Spray-type 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 an injection-type aerosol composition.

Background Art

[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% by mass of silver-supported zeolite as an inorganic antibacterial agent, 0.02 to 6.0% by mass of 3 octahedral aqueous smectite, which is a smectite group clay mineral, as a dispersant, and 30 parts by mass or more with respect to 100 parts by mass of silver-supported zeolite, 25 to 55% by mass of an alcoholic organic solvent, and water as the balance. Examples of the propellant include dimethyl ether and liquefied petroleum gas. The aerosol composition for antibacterial treatment is pressure-filled into a pressure-resistant container (aerosol sprayer), sprayed from the pressure-resistant container, and imparts antibacterial properties to an object. Due to the above configuration, the aerosol composition for antibacterial treatment of Patent Document 1 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

Summary of the Invention

Problems to be Solved by the Invention

[0004] An injection-type aerosol composition, which is an aerosol composition for antibacterial treatment, may be stored in a pressure-resistant container for a long period of time until it is used. However, it may be required to be easily redispersed by stirring after long-term storage (excellent storage stability). Furthermore, it may be required that the spray-type aerosol composition has little effect on the texture of the object to which it is sprayed (excellent texture retention). Furthermore, it may be required that the aerosol composition uniformly impart antibacterial properties to the object it is sprayed on (excellent uniformity). Furthermore, it may be required that the spray-type aerosol composition maintains excellent antibacterial properties (excellent antibacterial durability) even after the sprayed surface of the object is abraded. Furthermore, it may be required that the antibacterial aerosol composition quickly imparts antibacterial properties to the object it is sprayed on (i.e., exhibits excellent immediate antibacterial efficacy). However, spray-type aerosol compositions that offer superior storage stability, texture retention, uniformity, antibacterial durability, and rapid antibacterial action have not been sufficiently studied to date.

[0005] Therefore, the 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 rapid antibacterial effect. [Means for solving the problem]

[0006] The present invention relates to a spray-type aerosol composition comprising a stock solution and a liquefied gas, The aforementioned stock solution 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% by mass of aqueous smectite, a smectite group clay mineral, as a dispersant for the inorganic antibacterial agent, 0.5 to 3.2% by mass of a quaternary ammonium salt as a dispersant aid and antibacterial agent, and a mixed solvent of water and an alcoholic organic solvent. [Effects 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 rapid antibacterial effect. [Brief explanation of the drawing]

[0008] [Figure 1]A photograph of the actual vehicle with an aerosol sprayer installed. [Modes for carrying out the invention]

[0009] The following describes one embodiment of the present invention.

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

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

[0012] (Inorganic antibacterial agents) The aforementioned stock solution contains an inorganic antibacterial agent as an antimicrobial agent. The inclusion of an inorganic antibacterial agent in the undiluted solution makes it easier for the spray-type aerosol composition according to this embodiment to exhibit antibacterial durability. Examples of the inorganic antibacterial agents include silver-supported zeolite, zinc pyrithione, titanium dioxide, tungsten oxide, and copper nanoparticles. These may be used individually or in combination of two or more. As the inorganic antibacterial agent, silver-supported zeolite and zinc pyrithione are preferably used. In the aforementioned silver-supported zeolite, silver ions are supported on zeolite, which is a type of porous ceramic. The silver content in the silver-supported zeolite is not particularly limited as long as the antibacterial effect is exhibited. For example, it is 0.1 to 10.0% by mass. Such silver-supported zeolites include 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., which are commercially available.

[0013] The stock solution contains an inorganic antibacterial agent, preferably 0.04 to 0.5% by mass, more preferably 0.05 to 0.3% by mass. When the stock solution contains 0.04% by mass or more of the inorganic antibacterial agent, the aerosol composition of the spray type according to the present embodiment has an advantage that it is more likely to exhibit antibacterial durability. When the stock solution contains 0.5% by mass or less of the inorganic antibacterial agent, the aerosol composition of the spray type according to the present embodiment has an advantage that it is less likely to cause inability to spray.

[0014] (Organic antibacterial agent) The stock solution contains an organic antibacterial agent as an antibacterial agent. When the stock solution contains an organic antibacterial agent, the aerosol composition of the spray type according to the present embodiment is likely to exhibit texture retention and immediate antibacterial effect. Examples of the organic antibacterial agent include phenolic, isothiazolone, pyridine·quinoline, imidazole, thiazole, alcohol, organic halogen, carboxylic acid, ester, ether, organic nitrogen, nitrogen-containing sulfur, etc. These may be used alone or in combination of two or more. The organic antibacterial agent is a concept that does not include the quaternary ammonium salt. In addition, as the organic antibacterial agent, chlorine-based aromatic compounds (phenolic), isothiazoline, and organic nitrogen-sulfur compounds are preferably used.

[0015] [[ID=2,6]]The stock solution contains an organic antibacterial agent, preferably 0.2 to 1.8% by mass, more preferably 0.4 to 1.4% by mass. By containing 0.2% by mass or more of an organic antibacterial agent in the stock solution, the aerosol composition of the present embodiment has the advantage of being more likely to exhibit texture retention and immediate antibacterial effect. By containing 1.8% by mass or less of an organic antibacterial agent in the stock solution, the aerosol composition of the present embodiment has the advantage of being more likely to suppress the precipitation of an organic antibacterial agent insoluble in an alcoholic organic solvent.

[0016] (Aqueous smectite as a dispersant) The stock solution contains an aqueous smectite, which is a smectite group clay mineral as a dispersant for an inorganic antibacterial agent. The aqueous smectite is an unmodified smectite. By containing the aqueous smectite in the stock solution, the aerosol composition of the present embodiment can prevent sedimentation and aggregation of an inorganic antibacterial agent (silver-supported zeolite) in a mixed solvent of water and an alcoholic organic solvent, and exhibit excellent dispersibility. The smectite group clay mineral is a layered silicate mineral belonging to the smectite group, and a structural layer in which a layer composed of silicon and oxygen (silica tetrahedral layer) sandwiches a layer composed of aluminum and oxygen (aluminum octahedral layer) is stacked. Examples of the aqueous smectite include trioctahedral smectites such as saponite, stevensite, hectorite, and sauconite; 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, as commercially available products of saponite, Smecton SA (manufactured by Kunimine Industries Co., Ltd.), as commercially available products of stevensite, Smecton ST (manufactured by Kunimine Industries Co., Ltd.), as commercially available products of hectorite, trade name Smecton SWN (manufactured by Kunimine Industries Co., Ltd.), Smecton SWF (manufactured by Kunimine Industries Co., Ltd.), as commercially available products of montmorillonite, Kunipia-G (manufactured by Kunimine Industries Co., Ltd.), Kunipia-G10 (manufactured by Kunimine Industries Co., Ltd.), etc. can be used. From the viewpoint of making the inorganic antibacterial agent easier to disperse, the aqueous smectite is preferably a trioctahedral smectite, and more preferably at least one trioctahedral smectite selected from the group consisting of saponite, stevensite, and hectorite. The aqueous smectite may be a natural product, a refined product from a natural product, or a synthetic product.

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

[0018] (Quaternary ammonium salt as a dispersing agent) The aforementioned stock solution contains a quaternary ammonium salt as a dispersing agent and antibacterial agent. Because the stock solution contains the quaternary ammonium salt, the spray-type aerosol composition according to this embodiment can enhance the dispersion effect of the aqueous smectite dispersant, resulting in excellent storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect. Examples of the quaternary ammonium salts 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 ethyl sulfate, benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, stearyltrimethylammonium chloride, methyldidecyldimethylammonium sulfate, distearyldimethylammonium chloride, cetyltrimethylammonium saccharin, and stearyltrimethylammonium saccharin. These may be used individually or in combination of two or more. From the viewpoint of adsorption to hard surfaces, dialkylmethylethylammonium ethosulfate, N,N-dialkyl-N,N-dimethylammonium bicarbonate / carbonate, and tetraalkylammonium adipate are preferably used as the quaternary ammonium salts.

[0019] The stock solution contains 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, of the quaternary ammonium salt. By containing 0.5% by mass or more of the quaternary ammonium salt in the stock solution, the spray-type aerosol composition according to this embodiment can enhance the dispersion effect of the aqueous smectite dispersant, resulting in superior storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect. By having the stock solution contain 3.2% by mass or less of the quaternary ammonium salt, the spray-type aerosol composition according to this embodiment can achieve both a good texture and stability.

[0020] (Mixed solvent) The aforementioned mixed solvent is a mixture of water and an alcoholic organic solvent. Alcoholic organic solvents can exert a sterilizing effect. Examples of the aforementioned alcoholic organic solvents include ethanol, methanol, and isopropyl alcohol. The stock solution contains, from the viewpoint of improving handling, preferably 40-80% by mass, more preferably 45-75% by mass, and even more preferably 47-70% by mass, of water. The stock solution contains, from the viewpoint of improving handling, preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass, an alcoholic organic solvent.

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

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

[0023] (Other ingredients) The aforementioned stock solution may contain other components commonly used as stock solutions for spray-type aerosol compositions. Other ingredients include pH adjusters, fragrances, antioxidants, preservatives, colorants, and UV absorbers. The proportions of other ingredients can be those of conventional general formulations, as long as they do not contradict the purpose of the present invention.

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

[0025] The spray-type aerosol composition according to this embodiment contains, preferably 100 to 200% by mass, more preferably 118 to 185% by mass, of the liquefied gas relative to 100% by mass of the stock solution. The spray-type aerosol composition according to this embodiment contains 100% by mass or more of the liquefied gas relative to 100% by mass of the undiluted liquid, which makes it easier to obtain a good spray state. The spray-type aerosol composition according to this embodiment contains 200% by mass or less of the liquefied gas relative to 100% by mass of the stock solution, thereby increasing the relative amount of stock solution that can be filled into a pressure-resistant container, while also suppressing excessive spray pressure and resulting in a good user experience. The preferred injection pressure is 0.1 to 1.0 MPa.

[0026] <Method for preparing a spray-type aerosol composition> The spray-type aerosol composition according to this embodiment can be prepared by known methods such as pressurizing and filling a pressure-resistant container (aerosol sprayer) with the stock solution and the liquefied gas. For example, by filling a pressure-resistant container with the stock solution, then filling it with the liquefied gas by under-cup filling or the like, and then fixing the valve, a spray product containing the spray-type aerosol composition according to this embodiment can be obtained by filling a pressure-resistant container with the stock solution.

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

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

[0029] Furthermore, the present invention is not limited to the embodiments described above. Nor is it limited by the effects and advantages described above. Moreover, the present invention can be modified in various ways without departing from the spirit of the invention.

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

[0031] [Item 1] A spray-type aerosol composition comprising a mixture of a stock solution and a liquefied gas, The aforementioned stock solution is a spray-type aerosol composition containing an organic antibacterial agent and an inorganic antibacterial agent as antibacterial agents, 0.03 to 0.9% by mass of aqueous smectite, a smectite group clay mineral, as a dispersant for the inorganic antibacterial agent, 0.5 to 3.2% by mass of a quaternary ammonium salt as a dispersant aid and antibacterial agent, and a mixed solvent of water and an alcoholic organic solvent. [Item 2] A spray-type aerosol composition as described in item 1, which is a one-push, full-volume spray type. [Item 3] A spray-type aerosol composition for use inside a vehicle, as described in item 1 or 2. [Item 4] The stock solution is a spray-type aerosol composition according to any one of items 1 to 3, containing 0.2 to 1.8% by mass of the organic antibacterial agent. [Item 5] The stock solution is a spray-type aerosol composition according to any one of items 1 to 4, containing 0.04 to 0.5% by mass of the inorganic antibacterial agent. [Item 6] A spray-type aerosol composition according to any one of items 1 to 5, containing 100 to 200% by mass of the liquefied gas based on 100% by mass of the stock solution. [Examples]

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

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

[0034] (Storage stability) The spray-type aerosol composition was stored in an aerosol sprayer at 50°C for one month. The spray-type aerosol composition was then stirred in a pressure-resistant container, and the state of the spray-type aerosol composition inside 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 did not redisperse even after stirring. The results are shown in Tables 1 and 2 below.

[0035] (Maintain texture) A spray-type aerosol composition was applied to test specimens, and the texture of the specimens before and after application was checked by five people (monitoring test). The following evaluation criteria were used for evaluation. ○: More than 80% of people (4 or more) 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 or fewer) determined that there was no change in the feel of the test piece before and after the treatment. The results are shown in Tables 1 and 2 below.

[0036] (uniformity) Test specimens were placed on the front and rear seats of the actual vehicle. Then, as shown in the photograph in Figure 1, an aerosol sprayer was set up at the footwell of the rear seat on the driver's side, and spraying of the aerosol composition was started from the aerosol sprayer. The vehicle door was closed, and the entire contents of the aerosol sprayer were sprayed. After the completion of the procedure, the antibacterial activity value of the test specimens was measured according to the JIS L1902 antibacterial test (bacterial liquid absorption method). The following evaluation criteria were used for evaluation. ○: The absolute value of the difference in antibacterial activity 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) A spray-type aerosol composition was applied to the test specimens. After degrading the treated test specimens by abrasion testing, the antibacterial activity value of the test specimens was measured according to the JIS L1902 antibacterial test (bacterial solution absorption method). In the aforementioned abrasion test (washability tester: compliant with JIS K5600), 12,000 reciprocating abrasions were performed using a microfiber. The following evaluation criteria were used for evaluation. ○: The 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] (Immediate antibacterial effect) Test specimens inoculated with the bacterial solution were placed on the front and rear seats of the actual vehicle. Then, as shown in the photograph in Figure 1, an aerosol sprayer was set up at the footwell of the rear seat on the driver's side, and spraying of the aerosol composition was started from the aerosol sprayer. The vehicle door was closed, and the entire contents of the aerosol sprayer were sprayed. After the procedure was completed, the number of bacteria on the test specimens was checked. ○: The reduction rate from the initial bacterial count was 99% or more. ×: The reduction rate from the initial bacterial count 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, Examples 1 to 8, which fall within the scope of the present invention, all exhibited good storage stability, texture retention, uniformity, antibacterial durability, and immediate antibacterial effect. On the other hand, as shown in Table 2, Comparative Example 1 did not use an aqueous smectite as a dispersant or an inorganic antibacterial agent, but contained a large amount of quaternary ammonium salt as a dispersant aid, resulting in poor texture retention and uniformity. Comparative Example 2 did not use a quaternary ammonium salt as a dispersant, but instead used a large amount of aqueous smectite as a dispersant, resulting in poor texture retention, uniformity, and immediate antibacterial effect. Comparative Example 3 contained a large amount of aqueous smectite as a dispersant and a quaternary ammonium salt as a dispersing aid, resulting in poor storage stability, texture retention, and uniformity. Comparative Example 4 contained a small amount of quaternary ammonium salt as a dispersing aid, resulting in poor antibacterial durability and rapid antibacterial action. Comparative Example 5 did not use aqueous smectite as a dispersant, and therefore exhibited poor storage stability. Comparative Example 6 did not use aqueous smectite as a dispersant, but instead used polyoxyethylene sorbitan monooleate (20 E.O.) (Leodol TW0120V) as a dispersant, resulting in poor storage stability and texture retention. Comparative Example 7 did not use quaternary ammonium salts, inorganic antimicrobial agents, or organic antimicrobial agents as dispersing aids, and exhibited poor storage stability, texture retention, uniformity, antimicrobial durability, and immediate antimicrobial effect. Comparative Example 8 did not use an aqueous smectite as a dispersant, but instead used an acrylic thickener as a dispersant, resulting in poor storage stability and texture retention. Comparative Example 9 did not use aqueous smectite as a dispersant, but instead used cellulose nanofibers as a dispersant, resulting in poor storage stability and texture retention. Therefore, it can be seen that the present invention provides a spray-type aerosol composition that is excellent in storage stability, texture retention, uniformity, antibacterial durability, and rapid antibacterial effect.

Claims

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

2. The spray-type aerosol composition according to claim 1, wherein it is a one-push, full-volume spray type.

3. A spray-type aerosol composition according to claim 1 or 2, for use inside a vehicle.

4. The undiluted solution contains 0.2 to 1.8% by mass of the organic antibacterial agent, as described in claim 1 or 2.

5. The undiluted solution contains 0.04 to 0.5% by mass of the inorganic antibacterial agent, as described in claim 1 or 2.

6. The spray-type aerosol composition according to claim 1 or 2, comprising 100 to 200% by mass of the liquefied gas with respect to 100% by mass of the stock solution.

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