JP2022103579A - Antiviral agent for clothes - Google Patents

Abstract

To provide an antiviral agent for clothes that allows clothes to have antiviral activity for a long time by simple treatment of directly spraying the clothes with an alcohol solution of benzalkonium chloride or benzethonium chloride and an acid.SOLUTION: An antiviral agent for clothes contains at least one of benzalkonium chloride and benzethonium chloride, an acid or a salt thereof, ethanol, and water.SELECTED DRAWING: None

Description

The present invention relates to an antiviral agent for clothing that can impart antiviral activity to clothing by a simple treatment at home, workplace, or the like.

Conventionally, as an antibacterial / antiviral agent that imparts antibacterial activity and antiviral activity to textile products such as clothing, an antibacterial composition for textile products containing a cationic antibacterial compound composed of cetylpyridinium chloride and a cationic resin is obtained. Exists (Patent Document 1).

The antibacterial composition for textile products has high antibacterial activity against textile products and can be processed with washing resistance.

Further, such antibacterial / antiviral agents include quaternary ammonium salts such as benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, and cetrimid, and / or bactericidal and disinfecting components composed of biguanide compounds, amino acids, and nonionic compounds. There is a bactericidal disinfectant containing a surfactant (Patent Document 2).

When the base cloth such as cotton wool, gauze, or non-woven fabric is impregnated with an appropriate amount and used, the sterilizing and disinfecting agent prevents the sterilizing and disinfecting component from being adsorbed on the base cloth and effectively exerts the sterilizing and disinfecting effect. It is said that it can be done.

Further, as such an antibacterial / antiviral agent, a long-lasting surface containing a carbohydrate gum, a wetting agent, and an antibacterial agent such as cetrimid, benzalkonium chloride, cetylpyridinium chloride, cetylpyridinium chloride, and myristalkonium chloride. There is an antibacterial agent (Patent Document 3).

The long-lasting surface antibacterial agent is said to have an effect of capturing, killing or neutralizing microorganisms for a duration of at least about 1 hour, and has antiviral activity against influenza virus and the like.

Furthermore, such antibacterial / antiviral agents include antiviral agents containing at least one of a polyalkylene biguanide compound and a salt thereof, and antiviral processing agents containing benzalkonium chloride. Exists (Patent Document 4).

The antiviral fiber processing agent is excellent in safety and does not cause skin damage or the like. In addition, because it contains a specific antiviral agent and benzalkonium chloride, it is said that it can exhibit excellent antiviral properties synergistically.

Japanese Patent No. 4262362 Japanese Patent No. 5469829 Special Table 2015-514758 Japanese Unexamined Patent Publication No. 2019-210563

The antibacterial composition for textile products described in Patent Document 1 is obtained by selecting only cetylpyridinium chloride as an antibacterial composition among quaternary ammonium salts, and is said to have high antibacterial activity against textile products. , Antiviral activity is not mentioned, and it is unknown whether it has antiviral activity.

Further, in the bactericidal disinfectant described in Patent Document 2, the quaternary ammonium salt as a bactericidal disinfectant component is benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, cetrimid and the like, and is not particularly limited. , There is no mention of which one should be selected for better bactericidal effect. In addition, since this bactericidal disinfectant is used immediately after impregnating a base cloth such as cotton wool, gauze, or non-woven fabric with an appropriate amount, the sustainability of the bactericidal effect is not mentioned, and the bactericidal effect is long-term. The sustainability of is unknown. Furthermore, this disinfectant does not mention antiviral activity, and it is unclear whether it has antiviral activity.

Further, in the long-lasting surface antibacterial agent described in Patent Document 3, the quaternary ammonium salt as the antibacterial agent is the first of cetrimid, benzalkonium chloride, cetalconium chloride, cetylpyridinium chloride, and myristalconium chloride. Although quaternary ammonium salts are mentioned, they are not particularly limited, and it is not mentioned which one is excellent in antibacterial / antiviral activity. Furthermore, it is stated that this long-lasting surface antibacterial agent can be applied to various surfaces in various places such as homes, schools, churches, restaurants, day care, workplaces, cars, and hospitals. It just happens to have clothing inside, and it can never be said that it is suitable for clothing.

Furthermore, the antiviral fiber processing agent described in Patent Document 4 is an excellent antiviral agent having a synergistic effect by using benzalkonium chloride in combination with a special antiviral agent called a polyalkylene biguanide compound. It is said that it can exhibit its properties, and it is considered that sufficient antiviral activity cannot be obtained only with benzalkonium chloride.

However, in the present invention, it has been found that among the quaternary ammonium salts, benzalkonium chloride or an alcohol solution of benzethonium chloride and an acid exhibits sufficient antiviral activity.

Therefore, the present invention is an antivirus for clothing that can impart antiviral activity to clothing for a long time by a simple treatment of directly spraying benzalkonium chloride or an alcohol solution of benzethonium chloride and an acid on clothing. It provides an agent.

The antiviral agent for clothing of the present invention shall contain at least one of benzalkonium chloride and benzethonium chloride, an acid or a salt thereof, ethanol, and water.

In the antiviral agent for clothing of the present invention, the content ratio of at least one of the benzalkonium chloride and benzethonium chloride is 0.01 to 2.0 W / V%, and the content ratio of the acid or a salt thereof is 0.1 to 3. It is assumed that 0.0 W / V%, the content ratio of the ethanol is 10 to 65 W / V%, and the rest is water.

The antiviral agent for clothing of the present invention is assumed to be contained in a spray container.

The anti-virus agent for clothing of the present invention exerts more anti-virus activity by using at least one of benzalkonium chloride and benzethonium chloride in combination with an acid or ethanol.

Further, the antiviral agent for clothing of the present invention can impart antiviral activity to clothing for a long time by a simple treatment of directly spraying the clothing by storing it in a spray container.

Hereinafter, the content ratio and the like of each component of the antiviral agent for clothing of the present invention will be described in detail.

Benzalkonium chloride and benzethonium chloride contained in the antiviral agent for clothing of the present invention can further exhibit anti-virus activity when used in combination with an acid or ethanol described later.

The benzalconium chloride and benzethonium chloride may be used alone or in combination, and are RNA viruses having an envelope such as coronavirus (particularly SARS-CoV-2), influenza virus, Ebola virus, and human immunodeficiency virus. The envelope is easily destroyed and can be inactivated against DNA viruses having an envelope such as herpes virus, natural pox virus, and the like.

The content ratio of benzalkonium chloride and benzethonium chloride is 0.01 to 2.0 W / V%, preferably 0.03 to 1.0 W / V%, both when used alone and when used in combination. More preferably, it can be 0.04 to 0.06 W / V%. If this content ratio is less than 0.01, anti-wisle activity cannot be expected, and if it is more than 2.0 W / V%, anti-wisle activity can be further enhanced, but when it comes into contact with the skin or when inhaled, it can be expected. Not preferable in terms of safety.

The acid contained in the anti-virus agent for clothing of the present invention exerts more anti-virus activity when used in combination with the above-mentioned benzalkonium chloride, benzethonium chloride, and ethanol described later.

The acid can enhance the efficacy such as inactivation against a wide range of RNA viruses and DNA viruses regardless of the presence or absence of an envelope.

As the acid, 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 are preferable. These acids can be used alone or in combination.

The content ratio of the acid is 0.1 to 3.0 W / V%, preferably 0.2 to 2.5 W / V%, and more preferably 0.4, whether used alone or in combination. It can be set to ~ 1.0 W / V%. When the content ratio of this acid is in this range, the virus can be inactivated.

The acid salt contained in the antiviral agent for clothing of the present invention is a salt corresponding to the above-mentioned organic acid or inorganic acid. For example, when citrate is used as an acid, it is a salt such as sodium citrate, potassium citrate, calcium citrate, and when apple acid is used, sodium apple acid, potassium malate, calcium malate, etc. are used. It is a salt, and when phosphoric acid is used, it is a salt such as sodium phosphate, potassium phosphate, calcium phosphate and the like. As described above, the inclusion of the salt corresponding to the acid keeps the pH of the antiviral agent for clothing of the present invention within a predetermined range, and even if the ethanol or water described later volatilizes a little due to long-term storage or the like, the pH is adjusted. Since the large fluctuation of the pH is suppressed, the user can use the liquid in a predetermined range.

The content ratio of the salt of the acid is 0.1 to 3.0 w / V%, preferably 0.2 to 2.5 W / V%, and more preferably 0.4 to 1.0 W / V%. be able to. When the content ratio of the salt of this acid is in the above range, the pH of the antiviral agent for clothing of the present invention can be kept in a predetermined range.

Ethanol contained in the antiviral agent for clothing of the present invention exerts more anti-virus activity when used in combination with the above-mentioned benzalkonium chloride, benzethonium chloride, and the above-mentioned acid.

The ethanol can kill the virus by destroying the envelope of the virus and coagulating proteins such as enzymes. Furthermore, this ethanol improves the permeability of benzalkonium chloride, benzethonium chloride, acid or a salt thereof into clothing, and enhances the anti-wisle activity of these components even inside the fibers of clothing.

The content ratio of the ethanol is 10 to 65 W / V%, preferably 25 to 63 W / V%, and more preferably 50 to 60 W / V%. The content ratio of this ethanol is preferably high, but if it exceeds 60 W / V%, it has an adverse effect such as hardening of the texture of the fibers of clothing, which is not preferable.

The water contained in the antiviral agent for clothing of the present invention is a solvent for making the above-mentioned benzalkonium chloride, benzethonium chloride, acid or a salt thereof, and ethanol into a uniform solution. As this water, water of the Japanese Pharmacy standard is preferable, for example, tap water, normal water such as well water, and any of distillation, ion exchange treatment with an ion exchange membrane, and ultrafiltration treatment with an extrafiltration membrane. , Or purified water treated with normal water by a combination thereof, and sterilized purified water obtained by sterilizing purified water by heating or the like are preferable.

The content ratio of the water is the residue excluding the benzalkonium chloride, benzethonium chloride, acid or a salt thereof, and ethanol, which is 30 to 75 w / V%, preferably 32 to 65 W / V%, and more preferably 40. It can be set to ~ 50 W / V%.

In addition to the above-mentioned components, the antiviral agent for clothing of the present invention is, if necessary, a polyhydric alcohol such as glycerin, propylene glycol, butylene glycol or sorbitol, a polysaccharide such as hyaluronic acid or sodium hyaluronate, or a salt thereof. It is also possible to add a moisturizing agent, a thickener such as hydroxyethylmethylcellulose and hydroxypropylmethylcellulose, a fragrance and the like.

The antiviral agent for clothing of the present invention containing each of these components is used as it is by containing it in a spray container and spraying it directly onto clothing. Further, when the surface area of clothing is small, the clothing may be used by directly immersing the clothing in the antiviral agent for clothing of the present invention.

When the antiviral agent for clothing of the present invention is directly sprayed on clothing, it may be naturally dried, so that the clothing can be worn as it is. Further, when the clothes are directly immersed in the antiviral agent for clothes of the present invention, it is preferable to dry the clothes indoors or in the sun before wearing them.

The spray container may be a pump-type or trigger-type spray container, or an air-zole spray container.

The antiviral agent for clothing of the present invention preferably has an average particle size of 15 to 400 μm, more preferably 20 to 260 μm, at 20 cm from the spray port of the spray container. If the average particle size is in this range, it will exert antiviral activity even if ethanol volatilizes on the way when it adheres to clothing, and since it does not contain excess ethanol, it will cause fire that is close to us. Even if it catches fire, it can be prevented from spreading from the source of the fire. The average particle size is a value measured by a laser diffraction / scattering method.

When the spray container is an air spray container, it is preferable that the compressed gas is at least one nonflammable gas selected from nitrogen, carbon dioxide, nitrous oxide, helium, and argon. These gases can be used safely because they do not ignite even if there is fire near the user when sprayed.

The clothing includes suits, coats, jackets, jumpers, slacks, skirts, shirts, shirts, blouses, sweaters, gowns, pajamas, aprons, work clothes, masks, hats, ties, scarves, mufflers, gloves, socks, underwear, etc. However, it is not limited to these.

The materials for the clothing include natural fibers such as cotton, linen, silk and wool, synthetic fibers such as polyester and nylon, semi-synthetic fibers such as acetate, recycled fibers such as rayon, polynosic and cupra, and blended products of these various fibers. However, there is no particular limitation.

Next, examples of the antiviral agent for clothing of the present invention will be described in detail.

[Preparation method of Example sample and Comparative Example sample]
(Examples 1 to 3)
At room temperature of 20 ° C., an appropriate amount of purified water was placed in each Griffin beaker having a capacity of 200 ml, and 0.1 g of concentrated benzalconium chloride solution 50 (0.05 g as benzalconium chloride) and acid were added to each. Add 0.5 g of phosphoric acid, 0.25 g of trisodium phosphate as the salt corresponding to the acid, 10 g, 20 g, and 60 g of ethanol, add purified water to each, and stir the whole to 100 ml. An antiviral agent for clothing having the content ratio shown in 1 was prepared.

(Examples 4 to 6)
At room temperature of 20 ° C., an appropriate amount of purified water was placed in each Griffin beaker having a capacity of 200 ml, 0.05 g of benzethonium chloride, 0.5 g of phosphoric acid as an acid, and phosphoric acid as a salt corresponding to the acid. 0.25 g of trisodium and 10 g, 20 g, and 60 g of ethanol were added, purified water was further added to each, and the whole was stirred to make 100 ml to prepare an antiviral agent for clothing having the content ratio shown in Table 1.

(Comparative Example 1)
At room temperature of 20 ° C., put an appropriate amount of purified water in a Griffin beaker having a capacity of 200 ml, add 0.1 g of concentrated benzalconium chloride solution 50 (0.05 g as benzalconium chloride), and add phosphoric acid as an acid. 0.5 g and 0.25 g of trisodium phosphate as a salt corresponding to the acid were added, purified water was further added, and the whole was stirred to make 100 ml to prepare an antiviral agent for clothing having the content ratio shown in Table 2.

(Comparative Example 2)
At room temperature of 20 ° C., put an appropriate amount of purified water in a Griffin beaker having a capacity of 200 ml, add 0.1 g of concentrated benzalconium chloride solution 50 (0.05 g as benzalconium chloride), and add phosphoric acid as an acid. 0.5 g, 0.25 g of trisodium phosphate as a salt corresponding to the acid, 70 g of ethanol were added, purified water was further added, and the whole was stirred to make 100 ml, and the antiviral agent for clothing having the content ratio shown in Table 2 was added. Was prepared.

(Comparative Example 3)
At room temperature of 20 ° C., a suitable amount of purified water was placed in a Griffin beaker having a capacity of 200 ml, 0.05 g of benzethonium chloride, 0.5 g of phosphoric acid as an acid, and 0 of trisodium phosphate as a salt corresponding to the acid. .25 g was added, purified water was further added, and the whole was stirred to make 100 ml to prepare an antiviral agent for clothing having the content ratio shown in Table 2.

(Comparative Example 4)
At room temperature of 20 ° C., put an appropriate amount of purified water in a Griffin beaker having a capacity of 200 ml, add 0.05 g of benzethonium chloride, 0.5 g of phosphoric acid as an acid, and disodium phosphate as a salt corresponding to the acid. 0.25 g and 70 g of ethanol were added, purified water was further added, and the whole was stirred to make 100 ml to prepare an antiviral agent for clothing having the content ratio shown in Table 2.

(Comparative Example 5)
At room temperature of 20 ° C., put an appropriate amount of purified water in a Griffin beaker having a capacity of 200 ml, add 0.05 g of cetylpyridinium chloride, 0.5 g of phosphoric acid as an acid, and trisodium phosphate as a salt corresponding to the acid. 0.25 g was added, purified water was further added, and the whole was stirred to make 100 ml to prepare an antiviral agent for clothing having the content ratio shown in Table 2.

(Comparative Examples 6-9)
At room temperature of 20 ° C., an appropriate amount of purified water was placed in each Griffin beaker having a capacity of 200 ml, 0.05 g of cetylpyridinium chloride, 0.5 g of phosphoric acid as an acid, and phosphorus as a salt corresponding to the acid. 0.25 g of trisodium acid and 10 g, 20 g, 60 g, and 70 g of ethanol were added, purified water was added to each, and the whole was stirred to make 100 ml to prepare an antiviral agent for clothing having the content ratio shown in Table 2. ..

[Virus test method]
Examples Samples 1 to 6 and Comparative Example Samples 1 to 9 are each housed in a spray container (manufactured by Yoshino Kogyosho Co., Ltd., product name: TA trigger) and tested on clothing (antivirus test of JISL1922 textile products). It was carried out according to.

Two layers of cotton cloth (grain: 200 g / m ² ), polyurethane cloth (grain: 200 g / m ² ), and acetate cloth (grain: 200 g / m ² ) infused with feline calicivirus solution were layered, and the sample and comparative example were described above. The samples were sprayed on each, and after standing in the incubator for 12 hours, these cloths were washed out, and the virus infectivity titers were measured by the TCID50 method and compared with the virus infectivity titers in the untreated plot.

As for the evaluation criteria, a virus infectious titer (logTCID50 / mL) with a decrease of 2 or more as compared with the untreated group was judged to be good (○), and a virus infectious titer (logTCID50 / mL) as compared with the untreated group was judged as good. ) Was judged to be not good (x) if it had a decrease of less than 2. The results are shown in Tables 1 and 2.

[Cloth test method]
Examples Samples 1 to 6 and Comparative Example Samples 1 to 9 were each housed in a spray container (manufactured by Yoshino Kogyosho Co., Ltd., product name: TA trigger), and the effect on the cloth was investigated by the following method.

Two layers of cotton cloth (weight: 200 g / m ² ), polyurethane cloth (weight: 200 g / m ² ), and acetate cloth (weight: 200 g / m ² ) were layered, and the Example sample and Comparative Example sample were sprayed on each. After standing in the incubator for 1 hour, these cloths were washed out and the texture was confirmed by sensuality.

As for the evaluation criteria, those with no change in texture compared to the untreated plot were marked with ◯, and those with a change in texture compared with the untreated plot were marked with x. The results are shown in Tables 1 and 2.

The analysis of the amount of the active ingredient attached to the cloth was measured by absorption at 210 nm using a UV detector by liquid chromatography (LC-2010) manufactured by Shimadzu Corporation. In addition, benzalkonium chloride is quantified based on the internal standard method using benzethonium chloride as an internal standard, and benzethonium chloride is quantified based on a calibration curve using dibutyl phthalate as an internal standard. The quantification of pyridinium was performed based on the internal standard method using benzethonium chloride as an internal standard substance.

[Evaluation of Examples and Comparative Examples]
As shown in Examples 1 to 3 shown in Table 1, ethanol is 10 to 60 W / V%, benzalconium chloride is 0.05 W / V%, phosphoric acid is 0.5 W / V%, and phosphoric acid tri is. The anti-virus agent for clothing, which contained 0.25 W / V% of sodium and the content of the remaining purified water, showed effective anti-virus activity without any effect on the cloth.

Further, as in Examples 4 to 6 shown in Table 1, ethanol is 10 to 60 W / V%, benzethonium chloride is 0.05 W / V%, phosphoric acid is 0.5 W / V%, and phosphoric acid tri is. The anti-virus agent for clothing, which contained 0.25 W / V% sodium and the content of the remaining purified water, showed effective anti-virus activity without any effect on the cloth.

However, as shown in Comparative Examples 1, 3 and 5 shown in Table 2, ethanol was 0 W / V%, benzalkonium chloride, benzethonium chloride and cetylpyridinium chloride were 0.05 W / V%, and phosphoric acid. The anti-virus agent for clothing, which has 0.5 W / V%, 0.25 W / V% trisodium phosphate, and the content ratio of the remaining purified water, had no effect on the texture of the cloth, but was an effective anti-virus. Showed no activity.

Further, as shown in Comparative Examples 2 and 4 shown in Table 2, ethanol is 70 W / V%, benzalkonium chloride or benzethonium chloride is 0.05 W / V%, and phosphoric acid is 0.5 W / V. %, Trisodium Phosphate 0.25 W / V%, and the content of the remaining purified water, the antiviral agent for clothing showed effective antiviral activity, but had an effect on the texture to the cloth.

Further, as shown in Comparative Examples 6 to 8 shown in Table 2, ethanol is 10 to 60 W / V%, cetylpyridinium chloride is 0.05 W / V%, phosphoric acid is 0.5 W / V%, and phosphoric acid tri is. The anti-virus agent for clothing, which contained 0.25 W / V% of sodium and the content of the remaining purified water, had no effect on the texture of the cloth, but did not show effective anti-virus activity.

Furthermore, as in Comparative Example 9 shown in Table 2, etanol is 70 W / V%, cetylpyridinium chloride is 0.05 W / V%, phosphoric acid is 0.5 W / V%, and trisodium phosphate is 0. The anti-virus agent for clothing, which had a content of .25 W / V% and residual purified water, had an effect on the texture of the cloth and did not show effective anti-virus activity.

Claims (3)

An antiviral agent for clothing, which comprises at least one of benzalkonium chloride and benzethonium chloride, an acid or a salt thereof, ethanol, and water. The content of at least one of benzalkonium chloride and benzethonium chloride is 0.01 to 2.0 W / V%, the content of the acid or its salt is 0.1 to 3.0 W / V%, and the content of ethanol is contained. The antiviral agent for clothing according to claim 1, wherein the ratio is 10 to 65 W / V% and the rest is water. The antiviral agent for clothing according to claim 1 or 2, which is contained in a spray container.