HK1149221A - Novel hydroxy radical generation method, and anti-viral material utilizing hydroxy radical generated by the method - Google Patents

Description

Novel method for generating hydroxyl radical and antiviral material using hydroxyl radical generated by the method

Technical Field

The present invention relates to a method for efficiently generating hydroxyl radicals and an antiviral material which can reliably and significantly inactivate viruses by using the hydroxyl radicals generated by the method.

Background

The hydroxyl radical is represented by. OH, is a radical formed from hydroxyl groups, and is a group called active oxygen. Since hydroxyl radicals have a strong reactivity with active oxygen and a strong oxidizing ability, they can react with proteins, lipids, sugars, nucleic acids (DNA, RNA), etc., and in particular, can cause the chain oxidation of lipids.

Various studies have been made on a method for purifying harmful organic substances contained in the air and water by utilizing the properties of the hydroxyl radicals. As a method for generating hydroxyl radicals, the Fenton reaction (a reaction in which hydrogen peroxide and divalent iron ions are reacted under acidic conditions to generate hydroxyl radicals) is known; Haber-Weiss reaction (reaction of hydrogen peroxide with superoxide anion in the presence of ferric ion to generate hydroxyl radical); a method of irradiating hydrogen peroxide with ultraviolet rays; a method of irradiating ozone (ozone) and ultraviolet rays into the moisture; and a method of generating Corona (Corona) discharge or Plasma (Plasma) discharge in a gas or water containing much water (Japanese patent laid-open Nos. 2001-70946 and 2000-288547).

However, the above-mentioned method for generating hydroxyl radicals requires a method of irradiating hydrogen peroxide, ultraviolet rays, ozone, corona discharge, plasma discharge, or the like, and a method of generating hydroxyl radicals under conditions that may be harmful to the human body, and therefore, development of a method of generating hydroxyl radicals more safely and easily is desired.

Further, as a method for generating hydroxyl radicals, there is a method using a silver-supported photocatalyst (for example, Japanese patent laid-open No. 2004-337562), and viruses and bacteria are inactivated by the hydroxyl radicals generated by this method.

However, since inactivation of viruses by silver-loaded photocatalysts requires irradiation with light of a certain intensity, such as natural light or fluorescent light, there is a need for development of a method for inactivating viruses or bacteria by generating hydroxyl radicals regardless of the presence or absence of irradiation. Further, improvements are desired in terms of cost reduction, simplification of treatment, improvement of the hydroxyl radical generation rate, control of the hydroxyl radical generation amount, and the like.

Furthermore, antiviral agents using other conventionally known methods for inactivating viruses have not been known in the art, and have a low probability of inactivation, and various disadvantages in a method of applying an antiviral agent to a target virus (hereinafter, simply referred to as an application method). Even in the following antiviral agents (a) and (b) obtained by an ionic method and a gas method, which have relatively clear inactivation mechanisms, the virus inactivation effect is not significant, and the contents and types of applicable methods are also the same.

(a) An antiviral agent of a binary system comprising a cationic group such as a quaternary Ammonium group and a hydrocarbon chain (e.g., a saturated fatty acid) and having antiviral activity has been disclosed (see japanese patent No. 3222471).

The inactivation mechanism of viruses has a low inactivation rate because hydrophobic viral envelopes are approached by hydrocarbon chains and viruses having envelopes (paramyxovirus, coronavirus, poxvirus, etc.) are inactivated by cationic groups in the vicinity of the viruses.

In addition, the antiviral application products are obtained by fixing antiviral agents to cloths via covalent bonds, and the cloths are used for protective products, medical-staff clothing (wound covers, burn covers), patient medical supplies (sutures, bandages), and the like, and therefore, the applicable methods are limited.

(b) An antiviral agent has been disclosed (see japanese patent No. 3547140) which inactivates fungi, bacteria, and viruses as chlorine dioxide gas widely used as a bleaching agent, a disinfectant, and the like.

However, the mechanism of virus inactivation in this case is,

1) a hydrophilic substance mixed with chlorite anions (chlorite and the like) is contained in the hydrophobic particles, and moisture attached to the hydrophobic particles is absorbed into the hydrophobic particles.

2) The absorbed water chlorite is hydrolyzed to release hydronium ion, and the chlorine oxide gas released by the reaction with the chlorite ion of the hydrophobic particle inactivates the virus,

the probability of inactivating the virus is unknown, so the method has small application range.

Thus, conventional antiviral agents have limitations on the methods of application because the contents of the inactivation mechanism are unclear and the probability of virus inactivation is unclear even in the ionic system, the gas system, and other systems.

The "method of application" used in the following detailed description of the present invention has the same meaning as the method of application of an antiviral agent of the prior art.

Further, International publication No. WO 2005/013695A 1 discloses that dolomite (dolimite) is calcined, and when the calcined dolomite is still at a high temperature, water is added to hydrate a part of the calcined dolomite, and the calcined dolomite is pulverized or sieved to obtain a powder having a size in the range of 0.1 to 60 μm (the powder particles are secondary particles in which primary particles are aggregated, and the size of the primary particles constituting the secondary particles is in the range of 1 to 200 nm), and has an antiviral effect. However, no study has been made from the viewpoint of generation of hydroxyl radicals, and the content of the virus inactivation mechanism and the probability of virus inactivation have not been clarified yet.

In view of the above, the present inventors have experimentally studied in detail to obtain a method for generating hydroxyl radicals more safely, easily and efficiently, and have found several scientific facts about inactivation of viruses, as well as a mechanism for inactivating viruses and a method for specifically inactivating viruses.

Disclosure of Invention

The present invention addresses the problem of providing a method for generating hydroxyl radicals more safely, easily and efficiently than the conventionally known methods for generating hydroxyl radicals such as the Fenton reaction.

Another object of the present invention is to provide an antiviral material comprising a metal oxide powder and a hydroxide, which are capable of generating hydroxyl radicals, based on the knowledge that hydroxyl radicals effectively inactivate viruses.

In order to solve the above problems, the present invention provides the following methods:

(1) a method in which a hydroxyl radical is generated by bringing 1 or more kinds of metal oxide powder selected from the group consisting of alkali metals, alkaline earth metals, and metals of groups 4 to 12 of the periodic table or aluminum into contact with 1 or more kinds of hydroxides selected from alkali metal hydroxides, alkaline earth metal hydroxides, iron hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and ammonium hydroxide.

(2) In the method described in (1), the metal oxide powder and the hydroxide are both contained in the dolomite treated product obtained by calcining dolomite and then hydrating a part of the calcined dolomite.

(3) In the method described in (2), the dolomite treated product is obtained by calcining raw dolomite at a temperature of 700 to 1300 ℃ for 1 to 20 hours, cooling to normal temperature, and contacting 35 to 60 parts by weight of water with 100 parts by weight of dolomite.

(4) In the method described in (3), the dolomite treated product is calcined at a rate of temperature rise of 5 to 10 ℃/min and is held at a temperature of 700 to 1000 ℃ for 8 to 12 hours, and the air current is intermittently operated at this time.

(5) The method according to (1) or (2), wherein the weight ratio of the metal oxide powder to the hydroxide, that is, the ratio of the metal oxide powder to the hydroxide is in the range of 0.001 to 100.

(6) In the method described in (1), the metal oxide powder is 1 or more kinds of oxide powder selected from magnesium oxide, calcium oxide, manganese dioxide, iron trioxide, copper oxide, zinc oxide and aluminum oxide, and the hydroxide is 1 or more kinds of hydroxide selected from sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide and ammonium hydroxide.

In addition, the present invention provides an antiviral material comprising:

(7) a method in which a hydroxyl radical is generated by contacting 1 or more metal oxide powder selected from the group consisting of alkali metals, alkaline earth metals, and metals of groups 4 to 12 of the periodic table or aluminum with 1 or more hydroxide selected from alkali metal hydroxides, alkaline earth metal hydroxides, iron hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and ammonium hydroxide.

The method for generating a hydroxyl radical according to the present invention can safely, easily and efficiently generate a hydroxyl radical without using conditions that may be harmful to a human body, such as hydrogen peroxide, ultraviolet rays, and corona discharge.

The antiviral material having the method for generating a hydroxyl radical of the present invention can be used in various applications as an antiviral material for preventing viral infection, such as a mask, a curtain, and a protective clothing.

Detailed Description

The present invention is based on the novel knowledge that a hydroxyl radical is generated by bringing 1 or more metal oxide powders selected from the group consisting of alkali metals, alkaline earth metals, and metals of groups 4 to 12 of the periodic table or aluminum into contact with 1 or more hydroxides selected from alkali metal hydroxides, alkaline earth metal hydroxides, iron hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and ammonium hydroxide.

The present invention also provides an antiviral material having antiviral properties, which is a method for generating hydroxyl radicals by contacting 1 or more metal oxides selected from the group consisting of alkali metals, alkaline earth metals, and metals of groups 4 to 12 of the periodic table or aluminum with 1 or more hydroxides selected from alkali metal hydroxides, alkaline earth metal hydroxides, iron hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and ammonium hydroxide, and which inactivates viruses by hydroxyl radicals, and the present inventors have conducted the present invention based on newly discovered scientific facts such as (1) to (5) below.

(1) The fact that the hydroxyl radical alone has a great effect of inactivating viruses.

(2) Active oxygen other than hydroxyl radicals has no or little effect on virus inactivation alone.

(3) The fact that hydroxyl radicals, their viral inactivation mechanism, can inactivate a wide variety of viruses that work effectively.

(4) The fact that the hydroxyl radical is controlled by the combination and reaction of the metal oxide powder and hydroxide, the effect of virus inactivation is increased.

(5) The fact that the surface state of the metal oxide powder exerts an influence on the generation of hydroxyl radicals that inactivate viruses.

The present invention will be described in detail below.

< Metal oxide >

In the present invention, the powder of 1 or more kinds of metal oxides selected from the group consisting of alkali metals, alkaline earth metals, metals of groups 4 to 12 in the periodic table, and aluminum may generate hydroxyl radicals in the reaction with the hydroxide, and either of natural (representing metal oxides contained in minerals) and synthetic types may be used, or one or more kinds may be used. From the viewpoint of the efficiency of generation of hydroxyl radicals, the metal oxide powder is preferably a powder in which the metal oxide selected as the raw material has a large specific surface area, particularly a porous powder.

Natural metal oxide powder may be produced by chemical treatment or physical treatment of a mineral (for example, a mineral containing salt or Double salt). The metal oxide derived from a mineral source needs to be a metal oxide powder capable of generating hydroxyl radicals in the reaction with the hydroxide (see examples described later).

Among the above-mentioned metal oxides, magnesium oxide, calcium oxide, copper oxide, zinc oxide, silver oxide, aluminum oxide and the like are preferable from the viewpoint of easiness of reaction with a hydroxide. In particular, when the metal oxide contains magnesium oxide or calcium oxide as a basic metal oxide, it is easy to find out the generation of hydroxyl radicals and the inactivation of viruses by the generated hydroxyl radicals.

Even when the metal oxide is present in the mineral, the metal oxide powder derived from the mineral or the mineral powder containing the metal oxide (hereinafter referred to as metal oxide powder derived from the mineral) can be supplied to the reaction by crushing, chemical treatment, physical treatment, pulverization, or the like of the mineral.

However, it is necessary to generate hydroxyl radicals by reacting a metal oxide powder derived from minerals with a hydroxide. The metal oxide contains other mineral components that may be present in the mineral powder without inhibiting the hydroxyl radical generation reaction.

Examples of the mineral include dolomite minerals, tourmaline minerals (for example, Dravite (Dravite), schorl (schorl), li-tourmaline (elbaite), and others), Zeolite minerals (Zeolite type mineral), Kaolin minerals (Kaolin type mineral), medical stones, and others, and these minerals are crushed, chemically treated, physically treated, or pulverized to form a metal oxide powder, a coexisting system with a metal oxide powder and a hydroxide powder, or a coexisting system with a third component powder.

< hydroxide salt >

In the hydroxide used in the present invention, one or more kinds may be used if hydroxide ions can be supplied for the generation of hydroxyl radicals by the reaction with the metal oxide powder. Such a hydroxide is, for example, 1 or more kinds of hydroxides selected from alkali metal hydroxides, alkaline earth metal hydroxides, iron hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide and ammonium hydroxide, and sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide are preferably used from the viewpoint of smoothly and easily generating hydroxyl radicals.

As one kind of hydroxide, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, or calcium hydroxide and an aqueous solution thereof are used, and as plural kinds of hydroxides, for example, a mixture of sodium hydroxide and potassium hydroxide and an aqueous solution thereof, a mixture of magnesium hydroxide and calcium hydroxide and an aqueous solution thereof are used.

The hydroxide may be in the form of a solution (e.g., an aqueous sodium hydroxide solution), a Slurry (Slurry) (e.g., a Slurry containing sodium hydroxide), a solid (e.g., anhydrous sodium hydroxide), or the like, or may be in other forms.

Even if the hydroxide is solid, the reaction field due to moisture stratification or the like is formed by adsorption of water to the metal oxide powder and deliquescence of the reaction of the solid hydroxide (for example, anhydrous sodium hydroxide or the like), and the hydroxyl radical generating reaction proceeds.

When the hydroxide is an aqueous solution, for example, when the hydroxide is made to have a basic reaction at a concentration of 0.001 to 0.8 mol/liter (preferably 0.005 to 0.5 mol/liter), the hydroxyl radical generating reaction is favorably carried out.

Furthermore, the hydroxide of the alkaline earth metal can generate a hydroxyl radical alone without contacting the metal oxide. The alkaline earth metal oxide may be used in a solution state, a slurry state, a solid state, or the like, and when the alkaline earth metal oxide is in a solid state, a hydroxyl radical generating reaction proceeds by absorbing moisture or the like. The primary particle diameter of the alkaline earth metal hydroxide is preferably 1nm or more and 1000nm or less, more preferably 1nm or more and 400nm or less, particularly preferably 1nm or more and 200nm or less. Among such alkaline earth metal hydroxides, magnesium hydroxide and calcium hydroxide are preferred from the viewpoint of the amount and efficiency of generation of hydroxyl radicals.

< reaction for generating hydroxyl radical >

Specific examples of the method of bringing the metal oxide powder and the hydroxide into contact with each other to generate hydroxyl radicals include a method of mixing the metal oxide powder into an aqueous solution or slurry of the hydroxide to cause the mixture to react; a method of reacting a metal oxide powder and a hydroxide in a protic or aprotic organic solvent; and a method of bringing the metal oxide powder and the solid hydroxide into contact with each other to cause a reaction in a reaction field caused by moisture adsorption.

If the hydroxyl radical generating reaction is carried out in a state where the surface of the metal oxide powder is surrounded by alkaline mist of hydroxide, the amount and rate of generation of hydroxyl radicals can be controlled by adjusting the alkali concentration to change the intensity of the alkaline mist.

The ratio of the respective amounts of the metal oxide powder and the hydroxide in contact is a weight ratio of (metal oxide powder)/(hydroxide), and is preferably in the range of 0.001 to 100, more preferably in the range of 0.01 to 10. By adjusting the amount to fall within the above range, hydroxyl radicals can be efficiently generated.

For example, when the metal oxide is magnesium oxide and the hydroxide is magnesium hydroxide, the weight ratio of (metal oxide powder)/(hydroxide) is preferably 0.1 to 9, and when the metal oxide is magnesium oxide and the hydroxide is calcium hydroxide, the weight ratio of (metal oxide powder)/(hydroxide) is preferably 0.1 to 4.

When the metal oxide is magnesium oxide and the hydroxide is a mixture of magnesium hydroxide and calcium hydroxide, the weight ratio of (metal oxide powder)/(hydroxide) is preferably in the range of 0.1 to 2.5.

In the method for generating a hydroxyl radical according to the present invention, the generation of a hydroxyl radical can be promoted or controlled more effectively by adding an additive in addition to the metal oxide powder and the hydroxide. For example, Titanium oxide (Titanium oxide) or SrTiO₃、Ag-NbO₂Or AgGaO₂Etc. are appropriately added as additives.

In the method for generating hydroxyl radicals in the present invention, the metal oxide powder and the hydroxide are prepared separately as described above, or a mineral containing both the metal oxide and the hydroxide may be used as it is.

Examples of the case of using a mineral containing both a metal oxide and a hydroxide include a double salt (Ca. Mg (CO)) of a dolomite mineral (Calcium carbonate) and Magnesium carbonate (Magnesium carbonate)₃)₂) Treated powder obtained by the calcination and hydration (treatment) steps. Since the dolomite mineral is a mixture of a metal oxide and a hydroxide which cause a hydroxyl radical generating reaction by performing the calcination and hydration steps of the dolomite mineral under special operating conditions, it can be used as a powder.

The dolomite mineral is calcined by heating the raw dolomite at a temperature rise rate of 1-15 ℃/min, preferably 5-10 ℃/min, to 700-1300 ℃, preferably 700-1000 ℃ under atmospheric pressure, and holding the temperature range for 1-20 hours, preferably 8-12 hours. CO produced by thermal decomposition of dolomite during the calcination₂The gas can affect the decomposition process. When CO is present₂At high gas concentrations, decomposition reactions occur at high temperatures, and conversely when CO is present₂When the gas concentration is low, decomposition reaction occurs at a lower temperature. In order to promote the decomposition reaction, it is necessary to adjust the air flow, and it is preferable to carry out the air flow by feeding or stopping the air flow.

Then, after the dolomite which has been subjected to the calcination process is cooled to normal temperature (20 ℃. + -. 15 ℃ (JIS Z8703)), water is contacted with 35 to 60 parts by weight, preferably 45 to 50 parts by weight, of 100 parts by weight of the dolomite, and a part of the calcined dolomite is hydrated (treated). The contact time with water is preferably from 5 hours to 20 hours, and the water content in the dolomite treated product (treated product powder) after the completion of the treatment step is preferably in the range of 1 to 5%.

The above treated powder comprises magnesium oxide (MgO), calcium hydroxide (Ga (OH)₂) And magnesium hydroxide (Mg (OH)_1～2) As the reaction component, calcium carbonate and a trace amount of component are preferable. If other components are produced in the calcination and hydration step, the production reaction of hydroxyl radicals is inhibited. In addition, if the amount of magnesium oxide is decreased, the amount of hydroxyl radical generated is also decreased. Here, MgO, Ga (OH)₂And Mg (OH)_1～2The content of MgO in the treated powder of each component (A) is 2 to 22 wt%, preferably 5 to 15 wt%, Ga (OH)₂40 to 60% by weight, preferably 45 to 55% by weight, of Mg (OH)_1～25 to 25 wt%, preferably 10 to 20 wt%.

The dolomite-treated product is preferred to have a secondary particle diameter in the range of 0.1 to 60 μm, more preferred in the range of 0.1 to 10 μm, and particularly preferred in the range of 0.1 to 1 μm, for more efficient generation of hydroxyl radicals. The present inventors have confirmed that particularly when the secondary particle diameter is 1 μm or less, the generation of hydroxyl radicals is significant, and the antiviral effect caused thereby is significantly improved.

The metal oxide powder (particularly alkaline earth metal oxide powder) of the present invention and the metal oxide-containing powder of mineral origin containing both a metal oxide and a hydroxide have a specific surface area of 20m by BET method of 60% or more per unit volume of the metal oxide powder²Preferably 40m or more²More preferably,/g or more. Difficult to be powdered, and has a specific surface area of 80m²Large specific surface area (m) of/g or more²In the case of/g), the hydroxyl radical-forming reaction is easier to produce and is more favorable. Even if the specific surface area is less than 20m²There is also the possibility of reaction per gram, but at the same time it is difficult to generate hydroxyl radicals.

The "unit area" of the powder means a predetermined unit area sampled from the pulverized powder, and does not mean that powders having different particle diameters are artificially mixed. The "main amount of the metal oxide powder" in the present invention is a ratio of the main amount per unit volume of the metal oxide powder, and corresponds to, for example, 60% or more of the unit volume.

< identification of hydroxyl radical >

The confirmation of the hydroxyl radical is determined, verified or confirmed by the following method in a quantitative manner.

(a) A method of measuring the fluorescence intensity of a strongly fluorescent compound (fluorescein) produced by reacting an active oxygen detecting reagent of APF (2- [6- (4-amino) phenoxy-3H-xanthen-3-on-9-yl ] benzoic acid) or HPF (2- [6- (4-hydroxy) phenoxy-3H-xanthen-3-on-9-yl ] benzoic acid) with APF or HPF.

(b) Capturing hydroxyethyl radical generated by reaction of alcohol (Ethanol) and hydroxyl radical by POBN (alpha- (4-pyridine-1-oxide) -N-tertbutylnitrone), and measuring by ESR (Electron Spin Resonance).

(c) When the presence of hydroxyl radicals is confirmed, the formation or presence of hydroxyl radicals is confirmed by whether or not the purple color of DPPH (1, 1-diphenylyl-2-piperidinylhydrazyl) of the radical scavenger is lost.

< application of the method for generating hydroxyl radical according to the present invention to antiviral Material >

The "antiviral material" of the present invention means fibers and plastics having an antiviral effect, and various products such as masks and protective clothing comprising these fibers and plastics, and various applications such as other drugs, which are produced by the hydroxyl radical production method of the present invention. When an antiviral effect is imparted to various applications (for example, attachment, fixation, immobilization, support, incorporation, or other methods), it is desirable that the restriction on imparting a viral effect is small or no restriction is present. In the present invention, the use of the hydroxyl radical generating source as the solid powder enables the provision of an antiviral effect to various application methods, and the antiviral material can be used in a wide range almost without limitation.

In addition, a large amount of hydroxyl radicals generated in the contact between the magnesium oxide powder as the metal oxide powder and the aqueous solution of sodium hydroxide as the hydroxide can be confirmed by a measurement method using a reagent for active oxygen detection of APF and a method of measuring ESR by selectively capturing hydroxyl radicals generated by the reaction of hydroxyl radicals with alcohol by POBN.

The present inventors have inferred several reaction mechanisms such as a first-order reaction mechanism, a second-order reaction mechanism, and a reaction mechanism of hydrogen peroxide, which are intermediate reaction mechanisms, for the generation of hydroxyl radicals.

< inactivation mechanism of Virus >

The invention discovers the phenomenon that the hydroxyl free radical destroys the virus structure; a phenomenon of agglutination of viral proteins; the phenomenon of increasing the molecular weight of viral proteins, the phenomenon of formation of large blocks or clusters due to changes in protuberant proteins on the surface, and the phenomenon of inactivation of viruses caused by the large blocks or clusters (see examples described below).

< target Virus >

Viruses that are destroyed by the virus structure generated by hydroxyl radicals, the phenomenon of blocking viral surface protuberant proteins, and the phenomenon of aggregation of viral proteins can all be inactivated by the antiviral material of the present invention.

If a part of the subject viruses is exemplified, for example, influenza viruses (influenza viruses) (e.g., highly pathogenic avian influenza virus (high-pathogen-pathogenic) influenza viruses) (H5N1 HPAIV)/(Vietschna and hong Kong Co., Ltd.), (coronaviruses) (e.g., SARS (Sasa) virus), flaviviruses (flaviviruses) (e.g., hepatitis C virus (hepatitis C virus), dengue viruses (dengue viruses), Japanese B encephalitis virus (Japanese encephalitis virus), West Nivirus (West Nivirus), yellow fever virus (yellfevervirus), picornaviruses (piconaviruses) (e.g., poliovirus (poliovirus), hepatitis A virus (hepatitis A virus)), canine viruses (e.g., Marburg virus (Marburg virus)), and (pseudovirus)), and (pseudovirus (canine virus (Marburg) viruses) (e.g., parainfluenza virus (Marburg virus)), and (Marburg virus)) Paramyxoviruses (paramyxoviruses) (such as Measles virus (Measles virus), Mumps virus (Mumps virus)), herpes virus (Herpesvirus), human papilloma virus (papillomavirus), polyoma virus (polyomavirus), adenovirus (adenoviruses), parvovirus (paravirous), retrovirus (retroviruses) (such as human immunodeficiency virus (human immunodeficiency virus)), hepatitis virus (hepadnaviruses) (such as hepatitis B virus (hepatitis B virus)), and the like.

< application method >

The virus is inactivated by a suitable method for the antiviral material or by conferring antiviral properties in the area where humans or animals are in contact with the virus. The antiviral material is effective for inactivation of various viruses, and when an easily handleable powder is used as the antiviral material, the applicable method is not particularly limited in terms of the use, shape, size, use method, or the like.

Suitable methods are those for use in a state where virus inactivation function is found in, for example, diagnostic equipment, extracorporeal circulation equipment, protective articles, clinical examination equipment (e.g., gloves, various examination equipment, sterile cloth, masks, instrument covers, bandages, etc.), hospital equipment (e.g., surgical gowns, protective cloth, sterile cloth, masks, instrument covers, bandages, etc.), medical consumables (e.g., bandages, masks, etc.), household medical equipment (e.g., beddings and others), sanitary materials, health and hygiene tools, hospital buildings, food manufacturers, containers, food packaging materials, etc.

Further, the carrier for pharmaceutical preparations (solid, liquid, slurry, etc.) and the composition for pharmaceutical preparations other than the carrier for pharmaceutical preparations can be used. The solid carrier is selected from kaolin, Sucrose, Crystalline cellulose, mica, and agar.

< forms of application of the methods >

The antiviral material is disposed in a suitable means in such a manner that hydroxyl radicals can be generated. For example, the fixing may be performed by a method other than fixing, adhering, coating, fixing, incorporating, or carrying. When the hydroxide is in the form of a solution, it may be contained in a suitable means. In particular, a hydroxide is prepared, and the metal oxide provided in the applicable means and the prepared hydroxide are reacted to generate hydroxyl radicals. At that time, the antiviral material of the present invention is composed of the metal oxide and the preliminary hydroxide which are provided by the applicable method.

Even if the hydroxide is not prepared, in the presence of a virus in the presence of an environment in which the hydroxide is present, a hydroxyl radical is generated by the reaction between the hydroxide present in the virus and the metal oxide provided in the applicable means, and the virus is inactivated.

In the present invention, changes, partial modifications and additions may be made without departing from the scope of the invention in keeping with the objects thereof. For example, the present invention is applied to other biological agents (e.g., antibacterial agents) by hydroxyl radicals generated by its principle, which may cause destruction, aggregation, and the like.

Next, the present invention will be described in detail with reference to examples, which are part of specific examples, and therefore the scope of the present invention is not limited by the examples.

Examples

< example 1> "validation of hydroxyl radical"

Magnesium oxide (MgO) powder was put into 0.1 mol/l aqueous sodium hydroxide (NaOH) solution to react. Then, the reaction was carried out in an APF reagent (reagent for detecting active oxygen), and the presence or absence of hydroxyl radicals (. OH) and the quantification of the calibration curve confirmed the formation of a large amount of hydroxyl radicals (. OH).

< example 2> "validation of hydroxyl radical"

Magnesium oxide (MgO) powder was put into 0.1 mol/l aqueous sodium hydroxide (NaOH), and ethanol and POBN were further added. An experiment was conducted in which a hydroxyl radical and alcohol were reacted to generate a hydroxyethyl radical, which was supplemented with POBN, and the hydroxyethyl radical was measured by ESR (electron spin resonance). A typical peak pattern showing hydroxyl radical formation was detected on the ESR.

< example 3> "verification of reaction by mineral powder coexisting with reaction Source"

The generation of hydroxyl radicals (. OH) from the mineral powder in which the metal oxide and the hydroxide coexist was verified.

As a sample of mineral powder in which metal oxide and hydroxide coexist, double salt (Ca. Mg. (CO)) containing calcium carbonate and magnesium carbonate is used₃)₂) Dolomite (A) and (B)Calcining and processing the ore to obtain a sample. Dolomite ore produces completely different substances to be treated depending on the conditions of treatment (temperature rise rate, air flow conditions (presence or absence of air flow, air flow velocity, and others)).

Therefore, the experiment predicts that the treatment of the calcined product generates calcium carbonate (CaCO) according to the generation mechanism of hydroxyl radical (. OH)₃) Calcium hydroxide (Ca (OH)₂) And magnesium hydroxide (Mg (OH)_1～2) And magnesium oxide (MgO) (for example, raw dolomite is calcined at a temperature of 700 to 1000 ℃ for 10 hours at a temperature rise rate of 5 to 10 ℃/min, cooled to normal temperature, and then contacted with 45 to 55 wt% of water based on the weight of dolomite), and the specific surface area measured by the BET method is adjusted to 40m²Powder of more than one gram. In addition, in this sample, hydroxyl radicals (. OH) were generated to inactivate viruses.

Further, the antiviral material (dolomite-treated product) disclosed in International publication No. WO 2005/013695A 1 has a specific surface area of 18.43m²In g, the specific surface area of the above-mentioned sample of the present application is 40m²More than g.

< example 4> "verification of viral inactivation"

A verification experiment for the inactivation of hydroxyl radical SARS virus (SARS-CoV) was carried out by Plaque reduction neutralization assay (Plaque reduction).

The hydroxyl radical is calcium carbonate (CaCO)₃) Calcium hydroxide (Ca (OH)₂) And magnesium hydroxide (Mg (OH)_1～2) And sampling of example 3 of magnesium oxide (MgO).

The initial Control was an infectious plaque/ml (plaque/ml) of 200 ten thousand, but became 0 after the hydroxyl radical treatment.

< example 5> "verification of viral inactivation"

Experiments were conducted to verify the inactivation of hydroxyl radicals generated from magnesium oxide (MgO) powder and an aqueous solution of sodium hydroxide (NaOH) against sars viruses.

Even when the initial Control had a higher infectious cost than that of example 4, it was 0 after the hydroxyl radical treatment.

< example 6> "verification of viral inactivation"

2 groups of mice consisting of 5 mice were prepared, and 5 mice of 1 group were allowed to inhale highly pathogenic avian influenza virus (H5N1 HPAIV)/Vietnam Kaisha through the nose. Another group of mice were treated with the hydroxyl radical of example 3 and allowed to attract highly pathogenic avian influenza virus (H5N1 HPAIV)/Vietnam corporation.

In the mice of group 1 which had not been subjected to the hydroxyl radical treatment, the amount of virus in the nasal lavage fluid of the mice was 10 days after infection³Plaque/ml. On the other hand, the amount of virus in the group 1 mice subjected to the treatment with hydroxyl radicals was 0.

In addition, the mice of group 1 which had not been subjected to the hydroxyl radical treatment died after the first 10 days, followed by 2 days and 11 days, followed by 1 day and 12 days, and finally 1 day and 13 days.

However, the hydroxyl radical-treated 1 group of mice survived the entire population after 14 days.

< example 7> "verification of viral inactivation"

An inactivation test was conducted for highly pathogenic avian influenza virus (H5N1 HPAIV)/Vietnam corporation of hydroxyl radical under the same conditions as in example 4.

Initial Control infection value is 10⁷Plaques/ml but became 0 after hydroxyl radical treatment.

< example 8> "verification of Virus inactivation"

An inactivation test was conducted for highly pathogenic avian influenza virus (H5N1 HPAIV)/hong Kong corporation of hydroxyl radical under the same conditions as in example 4.

Initial Control infection was 5X 10⁶Plaques/ml but became 0 after hydroxyl radical treatment.

< example 9> "verification of Virus inactivation mechanism"

First, an anti-IgG antibody in which an anti-Spike antibody and colloidal Gold (Gold colloid) were bound was applied to a Spike (Spike) protein present on the surface of a SARS virus (SARS-CoV) particle, and the Spike protein on the surface of the virus particle was observed by an electron microscope. As a result, colloidal gold was distributed around the viral particles, and the distribution was consistent with the distribution of spike proteins of the virus. Then, after SARS virus (SARS-CoV) was exposed to hydroxyl radicals, an anti-IgG antibody in which an anti-spike antibody and colloidal gold were bound was allowed to act in the same manner, and the virus was observed with an electron microscope. As a result, colloidal gold was distributed in the form of a block, a cluster or a polymer, and collapse of the virus structure and inactivation of the virus were observed with the change of spike protein on the surface of the virion.

< example 10> "verification of Virus inactivation mechanism"

The SARS virus which had not been subjected to the treatment with a hydroxyl radical and the SARS virus which had been subjected to the treatment with a hydroxyl radical were subjected to an immunoblotting test (Western blotting) using an anti-spike antibody. When electrophoresis was performed without adding a reducing agent, the disappearance of the Band (Band) of the spike protein was confirmed in the sample subjected to the hydroxyl radical treatment. Electrophoresis was performed with the addition of a reducing agent, and the recovery of the spike protein band was confirmed. This means that the spike protein is oxidized by hydroxyl radicals, resulting in high molecular weight.

< example 11> "verification of Virus inactivation mechanism"

The immunoblotting test was carried out using an anti-spike antibody for SARS virus treated with a hydroxyl radical and for SARS virus treated with a hydroxyl radical scavenger added to the source of the hydroxyl radical. When electrophoresis was performed without adding a reducing agent, the disappearance of the spike protein band was confirmed in the sample treated with the hydroxyl radical. However, recovery of the spike protein band was confirmed in the sample to which the hydroxyl radical scavenger (Sodium salicylate) was added. This means the fact that the high molecular weight of the spike protein consisting of hydroxyl radicals is hindered by the hydroxyl radical scavenger.

< example 12> "verification of Virus inactivation mechanism"

In the sampling adjustment of example 3, the conditions for calcining and treating dolomite ore were changed to adjust the treated powder without magnesium oxide (MgO). That is, the dolomite is calcined at a temperature of 700 ℃ or lower, cooled to normal temperature, and then contacted with 45 to 50 parts by weight of water per 100 parts by weight of dolomite to obtain a dolomite treated product. In the samples of the dolomite-treated product containing no magnesium oxide (MgO), the virus could not be inactivated.

< example 13> "comparison of hydroxyl radical production amount"

The present inventors have obtained a virus agent and an antiviral agent of the above publication provided by trademarks of gargarite motors, which is also filed by the applicant of international publication No. WO2005/013695 a 1.

In addition, calcium hydroxide (Ca (OH)) was prepared as a reagent containing the antiviral agent disclosed in International publication No. WO 2005/013695A 1 as a component₂) (purity: 99.90%, Wako pure chemical industries, Ltd.), calcium carbonate (CaCO)₃) (purity: 99.90%, Wako pure chemical industries, Ltd.), magnesium hydroxide (Mg (OH)₂) (purity: 99.90%, manufactured by Wako pure chemical industries, Ltd.), magnesium oxide (MgO) (purity: 99.90%, manufactured by Wako pure chemical industries, Ltd.).

Subsequently, phosphate buffer (final concentration, 0.1M), HPF reagent (final concentration, 5. mu.M), and calcium hydroxide (Ca (OH))₂) (Standard reagent, final concentration 50mM) was added to the sample (sample No. 1).

Further, a phosphate buffer (final concentration: 0.1M), an HPF reagent (final concentration: 5. mu.M), and calcium carbonate (CaCO) were prepared₃) (sample No.2) having a final concentration of 50mM, manufactured by Wako pure chemical industries, Ltd.).

Separately, phosphate buffer (final concentration: 0.1M), HPF reagent (final concentration: 5. mu.M), and magnesium hydroxide (Mg (OH))₂) (sample No.3) having a final concentration of 50mM, manufactured by Wako pure chemical industries, Ltd.).

A sample (sample No.4) was prepared which had a composition of phosphate buffer (final concentration: 0.1M), HPF reagent (final concentration: 5. mu.M), and magnesium oxide (MgO) (final concentration: 50mM, manufactured by Wako pure chemical industries, Ltd.).

Further, a sample (sample No.5) was prepared which had a composition of a phosphate buffer (final concentration of 0.1M), an HPF reagent (final concentration of 5 μ M), and a virus agent (final concentration of 0.75%) described in international publication No. WO2005/013695 a1, provided by kojic corporation.

As a Control group (Control), a sample (sample No.6) consisting of a phosphate buffer (final concentration: 0.1M) and an HPF reagent (final concentration: 5. mu.M) was prepared.

Subsequently, samples Nos. 1, 2, 3, 4, 5 and 6 described above were incubated at room temperature (incorporation) for 15 minutes, and then fluorescence intensity was measured with a fluorescence spectrophotometer (ARVO MX, PerkinElmer Co., Ltd.) to quantify the amount of hydroxyl radical produced.

The results are shown in Table 1.

In Table 1, a virus agent described in International publication No. WO 2005/013695A 1, available from Mount Rice-Motors, is represented by BRP³(registered trademark).

TABLE 1

Sample (I)

Composition (I)

Amount of free radical generated

No.1	Ca(OH)2(50mM)	6236
			No.2	CaCO3(50mM)	Less than 10
No.3	Mg(OH)2(50mM)	11907
			No.4	MgO(50mM)	3918
No.5	BRP3(registered trademark) (1%)	15582
			No.6	H2O	Less than 10

From Table 1, it was judged that sample No.3 is inferior to sample No.5 only in the amount of radical generation.

< example 14> "comparison of hydroxyl radical production amount under light-shielding conditions"

The solution containing 0.1% of titanium oxide (Anatase type (Anatase), purity 99.9%, Wako pure chemical industries, Ltd.), 1% of silver (particle diameter less than 100nm, purity 99.5%, manufactured by SIGMA corporation), 1% of magnesium hydroxide (purity 95%, manufactured by Wako pure chemical industries, Ltd.), and 1% of dolomite processed product used in example 3 was adjusted as follows.

First, 1g of titanium oxide was added to 9mL of pure water to prepare a 10% titanium oxide suspension. Subsequently, 1mL of the suspension containing 10% titanium oxide was added to 9mL of pure water to prepare a suspension containing 1% titanium oxide.

In addition, silver was added to 1g of pure water 9mL to prepare a silver 10% suspension.

Further, 1g of magnesium hydroxide was added to 9mL of pure water to prepare a 10% suspension of magnesium hydroxide.

Further, a 10% suspension of the dolomite treated product was prepared.

Subsequently, the titanium oxide 1% suspension, the silver 10% suspension, and the magnesium hydroxide 10% suspension were mixed as follows.

HPF reagent (first chemical) 0.1. mu.L

20. mu.L of 0.5M phosphate buffer (pH7.0)

Pure water 69.9 μ L

Suspensions of titanium oxide 1% or

Silver 10% suspension or

10% magnesium hydroxide suspension or

10 mu L of 10% suspension of dolomite treatment

Thus, a sample for measurement containing a suspension of 0.1% titanium oxide, 1% silver, 1% magnesium hydroxide or 1% dolomite-treated matter was obtained.

In the above samples, 2 parts of titanium oxide and silver were prepared, one part was immediately shielded from light after adjustment, and the other part was irradiated with room light (fluorescent lamp) and then shielded from light. The indoor light irradiation time was 30 minutes for titanium oxide and 1 hour for silver. The magnesium hydroxide and dolomite treated matter were kept in a light-shielded state. For these samples, the amount of hydroxyl radicals generated was measured 1 hour after the preparation of the sample. A fluorescence spectrophotometer (manufactured by Varioskan flash, ThermoFisher Scientific) was used for the measurement. The results are shown in Table 2.

TABLE 2

1) When 0.1% of titanium oxide was irradiated with light for 30 minutes, the amount of hydroxyl radicals generated was 100%.

2) The room light was irradiated for 1 hour.

From these results, it can be seen that: according to the method for generating hydroxyl radicals of the present application, titanium oxide and silver are different from each other, and hydroxyl radicals can be generated even in the absence of light irradiation. Namely, it was found that the antiviral effect can be exhibited even under the light-shielding condition.

< example 15> "comparison of hydroxyl radical production amounts by Metal oxide and hydroxide"

The metal oxides and hydroxides or mixtures thereof shown in the following Table 3 were prepared as solutions containing 1 wt% in total.

First, 1g of calcium hydroxide (purity: 96%, Wako pure chemical industries, Ltd.) was added to 9mL of pure water to prepare a 10% suspension of calcium hydroxide.

Further, 1g of magnesium oxide (heavy, purity 99%, Wako pure chemical industries, Ltd.) was added to 9mL of pure water to prepare a 10% magnesium oxide suspension.

In addition, 0.45g of sodium hydroxide (purity: 97%, manufactured by Wako pure chemical industries, Ltd.) was added to 4.05mL of pure water to prepare a 10% suspension of sodium hydroxide.

Further, 0.45g of potassium hydroxide (85% purity, manufactured by SIGMA corporation) was added to 4.05mL of pure water to prepare a 10% suspension of potassium hydroxide.

In addition, 0.5g of copper oxide (particle size: less than 5 μm, purity: 98%, manufactured by SIGMA) was added to 4.5mL of pure water to prepare a 10% copper oxide suspension.

The method used in example 14 was performed on a suspension of 10% magnesium hydroxide and a suspension of 10% dolomite treated material.

Next, the measurement samples were mixed as follows.

HPF reagent (first chemical) 0.1. mu.L

20. mu.L of 0.5M phosphate buffer (pH7.0)

Pure water 69.9 μ L

Each suspension was 10. mu.L

Table 3 shows the concentrations and amounts of the metal oxides and/or hydroxides in the respective samples to be measured.

TABLE 3

These samples were left to stand in a light-shielded state for 1 hour after the preparation of the samples, and then the amount of hydroxyl radical generated was measured, and the results of relative comparison were shown in table 4, in which the amount of hydroxyl radical generated was 100% after irradiating a titanium oxide 0.1% solution with room light for 30 minutes, in the same manner as in example 14.

TABLE 4

< example 16> "duration of hydroxyl radical generation"

Similarly to example 15, a suspension of a metal oxide and/or hydroxide was mixed with various reagents as follows to prepare a sample to be measured.

HPF reagent (first chemical) 0.1. mu.L

20. mu.L of 0.5M phosphate buffer (pH7.0)

Pure water 69.9 μ L

Each suspension was 10. mu.L

Table 5 shows the concentrations and amounts of the metal oxides and/or hydroxides in the respective samples to be measured.

TABLE 5

The reagent was adjusted and then immediately shielded from light, and the amount of hydroxyl radicals generated after 1 hour and after 12 hours were measured, and the amount of hydroxyl radicals generated after irradiating a 0.1% titanium oxide solution with room light for 30 minutes was regarded as 100% and compared with each other as shown in Table 6, similarly to example 14.

TABLE 6

From these results, it can be seen that: according to the method for producing a hydroxyl radical of the present invention, a sufficient amount of hydroxyl radicals to inactivate viruses can be continuously produced from the start of production to 12 hours after 1 hour.

< example 17> "comparison of production amounts of hydroxyl radicals produced by combination of calcium hydroxide, magnesium oxide and magnesium hydroxide"

Magnesium oxide as a metal oxide, and magnesium hydroxide and/or calcium hydroxide as a hydroxide, the total of these metal oxide and hydroxide being as much as 1% by weight.

Specifically, a suspension of a metal oxide and/or hydroxide was mixed with various reagents as described below to prepare a sample to be measured in the same manner as in example 15.

HPF reagent (first chemical) 0.1. mu.L

20. mu.L of 0.5M phosphate buffer (pH7.0)

49.9 muL pure water

Each suspension was 30. mu.L

Table 7 shows the concentrations and amounts of the metal oxides and/or hydroxides in the respective samples to be measured.

TABLE 7

The obtained sample was left in a light-shielded state for 72 hours, and the amount of hydroxyl radical generated was measured, and the results of relative comparison were shown in table 8, with the amount of hydroxyl radical generated by calcium hydroxide alone being 100%.

TABLE 8

Calcium hydroxide (%)

Magnesium oxide (%)

Magnesium hydroxide (%)

Hydroxyl radical formation% of stability in Ca (OH)2

0	0	1	144.14
				0	0.1	0.9	139.94
0	0.2	0.8	153.5
				0	0.3	0.7	161.04
0	0.4	0.6	144.24
				0	0.5	0.5	158.43
0	0.6	0.4	143.28
				0	0.7	0.3	124.64
0	0.8	0.2	149.40
				0	0.9	0.1	127.64
0	1	0	77.84
				0.1	0	0.9	93.39
0.1	0.1	0.8	68.12
				0.1	0.2	0.7	71.61
0.1	0.3	0.6	83.3
				0.1	0.4	0.5	97.37
0.1	0.5	0.4	99.97
				0.1	0.6	0.3	98.33
0.1	0.7	0.2	114.02
				0.1	0.8	0.1	104.33
0.2	0	0.8	106.63
				0.2	0.1	0.7	100.61
0.2	0.2	0.6	127.02
				0.2	0.3	0.5	136.58
0.2	0.4	0.4	135.39

0.2	0.5	0.3	143.35
				0.2	0.6	0.2	149.31
0.2	0.7	0.1	152.09
				0.3	0	0.7	113.13
0.3	0.1	0.6	135.41
				0.3	0.2	0.5	144.06

< example 18> "hydroxyl radical produced by Using magnesium hydroxide"

Next, magnesium hydroxide (Mg (OH)) was pulverized₂) (purity: 99.90% and Wako pure chemical industries, Ltd.) to prepare magnesium hydroxide (Mg (OH) having a primary particle diameter in the range of 1 to 200nm₂) Powder and magnesium hydroxide (Mg (OH) having a primary particle diameter in the range of 200 to 400nm₂)。

Next, a phosphate buffer (final concentration: 0.1M), an HPF reagent (final concentration: 5. mu.M), and magnesium hydroxide (Mg (OH)) having a primary particle size in the range of 1 to 200nm were prepared₂) Sample of composition (sample No. 7).

Further, a phosphate buffer (final concentration: 0.1M), an HPF reagent (final concentration: 5. mu.M), and magnesium hydroxide (Mg (OH)) having a primary particle size in the range of 200 to 400nm were prepared₂) Sample of composition (sample No. 8).

Subsequently, after the above-described samples No.7 and No.8 were incubated at room temperature for 15 minutes, the fluorescence intensity was measured with a fluorescence spectrophotometer (ARVO MX, manufactured by perkin elmer) to quantify the amount of hydroxyl radicals generated.

The results can be determined as follows: in terms of the amount of radicals generated, sample No. 7> sample No. 8> sample No. 3.

Particularly, when the primary particle is in the range of 1nm to 200nm or less, the amount of hydroxyl radicals generated is clearly increased significantly.

From the above results, it can be seen that: magnesium hydroxide (Mg (OH)) in the range of 1 to 200nm as primary particles of the magnesium hydroxide powder₂) The amount of hydroxyl radicals generated is remarkably increased, and magnesium hydroxide (Mg (OH) is prepared so that the primary particles are in the range of 1 to 200nm or less₂) Has definite antiviral effect.

Also, magnesium hydroxide (Mg (OH)₂) And carbon dioxide (CO) including air and others₂) When the gas (2) is contacted, a part of the gas (2) is contacted with carbon dioxide (CO)₂) React to become magnesium carbonate (MgCO)₃)。

Mg(OH)₂+CO₂→MgCO₃+H₂O

For example, calcium carbonate (CaCO) was added to sample No.3 shown in Table 1₃) In this case, the amount of hydroxyl radicals produced decreases to 2811.

In addition, magnesium oxide (MgO) is mixed with air and other carbon dioxide (CO)₂) When the gas (2) is contacted, a part of the gas (2) is contacted with carbon dioxide (CO)₂) React to become magnesium carbonate (MgCO)₃)。

MgO+CO₂→MgCO₃

In addition, calcium hydroxide (Ca (OH)₂) And containing air and other carbon dioxide (CO)₂) When the gas (2) is contacted, a part of the gas (2) is contacted with carbon dioxide (CO)₂) React to become calcium carbonate (CaCO)₃)。

Ca(OH)₂+CO₂→CaCO₃+H₂O

In addition, calcium oxide (CaO) is mixed with a mixture containing air and other carbon dioxide (CO)₂) When the gas (2) is contacted, a part of the gas (2) is contacted with carbon dioxide (CO)₂) React to become calcium carbonate (CaCO)₃)。

CaO+CO₂→CaCO₃

From the above experiments, it can be seen that: the metal oxide powder or magnesium hydroxide powder capable of generating hydroxyl radicals for inactivating the virus of the present invention is stored together with CO₂In a non-contact state (making CO)₂In a closed (Block) state) is preferred.

That is, the antiviral material of the present invention is mixed with CO so as to generate sufficient hydroxyl radicals during use₂Storage in a non-contact state (CO)₂Closed state) is preferable.

The use of the antiviral material with CO as a material relating to the present invention₂In a non-contact state (CO)₂Sealed state), for example, by storing the antiviral material of the present invention in a packaging material, evacuating the packaging material and sealing the packaging material, for example, by storing the antiviral material of the present invention in a packaging material, and then passing the packaging material through a container containing no inert gas such as argon (Ar) or neon (Ne), or nitrogen (N)₂) Gas, oxygen (O)₂) Gas and others not containing CO₂Or does not contain such CO₂The mixed gas of the gases is used to replace the air in the packaging material and then sealed, or after the antiviral material according to the present invention is contained in the packaging material, the packaging material is filled with a non-reactive gas such as argon (Ar) or neon (Ne), or nitrogen (N) without containing the inactive gas such as argon (Ar) or neon (Ne)₂) Gas, oxygen (O)₂) Gas and others not containing CO₂Or does not contain such CO₂And (3) a method for sealing the gas mixture.

The antiviral material according to the present invention is stored in the above-mentioned manner, and the disease-resistant material contained in the packaging material according to the present inventionToxic materials, which are used by opening the packaging material and exposing the antiviral material of the present invention contained in the packaging material to the sun, which contains air and other CO₂The gas of (3) is a constituent of the antiviral material of the present invention during storage in the packaging material, and does not change into a carbonic acid compound the metal oxide powder or the magnesium hydroxide powder which can generate a hydroxyl radical which inactivates viruses, so that a sufficient hydroxyl radical which inactivates viruses can be generated when used.

Industrial applicability

The method for generating the hydroxyl free radical does not adopt conditions harmful to human bodies, and generates the hydroxyl free radical safely, simply and effectively. In addition, the antiviral material of the present invention having such a method for generating hydroxyl radicals can easily and clearly inactivate various viruses by placing the viruses in the vicinity of the hydroxyl radicals and in contact with the hydroxyl radicals, and thus can directly and indirectly provide a useful benefit to the industry or society.

Claims (7)

1. A method for producing a hydroxyl radical, characterized in that,

oxide powder of 1 or more metals selected from the group consisting of alkali metals, alkaline earth metals, metals of groups 4 to 12 of the periodic table, and aluminum, and their mixture

The hydroxyl radical is generated by contacting 1 or more hydroxides selected from alkali metal hydroxides, alkaline earth metal hydroxides, iron hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and ammonium hydroxide.

2. The method of claim 1,

either of the oxide powder and the hydroxide of the above metals is contained in the dolomite treated product obtained by calcining dolomite and then hydrating a part of the dolomite.

3. The method of claim 2,

the dolomite treated product is obtained by calcining raw dolomite at a temperature of 700 ℃ to 1300 ℃ for 1 to 20 hours, cooling the calcined dolomite to normal temperature, and then contacting 35 to 60 parts by weight of water with respect to 100 parts by weight of dolomite.

4. The method of claim 3,

the dolomite-treated matter is calcined at a temperature rise rate of 5 to 10 ℃/min, at a temperature of 700 to 1000 ℃ for 8 to 12 hours, and at this time, air flow is intermittently operated.

5. The method of producing a hydroxyl radical according to claim 1 or 2,

the amount ratio of the metal oxide powder to the metal hydroxide, i.e., the ratio of the metal oxide powder to the metal hydroxide, is in the range of 0.001 to 100.

6. The method of claim 1,

the metal oxide powder is selected from at least 1 of magnesium oxide, calcium oxide, manganese dioxide, iron (II) oxide, iron (III) oxide, copper oxide, zinc oxide or aluminum oxide,

the hydroxide is selected from more than 1 kind of hydroxide selected from sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide and ammonium hydroxide.

7. An antiviral material, comprising:

oxide powder of 1 or more metals selected from the group consisting of alkali metals, alkaline earth metals, metals of groups 4 to 12 of the periodic table, and aluminum, and their mixture

A method in which 1 or more hydroxides selected from alkali metal hydroxides, alkaline earth metal hydroxides, iron hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and ammonium hydroxide are contacted with each other to generate hydroxyl radicals.