JP7496596B2 - Hand sanitizer aerosol products - Google Patents

Description

This invention relates to an aerosol product that contains a disinfectant to kill or inactivate bacteria, mold, viruses, etc. that are attached to the user's hands or fingers.

Conventionally, disinfectants containing ethanol or other active ingredients have been known to kill or inactivate bacteria, mold, viruses, etc. that are attached to the user's hands and fingers.

For example, Patent Document 1 discloses a disinfectant composition that contains ethanol, arginine, and bicarbonate and has a basic liquid property. Furthermore, paragraph 0041 of the specification also describes that the disinfectant composition can be prepared in the form of an aerosol.

JP 2019-194164 A

However, as shown in the examples, the disinfecting composition of Patent Document 1 contains 80% by weight of ethanol, which means it is classified as an "alcohol" in Class 4 (flammable liquids) under the Fire Service Act, and so there are various restrictions on storage and handling methods, such as the need to store and keep it at a temperature lower than the flash point, the need to strictly prohibit open flames, and the need to be careful of static electricity.

Even if the disinfectant composition of Patent Document 1 were in the form of an aerosol, compressed liquefied petroleum gas such as propane or butane is generally used in aerosols, and there is a risk of the petroleum gas igniting when the disinfectant composition is sprayed. This means that there are various restrictions, such as a strict no-open flame policy and the need to be careful of static electricity.

The present invention aims to provide an aerosol product for disinfectant containing ethanol that can kill bacteria and inactivate viruses, particularly enveloped RNA and DNA viruses such as COVID-19, and non-enveloped viruses such as norovirus, poliovirus, and adenovirus, and that is not classified as a hazardous material under the Fire Service Act, will not ignite even if the compressed gas filled in it leaks, and can be stored and handled safely.

[1] That is, the present invention provides an aerosol product for hand sanitizer, comprising: an outer container; a bag body that is housed in the outer container and contains a hand sanitizer containing a lower alcohol having 1 to 3 carbon atoms at a concentration of 25 w/v % or more and less than 60 w/v %, an acid, a salt corresponding to the acid, a quaternary ammonium salt , and water and having a pH of 3.0 to 5.0 at 25° C ; and at least the surface that comes into contact with the hand sanitizer is formed from at least one selected from polyolefins and fluororesins; and a nonflammable compressed gas that fills the space between the outer container and the bag body.

[ 2 ] The aerosol product for hand sanitizer according to [1 ] above, characterized in that the non-flammable compressed gas is at least one selected from the group consisting of nitrogen, carbon dioxide, nitrous oxide, helium, and argon.

According to the present invention, an aerosol product of disinfectant containing ethanol contains hand disinfectant that can kill bacteria and inactivate viruses, particularly enveloped RNA and DNA viruses such as COVID-19, and non-enveloped viruses such as norovirus, poliovirus, and adenovirus. In addition, it does not fall under the category of hazardous materials such as "alcohols" under the Fire Service Act, and will not ignite even if compressed gas leaks, making it safe to store and handle.

FIG. 2 is a central cross-sectional view of the aerosol product for hand disinfection of the present invention.

The following is a detailed explanation of an embodiment of the hand sanitizer aerosol product of the present invention. Note that when the range in the explanation is indicated by "~", it includes the upper and lower limits.

The outer container 1 is the outermost member visible to the user in the hand sanitizer aerosol product of the present invention, and is the member that houses the bag body 2 inside. Since the inside of the outer container 1 is filled with non-flammable compressed gas, it has pressure resistance so that it will not break below a certain pressure, such as a metal such as an aluminum alloy or a synthetic resin with a certain thickness. In this embodiment, the outer container 1 is a hollow cylinder with a bottom and an opening at the top. The opening at the top is sealed by a mounting cup 3, as shown in Figure 1.

The bag body 2 is a flexible member that is housed in the outer container 1 and contains the hand sanitizer L described below. Since the bag body 2 is housed in the outer container 1, the hand sanitizer L contained in the bag body 2 does not come into direct contact with the outer container 1, so corrosion of the outer container 1 can be prevented. In addition, since the space between the outer container 1 and the bag body 2 is constantly pressed by the non-flammable compressed gas filled therein, the hand sanitizer L contained in the bag body 2 can be used up to the very end. Even if the aerosol product is turned upside down from the state shown in FIG. 1 and sprayed with the actuator 7 facing down, the hand sanitizer L is smoothly discharged. In addition, since the hand disinfectant L contained in the bag body 2 is acidic and stored at a pressure higher than normal pressure, there is a concern that the bag body 2 may deteriorate or break. Therefore, the bag body 2 is preferably made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, or fluororesins such as polytetrafluoroethylene, at least on the surface that contacts the hand disinfectant L, so as not to be hydrolyzed. Among polyethylenes, high-density polyethylene with a specific gravity of 0.92 to 0.96 and a deflection temperature under load of 130°C or less as specified in JIS K7191-3 is more preferable. Of course, the above polyolefins and fluororesins may be formed as copolymers. And, in order to prevent non-flammable compressed gas from flowing into the bag body 2 or to prevent the contained hand disinfectant L from leaking from the bag body 2 into the space S, other synthetic resins, metals such as aluminum, and metal oxides such as silicon dioxide and aluminum trioxide may be laminated on the outside of the above-mentioned polyolefins such as polyethylene and polypropylene or fluororesins to form a multi-layer film of two or more layers.

Next, we will explain the hand sanitizer L contained in the bag body 2.

In the present invention, the lower alcohol having 1 to 3 carbon atoms is an alcohol having 1 to 3 carbon atoms in the molecule, such as methanol, ethanol, and isopropyl alcohol. By using such a lower alcohol, it is possible to destroy the viral envelope or the bacterial cell membrane, as well as to kill viruses and bacteria by coagulating proteins such as enzymes, thereby preventing harm to the human body, such as illnesses caused by such viruses and bacteria.

The content of the lower alcohol having 1 to 3 carbon atoms in the hand sanitizer L is preferably 25% or more and less than 60% w/v, and more preferably 40 to 55% w/v. If the content of the lower alcohol having 1 to 3 carbon atoms is within this range, it will not be classified as a hazardous material under the Fire Service Act, and when combined with an acid, it will be sufficiently effective against viruses. The concentration is expressed as a percentage of grams (g) per 100 mL.

The acid in the present invention is a component that, when present together with ethanol, quaternary ammonium salts, etc., destroys the capsid that protects nucleic acid, thereby promoting the penetration of ethanol, quaternary ammonium salts, etc. into cells and enhancing the effectiveness of inactivating a wide range of RNA and DNA viruses, regardless of whether they are enveloped or not.

Specific examples of acids that are preferred include organic acids such as citric acid, malic acid, acetic acid, boric acid, lactic acid, formic acid, oxalic acid, and propionic acid, and inorganic acids such as phosphoric acid and sulfuric acid. These acids can be used alone or in combination of two or more.

The acid content of the hand disinfectant L is preferably 0.1 w/v% to 3.0 w/v%, and more preferably 0.2 w/v% to 2.5 w/v%. When the acid content is within this range, it can be effective in inactivating viruses and killing bacteria.

The acid salts contained in the hand disinfectant L are salts corresponding to the organic acids and inorganic acids described above. Specifically, for example, when citric acid is used as the acid, the salts are sodium citrate, potassium citrate, calcium citrate, etc., when malic acid is used, the salts are sodium malate, potassium malate, calcium malate, etc., and when phosphoric acid is used, the salts are sodium phosphate, potassium phosphate, calcium phosphate, etc. In this way, by including a salt corresponding to the acid, the hand disinfectant L has a pH in a predetermined range, and even if the lower alcohol having 1 to 3 carbon atoms or water in the hand disinfectant L volatilizes slightly after long-term use, large fluctuations in pH are suppressed, so that the user can use the hand disinfectant L in a predetermined range of liquidity.

The content of the acid salt in the hand sanitizer L is preferably 0.1 w/v% to 3.0 w/v%, and more preferably 0.2 w/v% to 2.5 w/v%. When the content of the acid salt is within this range, the pH of the hand sanitizer L can be maintained within a specified range.

The quaternary ammonium salt that can be incorporated into the hand disinfectant L is generally a compound consisting of a quaternary ammonium ion and a counter anion, as represented by the chemical formula N ⁺ RX ^- (R: alkyl group, X ^- : chloride ion, etc.). Specific examples of the quaternary ammonium salt include benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, didecyldimethylammonium chloride, hexadodecyltrimethylammonium bromide, and tetraammonium bromide. These quaternary ammonium salts can be used alone, or in combination of two or more. In this way, the inclusion of a quaternary ammonium salt makes it easier to destroy the envelope of enveloped RNA viruses such as coronaviruses (especially COVID-19), influenza viruses, Ebola viruses, and human immunodeficiency viruses, and enveloped DNA viruses such as herpes viruses and smallpox viruses, thereby making it possible to more easily inactivate them.

The content of the quaternary ammonium salt in the hand disinfectant L is preferably 0.01 w/v% to 2.0 w/v%, and more preferably 0.03 w/v% to 1.0 w/v%. When the content of the quaternary ammonium salt is within this range, enveloped RNA and DNA viruses are more easily inactivated.

The water of the present invention is a solvent for making a homogeneous solution of a lower alcohol having 1 to 3 carbon atoms, an acid, a salt of the acid, and a quaternary ammonium salt. Specifically, the water is preferably water conforming to the Japanese Pharmacopoeia standard, and examples of the water include ordinary water such as tap water and well water, purified water obtained by treating ordinary water by distillation, ion exchange treatment using an ion exchange membrane, ultrafiltration treatment using an ultrafiltration membrane, or a combination thereof, and sterilized purified water obtained by sterilizing purified water by heating or the like. The blending ratio of water is the remainder excluding the lower alcohol having 1 to 3 carbon atoms, an acid, a salt of the acid, and a quaternary ammonium salt used in the present invention, and is preferably 30 w/v% to 75 w/v%, and more preferably 32 w/v% to 65 w/v%.

In addition to the above-mentioned ingredients, hand disinfectant L may contain, as necessary, polyhydric alcohols such as glycerin, propylene glycol, butylene glycol, and sorbitol; moisturizing agents such as polysaccharides or salts thereof such as hyaluronic acid and sodium hyaluronate; thickeners such as hydroxyethyl methylcellulose and hydroxypropyl methylcellulose; fragrances; and colorants. For example, adding a moisturizing agent can further prevent rough skin.

Hand disinfectant L containing the above-mentioned components has a pH, which indicates the degree of acidity or alkalinity, of preferably 3.0 to 5.0 at 25°C, and more preferably 3.0 to 4.0. When the pH of hand disinfectant L is in this range, it is effective in killing bacteria and inactivating various viruses.

The non-flammable compressed gas of the present invention is a gas that is filled in the space S between the outer container 1 and the bag body 2, and is in a state of pressure higher than atmospheric pressure, and does not ignite or burn when exposed to fire at normal temperatures of about 10 to 30°C, which are normally used. The non-flammable compressed gas presses against the bag body 2, and the hand sanitizer L contained in the bag body 2 can be discharged to the outside. Specifically, the non-flammable compressed gas is preferably at least one selected from nitrogen, carbon dioxide, nitrous oxide, helium, and argon. If the non-flammable compressed gas is one of these gases, the aerosol product for hand sanitizer of the present invention can be safely stored and used since it does not ignite, etc.

The pressure of the non-flammable compressed gas filling the space S between the outer container 1 and the bag body 2 is preferably 0.10 MPa or more and less than 1.0 MPa at 35°C, and preferably 0.2 MPa or more and 0.5 MPa or less. When the pressure of the non-flammable compressed gas is within this range, the hand sanitizer L contained in the bag body 2 is smoothly discharged.

As shown in FIG. 1, the aerosol product is composed of an outer container 1, a bag 2, a mounting cup 3, a stem 4, an elastic spring 5, a tube 6, an actuator 7, etc. The bag 2 contained in the outer container 1 is constantly pressed by the non-flammable compressed gas that fills the space S between the outer container 1 and the bag 2. Therefore, when the actuator 7 is pressed down, the stem 4 is also pressed down against the biasing force of the elastic spring 5, and the stem hole 41 communicates with the inside of the bag 2, and the hand sanitizer L that is pressed by the non-flammable compressed gas through the bag 2 is discharged to the outside from the nozzle 71 of the actuator 7 through the tube 6 and the stem 4.

The hand disinfectant L of the present invention will be specifically described below. Note that the present invention is not limited to the following examples.

Example 1
At room temperature of 20°C, 50.7 g of ethanol as a lower alcohol having 1 to 3 carbon atoms, 0.4 g of phosphoric acid as an acid, 0.35 g of trisodium phosphate as a salt corresponding to the acid, 0.1 g of concentrated benzalkonium chloride solution 50 as a quaternary ammonium salt (0.05 g as benzalkonium chloride), 0.2 g of glycerin as a moisturizer, and the remainder, purified water, were added to a 200 ml Griffin beaker and stirred to obtain a total of 100 ml of hand disinfectant.

<Examples 2 to 4>
In Examples 2 to 4, the types and amounts of lower alcohols having 1 to 3 carbon atoms, acids, salts corresponding to the acids, and quaternary ammonium salts were formulated as shown in Table 1, and a total of 100 ml of hand disinfectant was obtained in the same manner as in Example 1.

<Comparative Example 1>
In Comparative Example 1, the types and amounts of a lower alcohol having 1 to 3 carbon atoms, an acid, a salt corresponding to the acid, and a quaternary ammonium salt were formulated as shown in Table 1, and a total of 100 ml of hand disinfectant was obtained in the same manner as in Example 1.

<Reference Example 1>
In addition, in order to determine whether the hand sanitizers of Examples 1 to 4 are hazardous materials under the Fire Service Act, a total of 100 g of an aqueous solution consisting only of ethanol and water as a standard and having an ethanol concentration of 60 w/w% was prepared in the same manner as in Example 1.

The hand sanitizer obtained in this manner was evaluated using the following methods:

[pH]
The pH was measured as a value corrected to 25° C. using a pH meter (manufactured by HORIBA, Ltd., product name F-52) calibrated with a pH 7 (neutral phosphate) standard solution (pH 6.86 at 25° C.) as the zero point and a pH 4 (phthalate) standard solution (pH 4.01 at 25° C.) or a pH 9 (borate) standard solution (pH 9.18 at 25° C.).

[Flash point and fire point]
In order for an alcohol-containing article to be classified as a "non-hazardous material" rather than an "alcoholic beverage" under the Fire Service Act, the alcohol-containing article must ultimately satisfy all three requirements: (1) the amount of flammable liquid is less than 60 w/v%, (2) the flash point is higher than the flash point of a 60 w/w% ethanol aqueous solution, and (3) the combustion point is higher than the combustion point of a 60 w/w% ethanol aqueous solution. For this reason, the flash point was measured by the tag-closed method in accordance with JIS K2265-1. Then, the combustion point was measured by the Cleveland open method in accordance with JIS K2265-4. The flash points of all of the examples 1 to 4 were higher than the flash point of a 60 w/w% ethanol aqueous solution. Similarly, the combustion points of all of the examples 1 to 4 were higher than the combustion point of a 60 w/w% ethanol aqueous solution. The results are shown in Table 1. In Comparative Example 1, the flash point and combustion point were not measured because the virus-inhibiting effect was not obtained.

[Virus suppression effect]
The virus suppression effect was evaluated by the following method. That is, first, the hand disinfectant and the virus solution were directly mixed, and after the reaction was stopped for a predetermined time, the cells were infected and cultured, and the virus infectivity was measured by the TCID ₅₀ method. The efficacy was measured using the cytopathic effect of the cells as an index, and the virus infectivity (log TCID ₅₀ /mL) was calculated from the 50% tissue culture infectivity (TCID ₅₀ ). The difference between the virus infectivity before the action and the virus infectivity after the action was calculated and used as the value of the decrease in the virus infectivity. The decrease in the virus infectivity thus obtained was evaluated as 4.0 or more, as ⊚, the decrease in the virus infectivity of 2.0 or more but less than 4.0 was evaluated as ◯, and the decrease in the virus infectivity of less than 2.0 was evaluated as x. Of these, ⊚ and ◯ were judged to be good, and x was judged to be bad. In addition, in this test, two types of virus solutions, influenza virus as an enveloped virus and feline calicivirus as a non-enveloped virus, were used, respectively. The time for which the hand disinfectant and the virus liquid were allowed to act was 180 seconds for Examples 1 to 3, and 30 seconds for Example 4.

The compositions and test results of Examples 1 to 4 and Comparative Example 1 are summarized in Table 1.

As shown in Table 1, the hand disinfectants of Examples 1 to 4 each contain a prescribed amount of a lower alcohol having 1 to 3 carbon atoms, an acid, a salt of the acid, and water, and have a pH of 3.2 to 3.5, which can inactivate both enveloped and non-enveloped viruses and significantly inhibit their proliferation. In addition, the flash point and combustion point are higher than those of a 60 w/w% aqueous ethanol solution, so they are non-hazardous materials under the Fire Service Act. In addition, although not specified in Table 1, nitrogen is used as the compressed gas in the aerosol product, so even if nitrogen leaks from the aerosol product, it will not ignite or cause a fire. From these facts, it was found that the aerosol product for hand disinfection of the present invention can be safely stored and handled.

Reference Signs List 1: Outer container 2: Bag body 3: Mounting cup 4: Stem 41: Stem hole 5: Elastic spring 6: Tube 7: Actuator 71: Spray nozzle S: Space L: Hand sanitizer

Claims (2)

An outer container;
A bag body is housed in the outer container, contains a hand disinfectant containing 25 w/v% or more and less than 60 w/v% of a lower alcohol having 1 to 3 carbon atoms, an acid, a salt corresponding to the acid, a quaternary ammonium salt, and water, and has a pH of 3.0 to 5.0 at 25°C, and at least the surface that comes into contact with the hand disinfectant is formed from at least one selected from polyolefins and fluororesins ;
An aerosol product for hand sanitizer, comprising a non-flammable compressed gas filled in the space between the outer container and the bag. The aerosol product for hand sanitizer according to claim 1, characterized in that the non-flammable compressed gas is at least one selected from the group consisting of nitrogen, carbon dioxide, nitrous oxide, helium, and argon .

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