount of dry silica sol deposited with no treatment and brushed with a silica sol having a concentration of 5.1% by mass was 0.25 g / g / m ^2. The air permeability of this non-woven fabric was determined according to JIS L1096 A method and fragile method. They were 59 and 62 cc / cm ² / sec, respectively.

(Antiviral evaluation)
About the obtained base-silica sol dried product complex, the base-silica sol was dried in the same manner as in Example 3 except that the addition amount of influenza virus solution was 0.05 ml and the incubation time was 0 minutes and 10 minutes. The titer was measured after the reaction between the product complex and the influenza virus solution. Moreover, the titer measurement after reaction with the influenza virus liquid was performed as a control material also about the soft type cotton nonwoven fabric used as a base material. The measurement results are shown in FIG.

  As can be seen from FIG. 2, when the virus solution comes into contact with the dried silica sol complex according to the present invention, it can be seen that the virus titer rapidly decreases to 1.6 at maximum in 0 minutes. Actually, it takes about 1 minute to perform the flow of the virus solution with 50 μL of PBS water twice, but the glycoprotein of HA is rapidly increased by the hydroxy radical generated from the substrate-silica sol dried product complex according to the present invention. It is clear that the degradation is disabled.

  Samples prepared by applying silica sol to the nonwoven fabrics described in Examples 3 and 4 and drying were immersed in purified water for 1 hour before ESR and antiviral tests and then naturally dried. Such a substrate-silica sol dried product composite and its application article are insoluble in water and can be washed with water. Moreover, since holes are regenerated after drying, the substrate-silica sol dried product composite and its applied articles can be used in contact with water repeatedly.

  As shown in the above examples, in the present invention, inactivation of influenza virus HA is used for evaluation in the evaluation of antiviral activity, and viruses having an envelope in which HA is present, that is, rubella virus, measles virus, SARS corona Effective for all viruses and Japanese encephalitis virus. Here, HA is one of two types of glycoproteins arranged in a spike shape outside the lipid membrane called the envelope of influenza virus etc. and is hemagglutinin (hemagglutinin). Has the ability to infect. When glycoproteins are decomposed by holes or hydroxyl radicals, the infectivity is lost, so it is used for the evaluation of virus titer.

  Gauze of commercial gauze mask (product name: soft cotton gauze mask, 6 layers of cotton gauze, size 135x95 mm, manufactured by Daiso Sangyo Co., Ltd.) and gauze overlapping part in Example 3 (size 135x95 mm, manufactured by Daiso Sangyo Co., Ltd.) Three pieces of the prepared silica sol-dried composite sheet (9 cm × 9 cm) used in Example 3 were sandwiched between the overlapping portions one by one to obtain an antiviral gauze mask. With this antiviral gauze mask, the decrease in virus titer is log 4.8, that is, 1,99.98% of the original virus can be reduced by 1,99.98%.

As mentioned above, although embodiment of this invention was clarified including the Example, embodiment of this invention is not limited to these. In particular, the environmental purification action of the substrate-silica sol dried product composite according to the present invention is due to the holes (h ⁺ ) of the silica sol dried product, and as a result of the environmental purification action, once contacted with water. Even if holes are lost due to generation of hydroxy radicals, considering that they can be regenerated by drying, multifaceted utilization can be expected. In other words, since it possesses holes, when it is used for a face mask, it exhibits an unprecedented unique function of inactivating viruses during passage through the mask. As a filter for an air purifier or an air conditioner, VOC (Volatile Hazardous Organic Compound) and bad odor that cause sick house syndrome can be decomposed, detoxified, and purified by being oxidized by holes without light irradiation.

Claims (13)

  A base material and a base material-silica sol dried product composite, wherein the base material and the base material are dried after silica sol is coated on the base material and retains holes.   2. The substrate-silica sol dried product composite according to claim 1, wherein the silica particles constituting the silica sol have a particle size of 4 nm to 0.7 μm.   3. The substrate-silica sol dried product composite according to claim 2, wherein the silica particles have a particle size of 8 to 20 nm.   The substrate-silica sol dried product composite according to claim 1, 2 or 3, wherein the drying atmosphere temperature after coating is 0 to 150 ° C.   The substrate-silica sol dried product composite according to claim 4, wherein the drying atmosphere temperature after coating is 2 to 50 ° C.   The substrate is fiber, woven fabric, non-woven fabric, paper, refractory, metal, wood, plastic, charcoal, bamboo charcoal, or a composite thereof, or a processed product using these as raw materials. 6. The substrate-silica sol dried product composite according to any one of 5 above. When the substrate is a fiber, a woven fabric, or a non-woven fabric, the amount of silica sol attached to the substrate is 0.1 to ² per mass (g / m ² ) per unit surface area of the substrate in a dry state. The substrate-silica sol dried product composite according to claim 6, which is in a range of 5 g.   8. The dried substrate-silica sol composite according to claim 1, wherein the dried substrate-silica sol complex generates hydroxy radicals when contacted with water.   The substrate-silica sol dried product composite according to any one of claims 1 to 8, which exhibits a virus inactivating action in the absence of light.   A mask comprising at least a breath-permeating portion of the member constituting the mask made of the substrate-silica sol dry matter composite according to any one of claims 1 to 9.   A mask comprising a gauze mask as a main body, and the base material-silica sol dry matter composite according to claim 5 attached to a breath transmitting portion thereof.   The base material-silica sol dry matter composite according to any one of claims 1 to 9, wherein a base material is a fiber, a woven fabric, or a non-woven fabric at least on one or both of an exhaust side and an intake side among members constituting an air treatment device. An air treatment device with the body attached as an air filter element. The treatment liquid containing 1% or more and 40% or less of silica by mass ratio is 0.1 to 0.1 per mass (g / m ² ) per unit surface area of the substrate in a dry state. A method for producing a dried substrate-silica sol composite, wherein the substrate is dried so as to have an atmospheric temperature of 0 to 150 ° C. after being applied so as to be in a range of 2.1 g.

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