Sprayable aerosol composition

Abstract

To provide a sprayable aerosol composition with superior storage stability, texture preservation, uniformity, long-lasting antimicrobial performance, as well as fast-acting antibacterial effects.SOLUTION: The present invention provides a sprayable aerosol composition comprising a mixture of a stock solution and a liquefied gas. The stock solution comprises: an organic antimicrobial agent and an inorganic antimicrobial agent as antimicrobial agents; an aqueous smectite, which is a smectite group clay mineral, serving as a dispersant for the inorganic antimicrobial agent, in an amount of 0.03-0.9 mass%; a quaternary ammonium salt functioning as both a dispersant auxiliary and an antimicrobial agent, in an amount of 0.5-3.2 mass%; and a mixed solvent of water and an alcohol-based organic solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a propellant aerosol composition. [Background technology]

[0002] As an aerosol composition for antibacterial treatment, for example, a composition containing an antibacterial composition and a propellant is known (for example, Patent Document 1). In Patent Document 1, the antibacterial composition contains 0.05 to 2.0 mass% of silver-supported zeolite, which is an inorganic antibacterial agent, as an antibacterial agent, 0.02 to 6.0 mass% of trioctahedral aqueous smectite, which is a smectite clay mineral, as a dispersant, and the amount is 30 mass parts or more per 100 mass parts of the silver-supported zeolite, 25 to 55 mass% of an alcoholic organic solvent, and the balance is water. Dimethyl ether and liquefied petroleum gas are listed as the propellant. The aerosol composition for antibacterial treatment is filled under pressure into a pressure-resistant container (aerosol sprayer) and sprayed from the pressure-resistant container to impart antibacterial properties to an object. The aerosol composition for antibacterial treatment of Patent Document 1, having the above-mentioned composition, has excellent dispersibility of the inorganic antibacterial agent and can stably impart antibacterial properties to an object. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2021-187819 A Summary of the Invention [Problem to be solved by the invention]

[0004] A spray-type aerosol composition that is an aerosol composition for antibacterial treatment may be stored for a long period of time in a pressure-resistant container until use, and it may be required to be easily redispersed by stirring after long-term storage (excellent storage stability). In addition, the spray-type aerosol composition is also required to be less likely to affect the texture of the object onto which it is sprayed (to be excellent in maintaining the texture). Furthermore, it may be required that the aerosol composition be capable of uniformly imparting antibacterial properties to an object onto which it is sprayed (excellent uniformity). In addition, after the jet-type aerosol composition is sprayed onto an object, it may be required that the composition maintain excellent antibacterial properties even if the sprayed surface of the object is worn away (excellent antibacterial durability). Furthermore, it may be required that the aerosol composition for antibacterial treatment can quickly impart antibacterial properties to an object onto which it is sprayed (excellent immediate antibacterial effect). However, a spray-type aerosol composition that is excellent in storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial action has not been sufficiently investigated so far.

[0005] Therefore, an object of the present invention is to provide a spray-type aerosol composition that is excellent in storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect. [Means for solving the problem]

[0006] The present invention provides a spray-type aerosol composition comprising a mixture of a concentrate and a liquefied gas, The concentrate relates to a spray-type aerosol composition containing an organic antibacterial agent and an inorganic antibacterial agent as antibacterial agents, 0.03 to 0.9 mass% of aqueous smectite, which is a smectite group clay mineral, as a dispersant for the inorganic antibacterial agent, 0.5 to 3.2 mass% of a quaternary ammonium salt as a dispersing aid and antibacterial agent, and a mixed solvent of water and an alcoholic organic solvent. Effect of the Invention

[0007] According to the present invention, it is possible to provide a spray-type aerosol composition that is excellent in storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect. [Brief description of the drawings]

[0008] [Figure 1]A photo of the aerosol sprayer installed on an actual vehicle. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, one embodiment of the present invention will be described.

[0010] The spray type aerosol composition according to this embodiment is a spray type aerosol composition in which a concentrate and a liquefied gas are mixed. The stock solution contains an organic antibacterial agent and an inorganic antibacterial agent as antibacterial agents, 0.03 to 0.9 mass% of aqueous smectite, which is a smectite group clay mineral, as a dispersant for the inorganic antibacterial agent, 0.5 to 3.2 mass% of a quaternary ammonium salt as a dispersing aid and antibacterial agent, and a mixed solvent of water and an alcoholic organic solvent. The concentrate may also contain a deodorant and / or a rust inhibitor as an optional component.

[0011] <Undiluted solution> The spray type aerosol composition according to this embodiment has a concentrate.

[0012] (Inorganic antibacterial agent) The concentrate contains an inorganic antibacterial agent as the antibacterial agent. By including an inorganic antibacterial agent in the concentrate, the spray type aerosol composition according to this embodiment is more likely to exhibit antibacterial durability. Examples of the inorganic antibacterial agent include silver-supported zeolite, zinc pyrithione, titanium oxide, tungsten oxide, copper fine particles, etc. These may be used alone or in combination of two or more. As the inorganic antibacterial agent, silver-supported zeolite and zinc pyrithione are preferably used. In the silver-loaded zeolite, silver ions are loaded onto zeolite, which is a type of porous ceramic. The amount of silver supported in the silver-supported zeolite is not particularly limited as long as the antibacterial effect is exhibited, but is, for example, 0.1 to 10.0 mass %. As such silver-supported zeolite, Zeomic AW10N (manufactured by Sinanen Zeomic Co., Ltd.), Zeomic AJ10N (manufactured by Sinanen Zeomic Co., Ltd.), Zeomic AK10N (manufactured by Sinanen Zeomic Co., Ltd.), etc. are commercially available.

[0013] The stock solution preferably contains 0.04 to 0.5% by mass, and more preferably 0.05 to 0.3% by mass, of the inorganic antibacterial agent. By containing 0.04% by mass or more of an inorganic antibacterial agent in the concentrate, the spray type aerosol composition according to this embodiment has the advantage of being more likely to exhibit antibacterial durability. By containing 0.5% by mass or less of an inorganic antibacterial agent in the concentrate, the spray type aerosol composition according to this embodiment has the advantage that it is less likely to become unable to spray.

[0014] (Organic antibacterial agent) The concentrate contains an organic antibacterial agent as the antibacterial agent. By containing an organic antibacterial agent in the concentrate, the spray type aerosol composition according to this embodiment is more likely to retain its texture and exhibit immediate antibacterial properties. Examples of the organic antibacterial agent include phenols, isothiazolones, pyridine-quinolines, imidazoles, thiazoles, alcohols, organic halogens, carboxylic acids, esters, ethers, organic nitrogens, and nitrogen-containing sulfurs, etc. These may be used alone or in combination of two or more. The organic antibacterial agent does not include the quaternary ammonium salt. As the organic antibacterial agent, chlorine-based aromatic compounds (phenol-based), isothiazolin, and organic nitrogen-sulfur compounds are preferably used.

[0015] The stock solution preferably contains 0.2 to 1.8% by mass, and more preferably 0.4 to 1.4% by mass, of the organic antibacterial agent. By containing 0.2% by mass or more of an organic antibacterial agent in the concentrate, the spray type aerosol composition according to this embodiment has the advantage that it is easier to maintain texture and exhibit immediate antibacterial properties. By containing 1.8% by mass or less of an organic antibacterial agent in the concentrate, the spray-type aerosol composition of this embodiment has the advantage that it is easier to inhibit precipitation of the organic antibacterial agent, which is insoluble in alcoholic organic solvents.

[0016] (Water-based smectite as a dispersant) The concentrate contains aqueous smectite, which is a smectite group clay mineral, as a dispersant for the inorganic antibacterial agent. The aqueous smectite is a non-organic smectite. Since the concentrate contains the aqueous smectite, the spray type aerosol composition according to the present embodiment can prevent precipitation and aggregation of the inorganic antibacterial agent (silver-supported zeolite) in a mixed solvent of water and an alcoholic organic solvent, thereby exhibiting excellent dispersibility. The smectite clay minerals are layered silicate minerals belonging to the smectite group, and are composed of stacked structural layers in which layers of silicon and oxygen (silica tetrahedron layers) are sandwiched between layers of aluminum and oxygen (aluminum octahedron layers). Examples of the aqueous smectite include trioctahedral smectites such as saponite, stevensite, hectorite, and sauconite, and dioctahedral smectites such as montmorillonite, beidellite, and nontronite. These may be used alone or in combination of two or more. As the aqueous smectite, commercially available products can be used as they are. For example, a commercially available saponite product is Sumecton SA (manufactured by Kunimine Kogyo Co., Ltd.), a commercially available stevensite product is Sumecton ST (manufactured by Kunimine Kogyo Co., Ltd.), a commercially available hectorite product is Sumecton SWN (manufactured by Kunimine Kogyo Co., Ltd.) or Sumecton SWF (manufactured by Kunimine Kogyo Co., Ltd.), and a commercially available montmorillonite product is Kunipia-G (manufactured by Kunimine Kogyo Co., Ltd.) or Kunipia-G10 (manufactured by Kunimine Kogyo Co., Ltd.) can be used. From the viewpoint of making the inorganic antibacterial agent more easily dispersible, the aqueous smectite is preferably a trioctahedral smectite, and more preferably at least one type of trioctahedral smectite selected from the group consisting of saponite, stevensite, and hectorite. The aqueous smectite may be any of natural products, products purified from natural products, and synthetic products.

[0017] The stock solution contains 0.03 to 0.9 mass %, preferably 0.05 to 0.7 mass %, and more preferably 0.1 to 0.6 mass % of aqueous smectite. When the concentrate contains 0.03% by mass or more of aqueous smectite, the spray type aerosol composition according to this embodiment can exhibit excellent dispersibility. When the concentrate contains 0.9% by mass or less of aqueous smectite, the spray type aerosol composition according to this embodiment can provide stable aerosol spray.

[0018] (Quaternary ammonium salt as a dispersing agent) The concentrate contains a quaternary ammonium salt as a dispersing agent and antibacterial agent. Since the concentrate contains the quaternary ammonium salt, the spray type aerosol composition of this embodiment can enhance the dispersion effect of the aqueous smectite, which serves as a dispersant, and as a result, the composition has excellent storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect. Examples of the quaternary ammonium salt include dialkylmethylethylammonium ethosulfate, N,N-dialkyl-N,N-dimethylammonium bicarbonate / carbonate, tetraalkylammonium adipate, alkyl(C16,18)trimethylammonium chloride, didecylmethylpoly(1-2)oxyethylammonium propionate, coconut alkyldimethylethylammonium ethylsulfate, benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, stearyltrimethylammonium chloride, methyldidecyldimethylammonium sulfate, distearyldimethylammonium chloride, cetyltrimethylammonium saccharin, stearyltrimethylammonium saccharin, etc. These may be used alone or in combination of two or more. As the quaternary ammonium salt, from the viewpoint of adsorptivity to hard surfaces, dialkylmethylethylammonium ethosulfate, N,N-dialkyl-N,N-dimethylammonium bicarbonate / carbonate, and tetraalkylammonium adipate are preferably used.

[0019] The stock solution contains the quaternary ammonium salt in an amount of 0.5 to 3.2% by mass, preferably 0.6 to 3.0% by mass, and more preferably 0.7 to 2.8% by mass. By containing 0.5% by mass or more of the quaternary ammonium salt in the concentrate, the spray type aerosol composition of this embodiment can enhance the dispersion effect of the aqueous smectite as a dispersant, and as a result, the composition has excellent storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect. When the concentrate contains 3.2% by mass or less of the quaternary ammonium salt, the spray type aerosol composition according to this embodiment can achieve both good texture and stability.

[0020] (Mixed Solvent) The mixed solvent is a mixed solvent of water and an alcoholic organic solvent. The alcohol-based organic solvent can exert a bactericidal effect. Examples of the alcoholic organic solvent include ethanol, methanol, and isopropyl alcohol. From the viewpoint of improving handleability, the concentrate contains water in an amount of preferably 40 to 80% by mass, more preferably 45 to 75% by mass, and even more preferably 47 to 70% by mass. From the viewpoint of improving handleability, the stock solution contains an alcoholic organic solvent in an amount of preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass.

[0021] (Deodorant) The concentrate may contain a deodorant as an optional component. The deodorant includes organic deodorants. Examples of the organic deodorant include methylated β-cyclodextrin and plant extract deodorants. The concentrate contains the deodorant in an amount of preferably 0.05 to 0.50% by mass, and more preferably 0.07 to 0.30% by mass.

[0022] (rust inhibitor) The stock solution may contain an anti-rust agent as an optional component. Examples of the rust inhibitor include organic acid amine salts, benzotriazole-based compounds, ammonium salt-based compounds, and fatty acid-based compounds. The stock solution preferably contains the rust inhibitor in an amount of 0.10 to 0.30% by mass, and more preferably 0.15 to 0.25% by mass.

[0023] (Other Ingredients) The concentrate may contain other ingredients commonly used in concentrates for propellant aerosol compositions. Other ingredients include pH adjusters, fragrances, antioxidants, preservatives, colorants, and ultraviolet absorbers. The blending ratio of the other components may be any conventional blending ratio as long as it does not contradict the object of the present invention.

[0024] <Liquefied gas> The spray type aerosol composition according to this embodiment further contains a liquefied gas in addition to the concentrate. Examples of the liquefied gas include dimethyl ether (DME), liquefied petroleum gas (LPG), 1,3,3-tetrafluoro-1-propene (HFO), etc. These may be used alone or in combination of two or more.

[0025] The spray aerosol composition according to this embodiment contains the liquefied gas in an amount of preferably 100 to 200% by mass, more preferably 118 to 185% by mass, based on 100% by mass of the concentrate. The spray-type aerosol composition according to the present embodiment contains 100% by mass or more of the liquefied gas relative to 100% by mass of the concentrate, so that a good spray state can be easily obtained. The spray-type aerosol composition of this embodiment contains 200% by mass or less of the liquefied gas per 100% by mass of the concentrate, thereby making it possible to increase the relative amount of concentrate that can be filled into a pressure-resistant container and to prevent the spray pressure from becoming too strong, resulting in a good usability. The preferred injection pressure is 0.1 to 1.0 MPa.

[0026] <Method of producing a spray-type aerosol composition> The spray-type aerosol composition according to the present embodiment can be prepared by a known method such as pressurizing and filling the concentrate and the liquefied gas into a pressure-resistant container (aerosol sprayer). For example, the concentrate is filled into a pressure-resistant container, and then the liquefied gas is filled by under-cup filling or the like, and then the valve is fixed, thereby obtaining a spray product in which the spray-type aerosol composition according to the present embodiment is filled into a pressure-resistant container.

[0027] The spray-type aerosol composition according to the present embodiment contains the quaternary ammonium salt in addition to the organic antibacterial agent, the inorganic antibacterial agent, the aqueous smectite, and the mixed solvent, and thus has excellent storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect.

[0028] Examples of objects to which the spray-type aerosol composition of this embodiment can be sprayed to impart antibacterial properties include textile products such as sheets, rugs, mats, sofas, carpets, clothing, towels, slippers, hats, nonwoven fabrics, tents, ropes, etc.; furniture such as chests of drawers, closets, cupboards, tables, chairs, sofas, etc.; electrical appliances such as refrigerators, gas ranges, range hoods, ventilation fans, lampshades, chandeliers, air conditioners, etc.; and residences such as interior and exterior walls, bathrooms, toilets, and kitchen areas. The spray-type aerosol composition according to this embodiment is particularly suitable for use in vehicle interiors. The spray-type aerosol composition according to this embodiment is preferably used as a one-push total spray type.

[0029] The present invention is not limited to the above-described embodiment. The present invention is also not limited to the above-described effects. Furthermore, the present invention can be modified in various ways without departing from the gist of the present invention.

[0030] [Disclosure items] Each of the following sections is a disclosure of a preferred embodiment.

[0031] [Item 1] A spray-type aerosol composition comprising a mixture of a concentrate and a liquefied gas, The concentrate is a spray-type aerosol composition containing an organic antibacterial agent and an inorganic antibacterial agent as antibacterial agents, 0.03 to 0.9 mass% of aqueous smectite, which is a smectite group clay mineral, as a dispersant for the inorganic antibacterial agent, 0.5 to 3.2 mass% of a quaternary ammonium salt as a dispersing aid and antibacterial agent, and a mixed solvent of water and an alcoholic organic solvent. [Item 2] 2. The spray-type aerosol composition according to item 1, which is a one-push total spray type. [Item 3] 3. The spray type aerosol composition according to item 1 or 2, which is for use in a vehicle interior. [Item 4] 4. The spray type aerosol composition according to any one of items 1 to 3, wherein the concentrate contains the organic antibacterial agent in an amount of 0.2 to 1.8% by mass. [Item 5] 5. The spray type aerosol composition according to any one of items 1 to 4, wherein the concentrate contains the inorganic antibacterial agent in an amount of 0.04 to 0.5% by mass. [Item 6] 6. The spray type aerosol composition according to any one of items 1 to 5, comprising 100 to 200% by mass of the liquefied gas relative to 100% by mass of the concentrate. EXAMPLES

[0032] The present invention will now be described in more detail with reference to examples and comparative examples, although the present invention is not limited to these examples in any way.

[0033] (Examples and Comparative Examples) A stock solution was obtained by mixing the materials for the stock solution shown in Tables 1 and 2 below in the blending ratios shown in Tables 1 and 2 below. The amount of silver supported in the silver-supported zeolite, which is the material for the stock solution, is 0.5 mass %. Next, the concentrate and the propellants shown in Tables 1 and 2 below were mixed in an aerosol sprayer, which is a pressure-resistant container, in the propellant ratios shown in Tables 1 and 2 below to obtain spray-type aerosol compositions. In Tables 1 and 2 below, the active ingredient concentration (%) means mass %, and the propellant ratio means the amount of propellant (mass %) relative to 100 mass % of the concentrate.

[0034] (Storage stability) The propellant aerosol composition was stored in an aerosol sprayer at 50° C. for one month. The spray type aerosol composition was then stirred in the pressure-resistant container, and the state of the spray type aerosol composition in the container was observed and evaluated according to the following criteria. ◯: The components in the spray type aerosol composition were redispersed by stirring. ×: The components in the spray type aerosol composition were not redispersed even when stirred. The results are shown in Tables 1 and 2 below.

[0035] (Maintains texture) The spray type aerosol composition was applied to a test piece, and five people checked the feel of the test piece before and after application (monitoring test). And the evaluation was performed according to the following criteria. ○: 80% or more people (four or more people) judged that there was no change in the feel of the test piece before and after application (the test piece was not sticky). ×: Less than 80% of people (3 people or less) judged that there was no change in the feel of the test piece before and after application. The results are shown in Tables 1 and 2 below.

[0036] (uniformity) Test pieces were placed on the front and rear seats of the actual vehicle. Then, as shown in the photograph of Figure 1, an aerosol sprayer was installed at the feet of the rear seat on the driver's side, spraying of the spray type aerosol composition was started from the aerosol sprayer, the door of the actual vehicle was closed, and the entire amount of the spray type aerosol composition in the aerosol sprayer was sprayed. After the construction was completed, the antibacterial activity value of the test piece was measured according to the JIS L1902 antibacterial test (bacterial liquid absorption method). And the evaluation was performed according to the following criteria. ○: The absolute value of the difference in antibacterial activity value between the front and back rows was 2.0 or less. ×: The absolute value exceeded 2.0. The results are shown in Tables 1 and 2 below.

[0037] (Antibacterial durability) The spray type aerosol composition was applied to the test piece, and the applied test piece was deteriorated by an abrasion test, and then the antibacterial activity value of the test piece was measured according to the JIS L1902 antibacterial test (bacterial liquid absorption method). In the abrasion test (washability tester: JIS K5600 compliant), 12,000 reciprocating abrasions were performed using microfiber. And the evaluation was performed according to the following criteria. ○: Antibacterial activity value was 2.0 or higher. ×: The antibacterial activity value was less than 2.0. The results are shown in Tables 1 and 2 below.

[0038] (Fast-acting antibacterial properties) The test specimens that had been ingested with the bacterial liquid were placed on the front and rear seats of the actual vehicle. Then, as shown in the photograph of Figure 1, an aerosol sprayer was installed at the feet of the rear seat on the driver's side, spraying of the jet-type aerosol composition was started from the aerosol sprayer, the door of the actual vehicle was closed, and the entire amount of the jet-type aerosol composition in the aerosol sprayer was sprayed. After the installation was completed, the number of bacteria on the test specimens was confirmed. ○: The reduction rate from the initial number of bacteria was 99% or more. ×: The reduction rate from the initial number of bacteria was less than 99%. The results are shown in Tables 1 and 2 below.

[0039] [Table 1]

[0040] [Table 2]

[0041] As shown in Table 1, in Examples 1 to 8 within the scope of the present invention, storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect were all good. On the other hand, as shown in Table 2, Comparative Example 1 did not use aqueous smectite as a dispersant or inorganic antibacterial agent, and contained a large amount of quaternary ammonium salt as a dispersion aid, and therefore had poor texture retention and uniformity. Comparative Example 2 did not use a quaternary ammonium salt as a dispersing aid, and contained a large amount of aqueous smectite as a dispersing agent, and was poor in texture retention, uniformity, and immediate antibacterial effect. Comparative Example 3 contained a large amount of aqueous smectite as a dispersant and a large amount of quaternary ammonium salt as a dispersion aid, and was poor in storage stability, texture retention, and uniformity. Comparative Example 4, in which the amount of quaternary ammonium salt serving as a dispersion aid was small, was poor in antibacterial durability and immediate antibacterial effect. Comparative Example 5 did not use aqueous smectite as a dispersant, and had poor storage stability. Comparative Example 6 did not use aqueous smectite as a dispersant, but used polyoxyethylene sorbitan monooleate (20E.O.) (Rheodol TW0120V) as a dispersant, and had poor storage stability and texture retention. Comparative Example 7 did not use a quaternary ammonium salt, an inorganic antibacterial agent, or an organic antibacterial agent as a dispersion aid, and was poor in storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect. Comparative Example 8 did not use aqueous smectite as a dispersant, but used an acrylic thickener as a dispersant, and was poor in storage stability and texture retention. Comparative Example 9 did not use aqueous smectite as a dispersant, but used cellulose nanofiber as a dispersant, and the storage stability and texture retention were poor. Therefore, it can be seen that the present invention can provide a spray-type aerosol composition that is excellent in storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect.

Claims

1. A spray-type aerosol composition comprising a mixture of a concentrate and a liquefied gas, The concentrate is a spray-type aerosol composition containing an organic antibacterial agent and an inorganic antibacterial agent as antibacterial agents, 0.03 to 0.9 mass% of aqueous smectite, which is a smectite group clay mineral, as a dispersant for the inorganic antibacterial agent, 0.5 to 3.2 mass% of a quaternary ammonium salt as a dispersing aid and antibacterial agent, and a mixed solvent of water and an alcoholic organic solvent.

2. 2. The spray-type aerosol composition according to claim 1, which is a one-push total spray type.

3. The spray type aerosol composition according to claim 1 or 2, which is for use in a vehicle interior.

4. 3. The spray type aerosol composition according to claim 1, wherein the concentrate contains the organic antibacterial agent in an amount of 0.2 to 1.8% by mass.

5. 3. The spray type aerosol composition according to claim 1, wherein the concentrate contains the inorganic antibacterial agent in an amount of 0.04 to 0.5% by mass.

6. 3. The spray type aerosol composition according to claim 1, comprising 100 to 200% by mass of the liquefied gas relative to 100% by mass of the concentrate.

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