Antiviral composition for hand spray and hand spray device filled with the same

Abstract

To provide a highly safe antimicrobial composition for hand-spraying and a hand sprayer filled therewith.SOLUTION: An antimicrobial composition for hand-spraying includes a cationic polymer and / or a salt thereof and a cationic surfactant. The cationic polymer and / or a salt thereof is 25-10000 ppm in concentration. The cationic surfactant is 25-10000 ppm in concentration. The antimicrobial composition is free of a propellant.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an antimicrobial composition for hand sprays and a hand spray device filled with the same. [Background technology]

[0002] In recent years, so-called "pandemics," in which infectious diseases transmitted by various pathogenic microorganisms spread rapidly in a short period of time, have become a problem, and deaths have been reported due to viral infections such as SARS (Severe Acute Respiratory Syndrome), norovirus, and avian influenza.

[0003] Therefore, active efforts are being made to develop antibacterial and antiviral agents that have antibacterial and antiviral effects against various bacteria and viruses.

[0004] Patent Document 1 discloses a disinfectant lubricant composition for conveyors, characterized by containing (A) 5-chloro-2-methyl-4-isothiazolin-3-one, (B) a cationic surfactant, and (C) water. It also discloses the use of benzalkonium chloride and polyhexamethylene biguanide hydrochloride as cationic surfactants and spraying the composition onto conveyors. Patent Document 2 discloses a disinfectant formulation imparting residual disinfecting properties, the disinfectant formulation comprising a polymer binder, a disinfecting compound, and a carrier, the polymer binder being an oxazoline homopolymer or an extended or modified polymer based on an oxazoline homopolymer. It also discloses the use of n-alkyldimethylbenzylammonium chloride (benzalkonium chloride) and polyhexamethylene biguanide (PHMB) as disinfectants and spray application of the disinfectant formulation. Patent Document 3 discloses a composition for spatial sterilization containing (A) at least one selected from the group consisting of benzalkonium chloride and benzethonium chloride, (B) ethanol, (C) water, and (D) dimethyl ether. The document also discloses that component (D) in the composition for spatial sterilization serves as a propellant when the composition is sprayed or sprayed on an aerosol to disperse it in space. Patent Document 5 discloses a disinfecting composition comprising: i) an alkoxysilylammonium film-forming compound; ii) benzalkonium chloride or benzethonium chloride; v) a polymeric biguanide (such as hexamethylene biguanide); and vi) a surfactant system including a) an alcohol ethoxylate; and b) an alkyl glucoside or alkyl polyglucoside. Patent Document 5 also discloses compositions with pH values ​​of 5.5 and 8.0. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-96997 [Patent Document 2] Japanese Patent Application Publication No. 2018-503681 [Patent Document 3] Patent No. 4632676 [Patent Document 4] Japanese Patent Publication No. 2020-185405 [Patent Document 5] Japanese Patent Application Laid-Open No. 2017-508808 [Patent Document 6] Japanese Patent Application Laid-Open No. 2005-288256 [Non-patent literature]

[0006] [Non-Patent Document 1] Japan Aerosol Manufacturers Association, Waterproofing Spray Liaison Committee, Subcommittee, "Voluntary Standards for Improving the Safety of Household Aerosol Waterproofing Spray Products, Revised March 7, 2016" (https: / / www.aiaj.or.jp / img / lm_12 / aerosol_4.pdf) Summary of the Invention [Problem to be solved by the invention]

[0007] Generally, if a mist of a disinfectant composition enters the lower respiratory tract such as the lungs or the trachea, it may have adverse effects on the human body. Therefore, it is desirable that the mist of the disinfectant composition has a diameter that does not reach the lower respiratory tract such as the lungs or the trachea. Patent Document 4 describes the correlation between droplet size and deposition in the respiratory tract: droplets with a diameter of about 10 microns are suitable for deposition in the oropharynx and nasal region; droplets with a diameter of about 2 to 4 microns are suitable for deposition in the central airways; and droplets with a diameter of less than 1 micron are suitable for delivery to the alveoli. Furthermore, Non-Patent Document 1 states that the rate of fine particles of 10 μm or less must be 0.6% or less as a guideline for preventing poisoning accidents. The above Patent Documents 1, 2, 3, and 5 describe spraying a disinfectant composition to form a mist, but do not describe how the composition should be specifically adjusted to obtain an average diameter that will prevent the mist of the disinfectant composition from reaching the lungs.

[0008] The present invention has been made in view of the above problems, and has as its object to provide a highly safe antimicrobial composition for hand sprays and a hand spray device filled with the same. [Means for solving the problem]

[0009] As mentioned above, the particle size of a mist of an antimicrobial composition must be 10 μm or more in order to be suspended in the air and prevent the mist from reaching the lower respiratory tract, such as the lungs or trachea. The proportion of mist with a particle size of 10 μm or less should be 0.6% or less, and for greater safety, the proportion of mist with a particle size of 10 μm or less should be 0.5% or less. As a result of extensive research into the composition of an antimicrobial composition suitable for ensuring such high safety, the inventors have found that by spraying an antimicrobial composition having a predetermined composition from a hand sprayer, the proportion of mist with a particle size of 10 μm or less in the mist generated by spraying the antimicrobial composition can be adjusted to 0.5% or less, thereby completing the present invention. The hand spray refers to a manually triggered sprayer such as that described in Patent Document 6.

[0010] That is, the antimicrobial composition for hand spray of the present invention comprises a cationic polymer and / or a salt thereof and a cationic surfactant, the concentration of the cationic polymer and / or the salt thereof is 25 to 10,000 ppm, the concentration of the cationic surfactant is 25 to 10,000 ppm, and the composition does not contain a propellant.

[0011] The antimicrobial composition for hand spray of the present invention contains 25 to 10,000 ppm of a cationic polymer and / or a salt thereof, and 25 to 10,000 ppm of a cationic surfactant, and does not contain a propellant, thereby making it possible to reduce the proportion of mist of the antimicrobial composition having a particle size of 10 μm or less to 0.5% or less. Therefore, almost no mist of the antimicrobial composition has a particle size large enough to reach the alveoli, minimizing the risk of the mist reaching the lungs or trachea and minimizing the effects on the human body. In other words, the present invention provides an antimicrobial composition for hand spray that can reliably inactivate bacteria and viruses while ensuring safety. One embodiment of the antimicrobial composition for hand spray of the present invention is preferably an aqueous solution containing a cationic polymer and / or a salt thereof and a cationic surfactant.

[0012] In this specification, the term "antimicrobial" refers to a concept that includes antiviral, antibacterial, antifungal, and antifungal properties. Therefore, the antimicrobial composition for hand spray of the present invention is an antimicrobial composition for hand spray that is antiviral, antibacterial, antifungal, and antifungal. Furthermore, the antimicrobial composition for hand spray of the present invention is preferably an antimicrobial composition for hand spray that is antiviral.

[0013] The antimicrobial composition for hand sprays of the present invention contains a cationic polymer and / or a salt thereof. The cationic polymer is preferably a polymeric biguanide and / or a polymeric guanidine, as these compounds have excellent antibacterial and antiviral properties. The polymeric biguanide is harmless to the human body and has excellent antimicrobial activity. Polymeric biguanide and / or a salt thereof are components used in food processing plants and medical settings, and are recognized as safe for the human body. Therefore, they are suitable components for forming fine particles into a mist.

[0014] The concentration of the cationic polymer and / or its salt in the antimicrobial composition for hand spray of the present invention is 25 to 10,000 ppm, preferably 250 to 5,000 ppm.

[0015] In the present invention, the compound constituting the polymer biguanide is not particularly limited, but is desirably a polyalkylene biguanide compound, preferably one represented by the following chemical formula (1).

[0016] [ka]

[0017] [In the formula, R a represents an alkylene group having 2 to 8 carbon atoms, and n represents an integer of 2 to 18.]

[0018] In the above chemical formula (1), R aThe alkylene group having 2 to 8 carbon atoms represented by the formula (I) includes linear alkylene groups such as ethylene, propylene, butylene, pentylene, hexylene (hexamethylene), heptylene (heptamethylene), and octylene (octamethylene), as well as branched alkylene groups such as isopropylene, isobutylene, isopentylene, dimethylpropylene, and dimethylbutylene, with linear alkylene groups being preferred.

[0019] In addition, from the viewpoint of antimicrobial effects such as virus inactivation, R a is preferably an alkylene group having 4 to 8 carbon atoms, and particularly preferably a hexamethylene group. Note that n in the above chemical formula (1) is an integer of 2 to 18, and in consideration of antimicrobial effects such as virus inactivation effects, ease of handling, etc., it is preferably an integer of 10 to 14, more preferably an integer of 11 to 13.

[0020] The polyalkylene biguanide compound represented by the above chemical formula (1) can be used in the form of a salt with an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid, or in the form of a salt with an organic acid such as acetic acid, lactic acid, or gluconic acid. Among such salts, hydrochloride, acetate, and gluconate are preferred, with hydrochloride being most preferred. The cationic polymer of the present invention desirably contains at least one compound selected from the group consisting of the polyalkylene biguanide compound represented by the above chemical formula (1) and salts thereof. The cationic polymer of the present invention may contain only one compound selected from the group consisting of the polyalkylene biguanide compound represented by the above chemical formula (1) and salts thereof, or may contain two or more compounds selected from the group consisting of the polyalkylene biguanide compound represented by the above chemical formula (1) and salts thereof.

[0021] In the present invention, the polyalkylene biguanide compound and / or salt thereof may be produced by a known method, such as the method described in British Patent No. 702,268, or may be a commercially available product, such as "Eccrineside BG (Eccrine is a registered trademark of Riko Kyosan Co., Ltd.)" (manufactured by Riko Kyosan Co., Ltd.), "Proxel IB" (manufactured by Arch Chemicals), or "Lonzavac BG" (manufactured by Lonza Japan Co., Ltd.).

[0022] In the present invention, the polyalkylene biguanide compound is a polyaminopropyl biguanide compound (R a is propylene) or polyhexamethylene biguanide compound (R a Preferably, the compound is a polyaminopropyl biguanide compound, and most preferably, the compound is a polyaminopropyl biguanide compound. Polyaminopropyl biguanide is known as a highly safe preservative that exerts its preservative effect in small amounts. Polyaminopropyl biguanide is water-soluble and does not partition into the oil phase, so its preservative power is not reduced in emulsion systems, and it is used as a disinfectant and preservative in industrial equipment, cosmetics, and pharmaceuticals. For this reason, it is produced in large quantities and is the easiest raw material to obtain.

[0023] In the present invention, the polymeric guanidine is not particularly limited, but is preferably a polymeric guanidine compound represented by the following chemical formula (2), and more preferably a polyhexamethylene guanidine compound.

[0024] [ka]

[0025] [In the formula, n is an integer of 1 or more, and A is nitric acid, formic acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid, phosphoric acid, fumaric acid, maleic acid, carbonic acid, sulfuric acid, or paratoluenesulfonic acid.]

[0026] The polymeric guanidine compound represented by the above chemical formula (2) can also be used in the form of a salt with nitric acid, formic acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid, phosphoric acid, fumaric acid, maleic acid, carbonic acid, sulfuric acid, or paratoluenesulfonic acid. The cationic polymer according to the present invention preferably contains at least one compound selected from the group consisting of the polymeric guanidine compound represented by the above chemical formula (2) and salts thereof. The cationic polymer according to the present invention may contain only one compound selected from the group consisting of the polymeric guanidine compound represented by the above chemical formula (2) and salts thereof, or may contain two or more compounds selected from the group consisting of the polymeric guanidine compound represented by the above chemical formula (2) and salts thereof.

[0027] As a polymeric guanidine compound having the structure represented by the above chemical formula (2), an antibacterial agent "AA-2100KII (trade name)" manufactured by Daiwa Chemical Industry Co., Ltd. is commercially available.

[0028] The antimicrobial composition for hand sprays of the present invention contains a cationic surfactant. The cationic surfactant is preferably a quaternary ammonium salt. This is because quaternary ammonium salts are water-soluble and have excellent antibacterial and antiviral properties.

[0029] The quaternary ammonium salt may be at least one selected from the group consisting of hexadecyltrimethylammonium salt (cetrimonium salt), didecyldimethylammonium salt, alkyldimethylbenzylammonium salt (benzalkonium salt), N,N-dimethyl-N-[2-[2-[4-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]benzenemethaneammonium salt (benzethonium salt), methylbenzethonium salt, dodecyldimethyl(2-phenoxyethyl)ammonium salt (domiphen salt), and [2-(lauroylmethylamino)ethyl]dimethyl(phenylcarbamoylmethyl)ammonium salt (dophanium salt). Quaternary ammonium salts exhibit excellent antibacterial and antiviral activity when used in combination with polymeric biguanides or polymeric guanidines, and also exhibit excellent antimicrobial activity. The quaternary ammonium salt in the present invention is preferably at least one selected from the group consisting of hexadecyltrimethylammonium salt (cetrimonium salt), alkyldimethylbenzylammonium salt (benzalkonium salt), N,N-dimethyl-N-[2-[2-[4-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]benzenemethaneammonium salt (benzethonium salt), dodecyldimethyl(2-phenoxyethyl)ammonium salt (domiphen salt), and [2-(lauroylmethylamino)ethyl]dimethyl(phenylcarbamoylmethyl)ammonium salt (dophanium salt).

[0030] The quaternary ammonium salt is preferably a chloride salt, a bromide salt, or an iodide salt, and more preferably a chloride salt or a bromide salt.

[0031] The cetrimonium salt is an alkyltrimethylammonium chloride having an alkyl group with 16 to 18 carbon atoms, has antibacterial and antiviral activity, and is also added to cosmetics and the like.

[0032] The benzalkonium salt (benzalkonium chloride) is a type of cationic surfactant, and its rational formula is C6H5CH2N + (CH3)2R·Cl ‐ (R=C8H 17 ~C 18 H 37 , long chain alkyl). The alkyl side chain R is C 12 H 25 Benzalkonium chloride (benzyldodecyldimethylammonium chloride, commonly known as BDDAC) has the highest antibacterial and antiviral activity, and the highest antimicrobial activity. In the present invention, the benzalkonium chloride is not particularly limited, but is preferably benzyldodecyldimethylammonium chloride.

[0033] The benzethonium salt is a type of cationic surfactant and has the same bactericidal action as the benzalkonium chloride, and is therefore used as an inverse soap for sterilization and disinfection.

[0034] The domiphen salt is a cationic surfactant that solubilizes fat and denatures proteins, and is believed to exert bactericidal and antiviral effects by rapidly destroying the outer membrane and cytoplasmic membrane of bacterial cell walls. The domiphen salt is preferably a bromide.

[0035] The concentration of the cationic surfactant in the antimicrobial composition for hand spray of the present invention is 25 to 10,000 ppm. If the concentration is less than 25 ppm, the antibacterial and antiviral activity is low, and if the concentration is more than 10,000 ppm, the viscosity becomes too high and the average particle size of the mist becomes too large. The concentration of the cationic surfactant in the antimicrobial composition for hand spray of the present invention is desirably 250 to 5,000 ppm.

[0036] The antimicrobial composition for hand spray of the present invention preferably has a pH of less than 5.0, and more preferably less than 4.0, because by making the pH weakly acidic, it is possible to adjust the skin, which has become alkaline due to dryness, to an optimum pH (pH = about 4 to 6). Furthermore, by setting the pH to less than 5.0, when the antimicrobial composition is sprayed using a hand sprayer, the proportion of mist with particle diameters of 10 μm or less in the generated mist can be reduced to less than 0.1%. Furthermore, keeping the pH below 5.0 exerts a strong antiviral effect against enveloped viruses such as COVID-19. The pH of the antimicrobial composition for hand spray is measured using a pH meter, such as a portable pH meter (model number D-71) manufactured by HORIBA.

[0037] The antimicrobial composition for hand sprays of the present invention does not contain a propellant. Propellant is generally a compressed gas or liquefied gas, which volatilizes from the liquid phase to form a gas (vapor) phase, such as dimethyl ether (DME), nitrogen, liquefied petroleum gas (LPG), or carbon dioxide. Because the antimicrobial composition for hand sprays of the present invention does not contain a propellant, the proportion of mist with a particle size of 10 μm or less in the mist generated by spraying can be reduced to 0.5% or less, and the average particle size of the refined mist can be made relatively large. This minimizes the mist's reach to the lungs or trachea, minimizes its effects on the human body, and provides a highly safe composition.

[0038] The microbial composition for hand spray of the present invention preferably has a mist with a particle diameter of 10 μm or less generated by spraying with a hand spray of 0.5% or less of the total. This minimizes the risk of the mist generated by spraying with the antimicrobial composition for hand spray of the present invention reaching the lungs or trachea, thereby providing a highly safe mist. Furthermore, the microbial composition for hand spray of the present invention more preferably has a mist with a particle diameter of 10 μm or less generated by spraying with a hand spray of 0.3% or less of the total, and even more preferably has a mist with a particle diameter of 0.1% or less of the total.

[0039] The antimicrobial composition for hand spray of the present invention preferably forms a mist with an average particle size (median size) of 49 to 70 μm upon spraying with a hand spray, thereby minimizing the risk of the mist produced by spraying the antimicrobial composition for hand spray of the present invention reaching the lungs or trachea, thereby providing a highly safe mist.

[0040] The antimicrobial composition for hand spray of the present invention preferably does not contain hypochlorous acid or free chlorine, because if fine particles containing such components enter the alveoli of humans or other animals, the effects on the human body or other animals are unpredictable. Furthermore, the antimicrobial composition for hand sprays of the present invention desirably does not contain water-soluble poly(meth)acrylamide. If the antimicrobial composition for hand sprays contains water-soluble poly(meth)acrylamide, the mist produced by the composition may dry and gel, resulting in the formation of microcapsules. If such microcapsules enter the alveoli of humans or other animals, they may have adverse effects on the human body or other animals. It is not desirable to make fine particles of components whose effects on the human body and other animals cannot be predicted.

[0041] The antimicrobial composition for hand spray of the present invention may further contain an alcohol, such as methanol, ethanol, propanol, or butanol, but ethanol is preferred as it has less adverse effects on the human body.

[0042] The antimicrobial composition for hand spray of the present invention is not particularly limited as long as it is in a dosage form suitable for hand spray, but is preferably a liquid formulation.

[0043] The antimicrobial composition for hand sprays of the present invention may contain various additives to the extent that the effects of the present invention are not impaired. Examples of such additives include fragrances, essential oils, viscosity modifiers, foam modifiers, enzymes, sugars, amino acids, etc. Examples of the fragrances and essential oils include geraniol, citronellol, eugenol, linalool, terpineol, thymol, menthol, limonene, perillaldehyde, etc., which are approved as food additives.

[0044] The method for granulating the antimicrobial composition for hand spray of the present invention can be carried out by a method commonly used in the field to which the present invention pertains, and is not particularly limited. For example, the manual trigger-type sprayer described in Patent Document 6 is preferably used. By using the antimicrobial composition for hand spray of the present invention as the internal solution of the sprayer, a highly safe hand spray device can be obtained.

[0045] The present invention also relates to a hand spray device filled with the antimicrobial composition for hand spray of the present invention. The nozzle diameter of the hand spray device used in the present invention is preferably 0.3 to 0.6 mm, because this makes it easy to adjust the average particle diameter of the mist to 49 μm to 70 μm. [Brief explanation of the drawings]

[0046] [Figure 1] FIG. 1 is a schematic diagram of a device containing the antimicrobial hand spray composition of the present invention. [Figure 2] FIG. 2 is a particle size distribution diagram showing the particle size distribution of the mists sprayed and generated in Example 5 and Test Example 1 of the present invention.

[0047] (Detailed Description of the Invention) The antimicrobial composition for hand spray of the present invention will now be described. The antimicrobial composition for hand spray of the present invention comprises a cationic polymer and / or a salt thereof and a cationic surfactant, wherein the concentration of the cationic polymer and / or the salt thereof is 25 to 10,000 ppm, the concentration of the cationic surfactant is 25 to 10,000 ppm, and the composition does not contain a propellant.

[0048] The antimicrobial composition for hand spray of the present invention contains 25 to 10,000 ppm of a cationic polymer and / or a salt thereof and 25 to 10,000 ppm of a cationic surfactant, and does not contain a propellant, thereby reducing the proportion of antimicrobial composition mist with a particle size of 10 μm or less to 0.5% or less. Furthermore, the average particle size (median diameter) of the mist formed by spraying the antimicrobial composition of the present invention is large, at 49 μm to 70 μm, minimizing the risk of the mist reaching the lungs or trachea and minimizing its effects on the human body. In other words, the present invention provides a hand spray composition that can reliably inactivate bacteria and viruses while ensuring safety. One embodiment of the antimicrobial composition of the present invention is preferably an aqueous solution containing a cationic polymer and / or a salt thereof and a cationic surfactant.

[0049] In this specification, the term "antimicrobial" refers to a concept that includes antiviral, antibacterial, antifungal, and antifungal properties. Therefore, the antimicrobial composition for hand spray of the present invention is an antimicrobial composition for hand spray that is antiviral, antibacterial, antifungal, and antifungal. Furthermore, the antimicrobial composition for hand spray of the present invention is preferably an antimicrobial composition for hand spray that is antiviral. The antimicrobial composition for hand spray of the present invention is effective against poxviruses, orthomyxoviruses (typical examples include human influenza viruses and avian influenza viruses), caliciviruses (typical examples include noroviruses and feline caliciviruses), paramyxoviruses, arenaviruses, rhabdoviruses, coronaviruses (including COVID-19), retroviruses, bunyaviruses, herpesviruses, adenoviruses, reoviruses, togaviruses, papovaviruses, picornaviruses, porvoviruses, and filoviruses.

[0050] The antimicrobial composition for hand sprays of the present invention contains a cationic polymer and / or a salt thereof. The cationic polymer is preferably a polymeric biguanide and / or a polymeric guanidine, as these compounds have excellent antibacterial and antiviral properties. The polymeric biguanide is harmless to the human body and has excellent antimicrobial activity. Polymeric biguanide and / or a salt thereof are components used in food processing plants and medical settings, and are recognized as safe for the human body. Therefore, they are suitable components for forming fine particles into a mist. The concentration of the cationic polymer and / or its salt in the antimicrobial composition for hand spray of the present invention is 25 to 10,000 ppm, preferably 250 to 5,000 ppm.

[0051] In the present invention, the compound constituting the polymer biguanide is not particularly limited, but is desirably a polyalkylene biguanide compound, preferably one represented by the following chemical formula (1).

[0052] [ka]

[0053] [In the formula, R a represents an alkylene group having 2 to 8 carbon atoms, and n represents an integer of 2 to 18.]

[0054] In the above chemical formula (1), R a The alkylene group having 2 to 8 carbon atoms represented by the formula (I) includes linear alkylene groups such as ethylene, propylene, butylene, pentylene, hexylene (hexamethylene), heptylene (heptamethylene), and octylene (octamethylene), as well as branched alkylene groups such as isopropylene, isobutylene, isopentylene, dimethylpropylene, and dimethylbutylene, with linear alkylene groups being preferred.

[0055] In addition, from the viewpoint of antimicrobial effects such as virus inactivation, R a is preferably an alkylene group having 4 to 8 carbon atoms, and particularly preferably a hexamethylene group. Note that n in the above chemical formula (1) is an integer of 2 to 18, and in consideration of antimicrobial effects such as virus inactivation effects, ease of handling, etc., it is preferably an integer of 10 to 14, more preferably an integer of 11 to 13.

[0056] The polyalkylene biguanide compound represented by the above chemical formula (1) can be used in the form of a salt with an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid, or in the form of a salt with an organic acid such as acetic acid, lactic acid, or gluconic acid. Among such salts, hydrochloride, acetate, and gluconate are preferred, with hydrochloride being most preferred. The cationic polymer of the present invention desirably contains at least one compound selected from the group consisting of the polyalkylene biguanide compound represented by the above chemical formula (1) and salts thereof. The cationic polymer of the present invention may contain only one compound, or two or more compounds, selected from the group consisting of the polyalkylene biguanide compound represented by the above chemical formula (1) and salts thereof.

[0057] In the present invention, the polyalkylene biguanide compound and / or salt thereof may be produced by a known method, such as the method described in British Patent No. 702,268, or may be a commercially available product, such as "Eccrineside BG (Eccrine is a registered trademark of Riko Kyosan Co., Ltd.)" (manufactured by Riko Kyosan Co., Ltd.), "Proxel IB" (manufactured by Arch Chemicals), or "Lonzavac BG" (manufactured by Lonza Japan Co., Ltd.).

[0058] In the present invention, the polyalkylene biguanide compound is a polyaminopropyl biguanide compound (R a is propylene) or polyhexamethylene biguanide compound (R a Preferably, the compound is a polyaminopropyl biguanide compound, and most preferably, the compound is a polyaminopropyl biguanide compound. Polyaminopropyl biguanide is known as a highly safe preservative that exerts its preservative effect in small amounts. Polyaminopropyl biguanide is water-soluble and does not partition into the oil phase, so its preservative power is not reduced in emulsion systems, and it is used as a disinfectant and preservative in industrial equipment, cosmetics, and pharmaceuticals. For this reason, it is produced in large quantities and is the easiest raw material to obtain.

[0059] In the present invention, the polymeric guanidine is not particularly limited, but is preferably a polymeric guanidine compound represented by the following chemical formula (2), and more preferably a polyhexamethylene guanidine compound. [ka] [In the formula, n is an integer of 1 or more, and A is nitric acid, formic acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid, phosphoric acid, fumaric acid, maleic acid, carbonic acid, sulfuric acid, or paratoluenesulfonic acid.]

[0060] The polymeric guanidine compound represented by the above chemical formula (2) can also be used in the form of a salt with nitric acid, formic acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid, phosphoric acid, fumaric acid, maleic acid, carbonic acid, sulfuric acid, or paratoluenesulfonic acid. The cationic polymer according to the present invention preferably contains at least one compound selected from the group consisting of the polymeric guanidine compound represented by the above formula (2) and salts thereof. The cationic polymer according to the present invention may contain only one compound selected from the group consisting of the polymeric guanidine compound represented by the above formula (2) and salts thereof, or may contain two or more compounds selected from the group consisting of the polymeric guanidine compound represented by the above formula (2) and salts thereof.

[0061] As a polymeric guanidine compound having the structure represented by the above chemical formula (2), an antibacterial agent "AA-2100KII (trade name)" manufactured by Daiwa Chemical Industry Co., Ltd. is commercially available.

[0062] The antimicrobial composition for hand sprays of the present invention contains a cationic surfactant. The cationic surfactant is preferably a quaternary ammonium salt. This is because quaternary ammonium salts are water-soluble and have excellent antibacterial and antiviral properties.

[0063] As the quaternary ammonium salt, at least one selected from the group consisting of hexadecyltrimethylammonium salt (cetrimonium salt), didecyldimethylammonium salt, alkyldimethylbenzylammonium salt (benzalkonium salt), N,N-dimethyl-N-[2-[2-[4-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]benzenemethaneammonium salt (benzethonium salt), methylbenzethonium salt, dodecyldimethyl(2-phenoxyethyl)ammonium salt (domiphen salt), and [2-(lauroylmethylamino)ethyl]dimethyl(phenylcarbamoylmethyl)ammonium salt (dophanium salt) can be used. When coexisting with a polymeric biguanide or polymeric guanidine, the quaternary ammonium salt exhibits excellent antibacterial and antiviral activity, and thus exhibits excellent antimicrobial activity. The quaternary ammonium salt in the present invention is preferably at least one selected from the group consisting of hexadecyltrimethylammonium salt (cetrimonium salt), alkyldimethylbenzylammonium salt (benzalkonium salt), N,N-dimethyl-N-[2-[2-[4-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]benzenemethaneammonium salt (benzethonium salt), dodecyldimethyl(2-phenoxyethyl)ammonium salt (domiphen salt), and [2-(lauroylmethylamino)ethyl]dimethyl(phenylcarbamoylmethyl)ammonium salt (dophanium salt).

[0064] The quaternary ammonium salt is preferably a chloride salt, a bromide salt, or an iodide salt, and more preferably a chloride salt or a bromide salt.

[0065] The cetrimonium salt is an alkyltrimethylammonium chloride having an alkyl group with 16 to 18 carbon atoms, has antibacterial and antiviral activity, and is also added to cosmetics and the like.

[0066] The benzalkonium salt (benzalkonium chloride) exhibits excellent antibacterial and antiviral activity when coexisting with a polymeric biguanide or polymeric guanidine, and exhibits excellent antimicrobial activity. The benzalkonium chloride used in the present invention is a type of cationic surfactant, and its rational formula is C6H5CH2N + (CH3)2R·Cl ‐ (R=C8H 17 ~C 18 H 37 , long chain alkyl). The alkyl side chain R is C 12 H 25 Benzalkonium chloride (benzyldodecyldimethylammonium chloride, commonly known as BDDAC) has the highest antibacterial and antiviral activity, and is highly antimicrobial. In the present invention, the benzalkonium chloride is not particularly limited, but is preferably benzyldodecyldimethylammonium chloride.

[0067] The benzethonium salt is a type of cationic surfactant and has the same bactericidal action as the benzalkonium chloride, and is therefore used as an inverse soap for sterilization and disinfection.

[0068] The domiphen salt is a cationic surfactant that solubilizes fat and denatures proteins, and is believed to exert bactericidal and antiviral effects by rapidly destroying the outer membrane and cytoplasmic membrane of bacterial cell walls. The domiphen salt is preferably a bromide.

[0069] The concentration of the cationic surfactant in the antimicrobial composition for hand spray of the present invention is 25 to 10,000 ppm, preferably 250 to 5,000 ppm. If the concentration of the cationic surfactant is less than 25 ppm, the antibacterial and antiviral activity will be low, and if it exceeds 10,000 ppm, the viscosity will be too high, resulting in an excessively large average particle size of the mist. Furthermore, the concentration of the cationic surfactant in the antimicrobial composition for hand spray of the present invention is preferably 250 to 5,000 ppm.

[0070] The antimicrobial composition for hand spray of the present invention preferably has a pH of less than 5.0, more preferably less than 4.0. By making the pH slightly acidic, it is possible to prevent skin that has become alkaline due to dryness. This is because the pH can be adjusted to the optimum value (pH = 4 to 6). Furthermore, by setting the pH to less than 5.0, when the antimicrobial composition is sprayed using a hand sprayer, the proportion of mist with particle diameters of 10 μm or less in the generated mist can be reduced to less than 0.1%. Furthermore, keeping the pH below 5.0 exerts a strong antiviral effect against enveloped viruses such as COVID-19. The pH of the antimicrobial composition for hand spray is measured using a pH meter, such as a portable pH meter (model number D-71) manufactured by HORIBA.

[0071] The antimicrobial composition for hand sprays of the present invention does not contain a propellant. Propellant is generally a compressed gas or liquefied gas, which volatilizes from the liquid phase to form a gas (vapor) phase, such as dimethyl ether (DME), nitrogen, liquefied petroleum gas (LPG), or carbon dioxide. Because the antimicrobial composition for hand sprays of the present invention does not contain a propellant, the proportion of mist with a particle size of 10 μm or less in the mist generated by spraying can be reduced to 0.5% or less, and the average particle size of the refined mist can be made relatively large. This minimizes the mist's reach to the lungs or trachea, minimizes its effects on the human body, and provides a highly safe composition.

[0072] The microbial composition for hand spray of the present invention preferably has a mist with a particle diameter of 10 μm or less generated by spraying with a hand spray of 0.5% or less of the total. This minimizes the risk of the mist generated by spraying with the antimicrobial composition for hand spray of the present invention reaching the lungs or trachea, thereby providing a highly safe mist. Furthermore, the microbial composition for hand spray of the present invention more preferably has a mist with a particle diameter of 10 μm or less generated by spraying with a hand spray of 0.3% or less of the total, and even more preferably has a mist with a particle diameter of 0.1% or less of the total.

[0073] The antimicrobial composition for hand spray of the present invention preferably forms a mist with an average particle size (median size) of 49 to 70 μm upon spraying with a hand spray, thereby minimizing the risk of the mist produced by spraying the antimicrobial composition for hand spray of the present invention reaching the lungs or trachea, thereby providing a highly safe mist.

[0074] (Method for measuring mist particle size and average particle size) The particle size (average particle size) of the mist generated by spraying the antimicrobial composition for hand spray of the present invention can be measured by commonly known methods, specifically, direct observation methods (optical microscope, electron microscope), laser diffraction / scattering methods, centrifugal sedimentation methods, electrical detection zone methods, photon correlation spectroscopy, etc. In the present invention, measurement is preferably performed using a laser diffraction / scattering method, and can be performed using a commercially available laser diffraction particle size distribution analyzer (for example, Matsubo Corporation, product name HELO&RODOS). Furthermore, the average particle size in the present invention represents the median diameter (50% diameter) unless otherwise specified. Note that particle size distribution by the laser diffraction / scattering method is measured on a volume basis, and the measurement results are output as a volume-based particle size distribution.

[0075] The antimicrobial composition for hand sprays of the present invention preferably does not contain hypochlorous acid or free chlorine. This is because if fine particles containing such components enter the alveoli of humans or other animals, the effects on the human body or other animals are unpredictable. It is undesirable to make fine particles of components whose effects on the human body or other animals are unpredictable.

[0076] The antimicrobial composition for hand sprays of the present invention desirably does not contain water-soluble poly(meth)acrylamide. If the antimicrobial composition for hand sprays contains water-soluble poly(meth)acrylamide, the mist produced by the composition may dry and gel, resulting in the formation of microcapsules. If such microcapsules enter the alveoli of humans or other animals, they may have adverse effects on the human body or other animals. It is therefore undesirable to microparticulate components whose effects on the human body or other animals cannot be predicted.

[0077] The antimicrobial composition for hand spray of the present invention may further contain an alcohol, such as methanol, ethanol, propanol, or butanol, but ethanol is preferred as it has less adverse effects on the human body.

[0078] The antimicrobial composition for hand sprays of the present invention may contain various additives to the extent that the effects of the present invention are not impaired. Examples of such additives include fragrances, essential oils, viscosity modifiers, foam modifiers, enzymes, sugars, amino acids, etc. Examples of the fragrances and essential oils include geraniol, citronellol, eugenol, linalool, terpineol, thymol, menthol, limonene, perillaldehyde, etc., which are approved as food additives.

[0079] The antimicrobial composition for hand spray of the present invention is not particularly limited as long as it is in a dosage form suitable for hand spray, but is preferably a liquid formulation.

[0080] The method for granulating the antimicrobial composition for hand spray of the present invention can be carried out by a method commonly used in the field to which the present invention pertains, and is not particularly limited. For example, the manual trigger-type sprayer described in Patent Document 6 is preferably used. By using the antimicrobial composition for hand spray of the present invention as the internal solution of the sprayer, a highly safe hand spray device can be obtained.

[0081] The present invention also relates to a hand spray device filled with the antimicrobial composition for hand spray of the present invention. The nozzle diameter of the hand spray device used in the present invention is preferably 0.3 to 0.6 mm, because this makes it easy to adjust the average particle diameter of the mist to 49 μm to 70 μm.

[0082] The spray device containing the antimicrobial hand spray composition of the present invention will now be described. FIG. 1 is a schematic diagram illustrating a spray device containing the antimicrobial hand spray composition of the present invention. FIG. 2 is a particle size distribution diagram showing the particle size distribution of the mists measured in Example 1 and Test Example 1.

[0083] The spray device shown in Figure 1 is a commercially available hand sprayer (trigger sprayer) that sprays by pulling a lever. As shown in Figure 1, tank 1 is a bottle-shaped synthetic resin molded product with a threaded opening at the top, and stores a mixed aqueous solution containing 25 to 10,000 ppm of a cationic polymer and / or its salt, and 25 to 10,000 ppm of a cationic surfactant. Tank 1 is preferably transparent or translucent so that the liquid level can be visually observed. Being able to visually observe the liquid level makes it possible to determine the end point and use it as a guide for when to replace the tank. A threaded cap 5 is screwed onto the threaded opening of tank 1, and pump 2 is attached to tank 1 by this.

[0084] Pump 2 has tube 4 that draws up the mixed aqueous solution and pump mechanism 21 that pressurizes the drawn-up chemical solution. Furthermore, lever 22 is provided on the front lower side of pump 2 so that it can swing. Nozzle 3 that communicates with pump mechanism 21 via a flow path 23 for the mixed aqueous solution is attached to the front upper side of pump 2. In the case of a trigger spray of this type, pulling lever 22 draws up and pressurizes the mixed aqueous solution, and the pressurized mixed aqueous solution is sprayed from nozzle 3.

[0085] The nozzle diameter of the nozzle 3 is not particularly limited, but is preferably 0.3 to 0.6 mm, for example.

[0086] Next, a method for producing the antimicrobial composition for hand spray of the present invention will be described. Note that the method for producing the antimicrobial composition for hand spray of the present invention is not limited to the following embodiment. The antimicrobial composition for hand spray of the present invention can be produced, for example, by stirring and mixing an aqueous solution containing a predetermined concentration of a cationic polymer and / or a salt thereof with an aqueous solution containing a predetermined concentration of a cationic surfactant, so that the concentration of the cationic polymer and / or a salt thereof is 25 to 10,000 ppm and the concentration of the cationic surfactant is 25 to 10,000 ppm, thereby producing a composition suitable for hand spray.

[0087] In addition, when producing the antimicrobial composition for hand spray of the present invention, a solvent such as water may be further added. As the solvent, any solvent commonly used in the field to which the present invention pertains can be used as long as it does not impair the effects of the present invention.

[0088] The present invention may also be a method for producing the antimicrobial composition for hand spray of the present invention. That is, the present invention may be a method for producing an antimicrobial composition for hand spray, which comprises adding an aqueous solution containing 25 to 20,000 ppm of a cationic surfactant to an aqueous solution containing 25 to 20,000 ppm of a cationic polymer and / or a salt thereof, and stirring and mixing the resulting mixture. The production method of the present invention preferably further comprises a step of adjusting the pH to less than 5. Suitable aspects of the cationic polymer and / or salt thereof, and the cationic surfactant in the production method of the present invention are the same as the suitable aspects of the cationic polymer and / or salt thereof, and the cationic surfactant in the antimicrobial composition for hand spray of the present invention. [Example]

[0089] Example 1 To 100 parts by weight of an aqueous solution of polyaminopropyl biguanide having a concentration of 2000 ppm as component (A), 100 parts by weight of an aqueous solution of benzethonium chloride having a concentration of 3000 ppm as component (B) was added to obtain a mixed aqueous solution of polyaminopropyl biguanide having a concentration of 1000 ppm and benzethonium chloride having a concentration of 1500 ppm (referred to as "stock solution" in Table 1, and represented as component (A) 1000 ppm, component (B) 1500 ppm). Example 2 To 100 parts by weight of an aqueous solution of polyaminopropyl biguanide having a concentration of 2000 ppm as component (A), 100 parts by weight of an aqueous solution of hexadecyltrimethylammonium hydrochloride (cetrimonium hydrochloride) having a concentration of 2000 ppm as component (B) was added, to obtain a mixed aqueous solution of polyaminopropyl biguanide having a concentration of 1000 ppm and hexadecyltrimethylammonium hydrochloride having a concentration of 1000 ppm (referred to as "stock solution" in Table 1, and represented as component (A) 1000 ppm, component (B) 1000 ppm). Example 3 To 100 parts by weight of an aqueous solution of polyaminopropyl biguanide having a concentration of 2000 ppm as component (A), 100 parts by weight of an aqueous solution of dodecyldimethyl(2-phenoxyethyl)ammonium bromide (domiphen bromide) having a concentration of 2000 ppm as component (B) was added, to obtain a mixed aqueous solution of polyaminopropyl biguanide having a concentration of 1000 ppm and dodecyldimethyl(2-phenoxyethyl)ammonium bromide having a concentration of 1000 ppm (referred to as "stock solution" in Table 1, and represented as component (A) 1000 ppm and component (B) 1000 ppm). Example 4 100 parts by weight of an aqueous solution of polyaminopropyl biguanide with a concentration of 2000 ppm as component (A) was added to 100 parts by weight of an aqueous solution of dophanium chloride with a concentration of 2000 ppm as component (B), to obtain a mixed aqueous solution of polyaminopropyl biguanide with a concentration of 1000 ppm and dophanium chloride with a concentration of 1000 ppm (referred to as "stock solution" in Table 1, and represented as component (A) 1000 ppm and component (B) 1000 ppm). Example 5 100 parts by weight of a 20 wt % aqueous solution of polyhexamethylene biguanide hydrochloride (PHMB) (molecular weight 2634, trade name: Lonzaproxel IB, manufactured by Lonza Japan) was diluted with water to a concentration of 2000 ppm as component (A), and 100 parts by weight of a 2000 ppm aqueous solution of benzalkonium chloride (benzyldodecyldimethylammonium chloride) was added as component (B) to obtain a mixed aqueous solution of polyhexamethylene biguanide hydrochloride (PHMB) with a concentration of 1000 ppm and benzyldodecyldimethylammonium chloride with a concentration of 1000 ppm (referred to as "stock solution" in Table 1; component (A) 1000 ppm, component (B) 1000 ppm). The pH of the resulting mixed aqueous solution was 3.2. The pH was measured using a pH meter. A portable pH meter (model number D-71) manufactured by HORIBA was used as the pH meter. Example 6 An aqueous solution of polyhexamethyleneguanidine with a concentration of 2000 ppm was prepared by diluting the antibacterial agent "AA-2100KII" manufactured by Yamato Chemical Industry Co., Ltd. with water. This was designated as component (A), and 100 parts by weight of an aqueous solution of benzethonium chloride with a concentration of 3000 ppm was added as component (B) to 100 parts by weight of this component (A), to obtain a mixed aqueous solution of polyhexamethyleneguanidine with a concentration of 1000 ppm and benzethonium chloride with a concentration of 1500 ppm (referred to as "undiluted solution" in Table 1, and represented as component (A) 1000 ppm and component (B) 1500 ppm). Example 7 To 100 parts by weight of an aqueous solution of hexadecyltrimethylammonium hydrochloride (cetrimonium hydrochloride) at a concentration of 2000 ppm as component (B) was added 100 parts by weight of an aqueous solution of polyhexamethyleneguanidine at a concentration of 2000 ppm, which was prepared in the same manner as in Example 6, to obtain a mixed aqueous solution of polyhexamethyleneguanidine at a concentration of 1000 ppm and hexadecyltrimethylammonium hydrochloride at a concentration of 1000 ppm (referred to as "stock solution" in Table 1, and represented as component (A) 1000 ppm and component (B) 1000 ppm). Example 8 To 100 parts by weight of an aqueous solution of polyhexamethyleneguanidine (component (A)) at a concentration of 2000 ppm, prepared in the same manner as in Example 6, was added 100 parts by weight of an aqueous solution of dodecyldimethyl(2-phenoxyethyl)ammonium bromide (domiphen bromide) at a concentration of 2000 ppm as component (B), to obtain a mixed aqueous solution of polyhexamethyleneguanidine at a concentration of 1000 ppm and dodecyldimethyl(2-phenoxyethyl)ammonium bromide at a concentration of 1000 ppm (referred to as "stock solution" in Table 1, and represented as component (A) 1000 ppm and component (B) 1000 ppm). Example 9 To 100 parts by weight of an aqueous solution of 2000 ppm of dophanium chloride as component (B) was added 100 parts by weight of an aqueous solution of 2000 ppm of polyhexamethylene guanidine as component (A), prepared in the same manner as in Example 6, to obtain a mixed aqueous solution of 1000 ppm of polyhexamethylene guanidine and 1000 ppm of dophanium chloride (referred to as "stock solution" in Table 1, and represented as 1000 ppm of component (A) and 1000 ppm of component (B)). Example 10 To 100 parts by weight of an aqueous solution of 2000 ppm of polyhexamethylene guanidine (component (A)) prepared in the same manner as in Example 6 was added 100 parts by weight of an aqueous solution of 2000 ppm of benzalkonium chloride (benzyldodecyldimethylammonium chloride) as component (B), to obtain a mixed aqueous solution of polyhexamethylene guanidine with a concentration of 1000 ppm and benzalkonium chloride (benzyldodecyldimethylammonium chloride) with a concentration of 1000 ppm (referred to as "stock solution" in Table 1, and represented as component (A) 1000 ppm and component (B) 1000 ppm).

[0090] (Spray Device Manufacturing and Test Example 1) 100 g of the mixed aqueous solution obtained in each Example was sealed in a hand spray device with a nozzle diameter of 0.3 mm to form the antimicrobial composition for hand spray according to Examples 1 to 10. Next, 57 g of the mixed aqueous solution of polyhexamethylene biguanide hydrochloride and benzyldodecyldimethylammonium chloride (benzalkonium chloride) obtained in Example 5 was mixed with 28 g of dimethyl ether (DME) as a propellant to prepare an antimicrobial composition solution for aerosols according to Test Example 1. The pH of the obtained antimicrobial composition solution for aerosols was 3.2. The obtained antimicrobial composition solution for aerosols was sealed in a spray device with a nozzle diameter of 0.3 mm, and this was used as the spray device according to Test Example 1. As a result, spray devices filled with the antimicrobial compositions (mixed aqueous solutions) of Examples 1 to 10 and spray devices filled with the antimicrobial composition of Test Example 1 (antimicrobial composition solution for aerosols) were obtained.

[0091] (Evaluation of spray results) The antimicrobial compositions of Examples 1 to 10 and Test Example 1 were sprayed from each spray device, and the average particle size of the antimicrobial compositions sprayed from the spray nozzle was measured using a laser diffraction particle size distribution analyzer (Matsubo Corporation, product name: HELO&RODOS). The analysis software used for the measurements was PAQXOS4.0. The average particle size is the median diameter (D50). The proportion (volume %) of mist with particle diameters of 10 μm or less was also measured. The results obtained are shown in Table 1 below.

[0092] [Table 1]

[0093] The results shown in Table 1 above indicate that when a composition containing 1000 ppm of a cationic polymer and / or its salt and 1000 ppm or 1500 ppm of a cationic surfactant, but no propellant, was sprayed as in Example 1, a mist with an average particle size of 48.1 to 56.9 μm was formed, and the proportion of mist with a particle size of 10 μm or less was low at 0.02% to 0.16%, demonstrating high safety. On the other hand, in Test Example 1, the relative amount of propellant was too high, resulting in a small average particle size of 29.0 μm and a high proportion of mist with particle sizes of 10 μm or less, at 8.84%. [Explanation of symbols]

[0094] 1: Tank 2: Pump 3: Nozzle 4: Tube 5:Threaded cap 21: Pump mechanism 22: Lever 23: Flow path

Claims

1. An antiviral composition for hand spray use, the nozzle diameter of which is 0.3 to 0.6 mm, The antiviral composition for hand spray contains a cationic polymer and / or a salt thereof, and a cationic surfactant, the concentration of the cationic polymer and / or salt thereof is 250 to 5000 ppm; The concentration of the cationic surfactant is 250 to 5000 ppm; Contains no propellants the cationic polymer is a polyhexamethylene biguanide compound and / or a polyaminopropyl biguanide compound; the cationic surfactant is at least one selected from the group consisting of domiphen bromide, dophanium chloride, and benzalkonium chloride; The antiviral composition for hand sprays, wherein when the antiviral composition for hand sprays is sprayed using a hand sprayer having a nozzle diameter of 0.3 mm to form a mist, the proportion of mist particles having a particle diameter of 10 μm or less is 0.1% or less of the total.

2. The antiviral composition for hand spray according to claim 1, wherein the antiviral composition for hand spray is sprayed using a hand sprayer having a nozzle diameter of 0.3 mm and becomes a mist having an average particle diameter (median diameter) of 49 to 70 μm.

3. The antiviral composition for hand spray according to claim 1 or 2 is filled in the container, A hand spray device characterized in that the nozzle diameter is 0.3 to 0.6 mm.

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