JP6078417B2 - All-injection aerosol products - Google Patents

Description

  The present invention relates to a full-injection aerosol product.

High parts such as the ceiling of the bathroom and the upper part of the wall cannot be sprayed with a chlorinated mold remover from the viewpoint of safety, and are difficult to care for and molds easily propagate. There is a demand for a method that can reduce the time and effort of cleaning by preventing the growth of molds in such places and can easily maintain a clean space.
In recent years, many antiperspirant sprays (aerosols) using inorganic antibacterial agents such as silver, which have a high sterilizing and deodorizing effect, have been commercialized, but it is difficult to use these as an antifungal agent for bathrooms. . For example, in order to use the antiperspirant spray as an antifungal agent for the entire bathroom, it is necessary to spray a large amount of medicine continuously and uniformly on a wide surface, and there is a concern that the user may inhale during spraying. .
As a method for easily spraying an inorganic antibacterial agent, there is a method using a smoke-proof type antifungal agent. However, this method produces smoke and some consumers do not like it.
The all-injection-type aerosol agent is expected to be a mildew-repellent agent instead of a smoke agent because it does not generate smoke (becomes mist) and can be treated with chemicals at once in a closed space with a simple operation.
Patent Document 1 discloses a full-injection aerosol spray in which a compressed gas is combined as a propellant with a content liquid containing a specific inorganic antibacterial agent, photocatalyst particles, and a low boiling point solvent having a boiling point of 60 ° C. or less.

JP 2006-83086 A

  However, all-injection aerosols containing an inorganic antibacterial agent such as silver as an active ingredient have a problem in that the active ingredient adheres unevenly to the target surface. For example, when the mold prevention treatment is performed using the all-injection aerosol spray described in Patent Document 1, it is not a problem if the treatment space is a space with a low ceiling such as an automobile, but there is a certain amount of height. In the case of a space, for example, a bathroom, there is a problem that the active ingredient adheres unevenly to a surface to be treated, particularly a high place such as a ceiling, and a sufficient antifungal effect is not exhibited depending on the part.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an all-injection-type aerosol product in which an inorganic chemical agent is uniformly dispersed over the entire surface to be treated and exhibits an excellent microbial control effect. And

As a result of intensive studies, the present inventors have found that the adhesion of the active ingredient is not uniform in the technique described in Patent Document 1. (1) The injection force of the compressed gas, which is a propellant, makes the inorganic agent uniform. (2) Since the low boiling point solvent added to the content liquid tends to volatilize, the sprayed content liquid thickens and dries immediately after adhering to the surface to be treated. It was estimated that this was caused by difficulty in spreading on the surface to be processed. As a result of further investigation based on such knowledge, it has been found that the above problem can be solved by combining a specific boiling point solvent and a specific propellant at a specific ratio with respect to a specific inorganic drug. It was.
The present invention is based on the above findings and has the following aspects.

[1] A full-injection aerosol product in which a container is filled with contents,
The content contains an inorganic drug (A) having a transition metal, a solvent (B) having a boiling point of 70 to 200 ° C., and a propellant (C) containing dimethyl ether,
A mass injection type aerosol product, wherein a mass ratio (B / C) of the solvent (B) to the propellant (C) is 0.1 to 1.0.
[2] The all-injection aerosol product according to [1], wherein the content further contains a nonionic surfactant (D) having an HLB of 2 or more and less than 16.
[3] The all-injection aerosol product according to [1] or [2], wherein the content further contains a water-soluble polymer compound (E).
[4] The all-injection-type aerosol product according to any one of [1] to [3], which is for bathroom mold prevention.

  ADVANTAGE OF THE INVENTION According to this invention, the inorganic chemical | medical agent can be uniformly spread | diffused over the whole process target surface, and the whole quantity injection type aerosol product which exhibits the outstanding microbial control effect can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view showing a state before use (before pressing a push button) of an all-injection aerosol product 1 according to an embodiment of the present invention. It is a perspective view which shows the state at the time of use of the whole quantity injection type aerosol product 1 (state in which the content is injected after pressing the push button). It is III-III sectional drawing of the whole quantity injection type aerosol product 1. FIG. It is the schematic explaining the evaluation method of the fungicidal effect in [Example]. It is the schematic explaining the evaluation method of the sustainability of the fungicidal effect in [Example].

The total injection type aerosol product of the present invention is a container filled with contents,
The contents include an inorganic drug (A) having a transition metal (hereinafter also referred to as “component (A)”) and a solvent (B) having a boiling point of 70 to 200 ° C. (hereinafter referred to as “component (B)”). And a propellant (C) containing dimethyl ether (hereinafter also referred to as “component (C)”),
The mass ratio (B / C) of the component (B) to the component (C) is 0.1 to 1.0.

<(A) component>
(A) A component is an inorganic chemical | medical agent which has a transition metal.
The component (A) exhibits a microbial inhibitory effect (control effect) such as antibacterial, sterilizing, antifungal and antifungal. By exerting the microorganism suppressing effect, it is possible to suppress the odor due to the growth of microorganisms, and to exhibit a deodorizing effect.
The “inorganic drug having a transition metal” refers to a drug having at least one selected from the group consisting of a single transition metal and a compound thereof (transition metal compound) as an active ingredient.
(A) Silver, copper, zinc, nickel etc. are mentioned as a transition metal in a component.
The transition metal compound may be an inorganic compound or an organic compound. Examples of the transition metal compound include salts of transition metal ions and counter ions. Examples of the salts include chloride salts, nitrates, sulfates, sulfonates, carbonates, formates, and acetates.
(A) As an active ingredient of a component, since it is excellent in the microorganisms inhibitory effect and the deodorizing effect, silver, copper, zinc, or these compounds are preferable, and silver or a silver compound is more preferable.

  The component (A) may be composed of only the active ingredient, or may be a carrier in which the active ingredient is supported (hereinafter also referred to as a carrier). Examples of the carrier include substances such as zeolite, silica gel, low molecular glass, calcium phosphate, silicate, and titanium oxide. Examples of the carrier include a zeolite antibacterial agent supporting a transition metal compound such as silver oxide, silver nitrate, copper sulfate, and zinc chloride, a silica gel antibacterial agent, a titanium oxide antibacterial agent, and a silicate antibacterial agent. It is done. By using such a component (A), the effect of suppressing microorganisms when treated in a bathroom can be further exhibited.

The volume average particle diameter of the component (A) is preferably 0.01 to 1000 μm, more preferably 0.5 to 100 μm, and further preferably 1 to 5 μm.
The volume average particle diameter is a value determined by a laser diffraction / scattering particle size distribution measuring device (LA910, manufactured by Horiba, Ltd.), and can be measured as follows. (A) A component is disperse | distributed to distilled water so that it may become 1 mass% of solid content, and it is set as a sample. This sample is put into a laser diffraction / scattering type particle size distribution measuring apparatus, and the particle size distribution is measured by irradiating a laser after dispersion by ultrasonic waves in the apparatus. The diameter at which the cumulative volume frequency is 50% (volume) is defined as the average particle diameter.

(A) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the component (A) is preferably 0.05% by mass or more and less than 10% by mass, and more preferably 0.5% by mass or more and 2% by mass or less with respect to the total mass of the contents filled in the container. When the content of the component (A) is 0.05% by mass or more, a microorganism suppressing effect is sufficiently obtained. Even when the content of the component (A) is 10% by mass or more, further improvement in the effect cannot be expected, and the dispersibility in the contents may be lowered.
In addition, when (A) component is a support body, content of (A) component is the quantity as a support body.

<(B) component>
(B) A component is a solvent whose boiling point is 70-200 degreeC.
The component (B) contributes to improving the dispersibility of the chemical solution (mixture of components other than the component (C)) and improving the adhesion / spreading property of the chemical solution to the treated surface. For example, when the boiling point is 70 to 200 ° C., a uniform microorganism suppressing effect can be exhibited in the entire bathroom including the ceiling and wall surface. On the other hand, if the boiling point is lower than 70 ° C., the component (B) is volatilized rapidly from the injected chemical solution after the contents are injected, and the adhesion and spread of the chemical solution on the surface to be treated deteriorates. There is a possibility that the effects of the components may not be sufficiently exhibited, the effects may be uneven depending on the site, and the sustainability of the effects may be reduced. When the boiling point is higher than 200 ° C., the chemical solution attached to the surface to be treated such as the ceiling or wall surface is slowly dried after the contents are jetted, and the chemical solution flows down from the surface to be treated in a high humidity environment such as a bathroom. There is a possibility that the effect of the component A) is not sufficiently exhibited, or the effect is uneven depending on the part.
(B) 70-180 degreeC is preferable and the boiling point of a component has more preferable 70-150 degreeC.

  As the component (B), for example, ethanol, 2-propanol, propylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, elene glycol monoethyl ether acetate, ethylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol Examples include dimethyl ether, dipropylene glycol dimethyl ether, and isoparaffin hydrocarbons. Examples of the isoparaffinic hydrocarbon include trade name “Neothiozole” (manufactured by Chuo Kasei Co., Ltd.), trade name “IP Solvent” (manufactured by Idemitsu Kosan Co., Ltd.), and the like.

(B) A component can be used individually by 1 type or in combination of 2 or more types.
The content of the component (B) in the content is preferably 10% by mass or more and less than 50% by mass, and more preferably 20% by mass or more and 40% by mass or less, with respect to the total mass of the content filled in the container. . By making content of (B) component 10 mass% or more and less than 50 mass%, the dispersibility of a chemical | medical solution and the adhesiveness and spreadability to the process target surface of a chemical | medical solution will become favorable, and sufficient effect can be exhibited. On the other hand, if the amount is less than 10% by mass, the dispersibility of the chemical solution may be deteriorated, and if it is 50% by mass or more, the adhesion of the injected chemical solution to the surface to be processed is deteriorated, and the effect may not be sufficiently exhibited. is there.

<(C) component>
The component (C) is a propellant and contains at least dimethyl ether.
The component (C) contributes to the improvement of the sprayability of the chemical solution and the reachability to the surface to be processed (ceiling, wall surface, etc.).
Component (C) contains at least dimethyl ether, so that the dispersibility and spraying power of the chemical solution are improved, and the chemical solution reaches the high place such as the ceiling when the aerosol spray product of the present invention is used in a bathroom or the like. And adhesion are improved.

Component (C) may further contain a propellant other than dimethyl ether. Examples of the other propellant include liquefied gas other than dimethyl ether (liquefied petroleum gas, chlorofluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroolefin, etc.), compressed gas (carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc.) Etc. Of these, liquefied gas is preferable from the viewpoint of injection force (injection momentum).
Another propellant can be used individually by 1 type or in combination of 2 or more types as appropriate.

(C) 50-100 mass% is preferable with respect to the total mass of (C) component, and, as for the ratio of the dimethyl ether in a component, 70-100 mass% is more preferable. The above effect is sufficiently obtained when the proportion of dimethyl ether is 50% by mass or more.
On the other hand, there is no problem even if other propellants are blended slightly as component (C) for the purpose of adjusting the jetting performance, but problems may arise when the amount of other propellants increases. For example, when the component (C) is only liquefied petroleum gas (LPG), there is a possibility of causing a problem in compatibility with other components (particularly in a system in which water is mixed). Moreover, in the case of only compressed gas, there is a possibility that the momentum of injection is insufficient, the medicine cannot be delivered firmly to the ceiling of the bathroom, and the effect cannot be fully exhibited.
The component (C) is particularly preferably composed only of dimethyl ether.

  (C) 50 mass% or more and 90 mass% or less are preferable with respect to the total mass of the content with which a container is filled, and 60 mass% or more and 80 mass% or less are more preferable. By setting the content of the component (C) to 50% by mass or more and 90% by mass or less, the reachability and adhesion of the chemical solution to the treatment target surface are improved, and a sufficient effect can be exhibited. On the other hand, if the amount is less than 50% by mass, the adhesion of the chemical solution to the surface to be treated, particularly high places such as the ceiling, is deteriorated, and if it exceeds 90% by mass, the dispersibility of the chemical solution may be deteriorated.

  In the content, the mass ratio (B / C) of the component (B) to the component (C) is 0.1 to 1.0, and preferably 0.2 to 0.5. When B / C is 0.1 to 1.0, the dispersibility of the chemical solution and the adhesion / spreading property to the surface to be processed are good. On the other hand, when B / C is less than 0.1, the spreadability of the chemical solution on the surface to be treated is reduced, the distribution of the component (A) on the surface to be treated is non-uniform, and the effect of suppressing microorganisms may be reduced. There is. When B / C exceeds 1, the injection force decreases, and the reachability and adhesion of the chemical solution to the ceiling, wall surface, and the like decrease. Furthermore, the viscosity of the chemical solution adhering to the ceiling, wall surface, etc. is likely to increase, the spreadability is reduced, and the microbial control effect is reduced.

<Optional component>
[(D) component]
In addition to the components (A) to (C), the content is a nonionic surfactant (D) having an HLB (Hydrophile-Lipophile Balance) of 2 or more and less than 16 (hereinafter also referred to as “component (D)”). ) Is further preferably contained. Thereby, the uniformity (uniform dispersibility) of spreading of the chemical solution on the surface to be processed is improved, and the effect of suppressing microorganisms and the sustainability thereof are improved.

The HLB in the present invention is indicated by IOB × 10 in the organic conceptual diagram.
The organic conceptual diagram was proposed by Satoshi Fujita, and details thereof are described in “Pharmaceutical Bulletin”, 1954, vol. 2, 2, pp. 163-173, “Area of Chemistry”, 1957, vol. 11, 10, pp. 719-725, "Fragrance Journal", 1981, vol. 50, pages 79-82 and the like. That is, the source of all organic compounds is methane (CH ₄ ), all other compounds are all regarded as derivatives of methane, and certain numbers are set for the carbon number, substituent, transformation part, ring, etc. Add scores to determine organic and inorganic values. This value is plotted on a diagram with the organic value on the X axis and the inorganic value on the Y axis. This organic conceptual diagram is also shown in “Organic conceptual diagram-basics and application” (by Yoshio Koda, Sankyo Publishing, 1984).
The IOB in the organic conceptual diagram refers to the ratio of the inorganic value (IV) to the organic value (OV), that is, “inorganic value (IV) / organic value (OV)”.

The HLB of the component (D) is 2 or more and less than 16, and preferably 6 or more and 12 or less. When the HLB is 2 or more, the uniform dispersibility of the component (A) is improved. Even when the HLB is 16 or less, the uniform dispersibility of the component (A) is improved, and the sustainability of the effect in a high humidity environment such as a bathroom is also improved.
Specific examples of the component (D) include, for example, sorbitan fatty acid esters having a HLB of 2 to less than 16, glycerin fatty acid esters, polyglycerin fatty acids, sucrose fatty acid esters, propylene glycol fatty acid esters, glycerin alkyl ethers, polyoxyethylene (POE) -sorbitan fatty acid esters, POE-glycerin fatty acid esters, POE-propylene glycol fatty acid esters, POE-alkyl ethers, POE-polyoxypropylene (POP) -alkyl ethers, alkanolamides and the like.
As the component (D), a fatty acid ester of a polyhydric alcohol or an ethylene oxide adduct thereof is preferable, and a sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, or glycerin fatty acid ester that is liquid at room temperature is particularly preferable.
Examples of sorbitan fatty acid esters include monooleate and monolaurate. Examples of the glycerin fatty acid ester include glyceryl monocaprylate.

(D) A component can be used individually by 1 type or in combination of 2 or more types.
The content of the component (D) is preferably 0.3% by mass or more and 3% by mass or less, more preferably 0.5% by mass or more and 3.0% by mass or less, with respect to the total mass of the contents filled in the container. preferable. When the content of component (D) is 0.3% by mass or more, the uniform dispersibility of the chemical solution and the sustainability of the microbial control effect are sufficiently improved, and when it is 3% by mass or less, the uniform dispersibility of the chemical solution Will improve.

[(E) component]
In addition to the components (A) to (C) or in addition to the components (A) to (D), the content is also referred to as a water-soluble polymer compound (E) (hereinafter also referred to as “component (E)”). ) Is further preferably contained. Thereby, the sustainability (especially the sustainability in a high-humidity environment) of the microorganisms suppression effect improves.
In the present invention, the “water-soluble polymer compound” refers to a compound having a molecular weight of 1,000 or more that can be dissolved in 100 g of water at 20 ° C. in an amount of 1 g or more.

  As the component (E), for example, an acrylic polymer compound (a homopolymer or copolymer of an acrylic monomer selected from the group consisting of acrylic acid, acrylic ester and acrylamide, or the acrylic monomer) And other monomers such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, copolymers of acrylic acid and acrylate, etc.), vinyl polymer compounds (polyvinyl alcohol, polyvinyl Methyl ether, polyvinyl pyrrolidone, etc.), polyoxyethylene polymer compounds (eg, polyoxyethylene polyoxypropylene copolymer of polyethylene glycol), synthetic water-soluble polymer compounds such as cationic polymers; plant polymers (eg, , Gum arabic, guar gum, carraghi Nan, etc.), microbial polymers (e.g., xanthan gum, natural polymer compounds such as dextrin), and the like; cellulose polymers (cellulose, carboxymethyl cellulose, hydroxyethyl cellulose and the like); and the like. Among these, acrylic polymer compounds are preferable.

(E) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the component (E) is preferably 0.3% by mass or more and 3% by mass or less, and more preferably 0.5% by mass or more and 3% by mass or less with respect to the total mass of the contents filled in the container. (E) By making content of a component into 0.3 mass% or more, the sustainability of the microorganisms inhibitory effect is fully improved, and when it is 3 mass% or less, the uniform dispersibility of a chemical | medical solution and to a process target surface Sprayability is improved.

[Other optional ingredients]
The said content may further contain other components other than (A)-(E) component in the range which does not impair the effect of this invention as needed.
For example, when blending the component (E), an appropriate amount of water may be contained in order to improve the solubility of the component (E).

<Manufacturing method of all-injection aerosol products>
The all-injection aerosol product of the present invention can be produced by a conventional method.
For example, it can manufacture by mixing components other than (C) component, preparing a chemical | medical solution, and filling this chemical | medical solution and (C) component in a container, respectively.
The filling amount of the chemical solution, that is, the amount of the chemical solution used for one treatment (treatment amount) takes into consideration the size of the space to be treated, the area of the treatment surface, the amount of the component (A) used for the treatment of the space, etc. appropriately be determined, but not limited to, preferably an amount that the amount of the chemical liquid per space 1 m ³ of processing is 1 to 5 g, the amount to be 2~4g is more preferable.
The amount of the component (A) can be determined in consideration of the size of the space to be processed, but is preferably an amount such that the amount of the component (A) per 1 m ^{3 of} processing space is 1.5 mg to 250 mg. .
The filling amount of the component (C) can be appropriately determined in consideration of the filling amount of the chemical solution, the desired B / C value, and the like.

It does not specifically limit as a container, A well-known thing can be used as a container of the whole quantity injection type aerosol product. As a container for all-injection aerosol products, the pressure resistance is designed so that almost all of the contents of the container can be injected outside the container by a single operation (opening a valve, etc.) by any means of injection. A container is used.
Hereinafter, an embodiment of a full-injection aerosol product will be described with reference to the accompanying drawings. However, the all-injection-type aerosol product in the present invention is not limited to this embodiment, and the shape of the container and the like can be changed as appropriate.

  1-3 illustrate an embodiment of a full-injection aerosol product. FIG. 1 is a perspective view showing a state before use (before pressing a push button) of the full-amount aerosol product 1 of the present embodiment. FIG. 2 is a perspective view showing a state in use of the all-injection-type aerosol product 1 (a state in which contents are ejected after a push button is pressed). FIG. 3 is a cross-sectional view of the full-injection aerosol product 1 taken along the line III-III (for convenience of explanation, the spray can 2 portion is shown in a side view).

The all-injection aerosol product 1 includes a content (not shown), a spray can (container) 2 for storing the content, and a nozzle cap 3 attached to the spray can 2.
As shown in FIG. 3 (not shown in FIGS. 1 and 2), the all-injection aerosol product 1 further includes a plastic cap cover 11 that covers the nozzle cap 3. The cap cover 11 can be easily removed from the nozzle cap 3.

The spray can 2 is a metal pressure vessel made of, for example, steel or aluminum. The spray can 2 is provided so as to protrude from the center of the upper portion thereof, and is supported by being urged upward and supported so as to be movable in the vertical direction, and by pressing the stem 4 downward. And a valve mechanism (not shown).
The nozzle cap 3 is an injection device that injects the contents contained in the spray can 2 in full quantity. The nozzle cap 3 includes a cap body 5 attached to the upper part of the spray can 2, a push button 6 for pressing the stem 4 of the spray can 2, and the stem 4 of the spray can 2 by pressing the stem 4. And an ejection nozzle 7 for ejecting the ejected contents.

  The cap body 5 is a plastic cover member that covers the top of the spray can 2. As a material of the cap body 5, for example, polyolefin plastics such as polyethylene (PE) and polypropylene (PP) are preferable, and other plastic materials having elasticity such as polyethylene terephthalate (PET) can be used. The thickness of the cap body 5 is about 1 to 5 mm.

  The cap body 5 has a shoulder cover 8 that forms a substantially cylindrical peripheral wall having a substantially equal outer diameter to the body 2 a of the cylindrical spray can 2, and the lower end of the shoulder cover 8 has the spray can 2. The upper end of the body 2a is fitted. Specifically, a ring-shaped recess 9 is provided at the upper end of the body 2a of the spray can 2 over the entire outer peripheral surface. On the other hand, a ring-shaped convex portion 10 is provided on the lower end portion of the shoulder cover 8 over the entire circumference of the inner peripheral surface. The cap body 5 can be put on the upper portion of the spray can 2 by fitting the convex portion 10 of the shoulder cover 8 into the concave portion 9 of the spray can 2. Further, the nozzle cap 3 has such a fitting structure, thereby preventing the cap body 5 placed on the spray can 2 from being easily detached when the push button 6 is pressed.

The cap body 5 has a ceiling portion 12 that covers the upper surface of the shoulder cover 8.
The ceiling portion 12 has a front wall 12a that rises in a dome shape from the front side of the shoulder cover 8, a flat plate-like back wall 12b that forms the back side of the front wall 12a, and a flat surface on the back side of the back wall 12b. And a flat wall 12c to be formed.
The front wall 12 b is provided with a nozzle opening 13 that allows the spray nozzle 7 provided on one end side of the push button 6 to face outward. The flat wall 12c is provided with a button opening 14 that allows the operation portion 16 provided on the other end side of the push button 6 to face outward. The back wall 12 b is provided so as to block between the nozzle opening 13 and the button opening 14.

The push button 6 is a plastic operation member attached to the cap body 5, and includes a support portion 15 provided on one end side thereof and an operation portion provided on the other end side, that is, on the side opposite to the support portion 15. 16.
The support portion 15 is provided with a pair of support shafts 15 a, 15 a protruding in opposite directions from the surfaces facing each other, and the pair of support shafts 15 a, 15 a is a pair of bearings provided inside the cap body 5. The shafts 17 and 17 are pivotally supported. Thereby, the support part 15 is supported by the cap main body 5 so that rotation is possible.
The operation unit 16 can swing in the vertical direction with the support unit 15 as a fulcrum. Therefore, the push button 6 can press the stem 4 of the spray can 2 by pressing the operation portion 16 facing outward from the button opening 14.
Further, the push button 6 is arranged at the center of the lower surface of the push button 6, and is fitted with the stem 4 of the spray can and communicated with the fitting portion 18, and is ejected from the stem 4. A flow path 19 for guiding the contents to the injection nozzle 7 is provided.

  The injection nozzle 7 is a nozzle member attached to one end side of the push button 6. Specifically, the injection nozzle 7 has a shape that extends forward from the mounting position of the push button 6 and is bent obliquely upward so that the tip thereof faces outward from the nozzle opening 12. have. The injection nozzle 7 communicates with the flow path 19 of the push button 6 and injects the contents ejected from the stem 4 through the ejection port 7a provided at the tip thereof.

The nozzle cap 3 is provided with a lock mechanism 20 for fixing the push button 6 at a fixed position when the push button 6 is pressed. Specifically, the lock mechanism 20 is disposed on the cap body 5 side and is disposed on the push button 6 side with a locking portion 21 that locks the push button 6 in a fixed position. And a locked portion 22 that is locked to the locking portion 21. For example, the locking portion 21 is located at the upper end portion on the back side of the shoulder cover 8, and is formed of a protruding portion in which a part of the flat wall 12 c slightly protrudes along the peripheral edge portion of the button opening 14. On the other hand, the locked portion 22 is composed of, for example, a protruding portion that protrudes from the side surface of the push button 6 that faces the back side of the shoulder cover 8.
In this locking mechanism 20, when the push button 6 is pushed down against the biasing force of the stem 4 biased upward, the latched portion (projection portion) 22 becomes the latching portion (projection portion) of the shoulder cover 8. The sliding part 21 gets over the locking part 21 while being in sliding contact with the part 21. At this time, when the pressing on the push button 6 is released, the stem 4 biased upward presses the push button 6 upward, but the locked portion 22 of the push button 6 is the locking portion of the shoulder cover 8. It will be in the state latched by this latching | locking part 21 without getting over 21. FIG. As a result, the push button 6 is fixed (that is, when the push button 6 is pressed, the stem 4 is pressed, and the content ejected from the stem 4 is ejected from the ejection port 7 a of the ejection nozzle 7. Position).

  The all-injection-type aerosol product 1 having the above-described structure is operated when the user presses the push button 6 of the nozzle cap 3 with a finger or the like, usually in a state of being placed on the floor surface or the like. That is, in the aerosol device 1, when the push button 6 of the nozzle cap 3 is pressed and the stem 4 of the spray can 2 is pressed, the contents ejected from the stem 4 by the pressure of the propellant are discharged from the spray nozzle 7. It is sprayed in the form of a mist from the injection port 7a. Moreover, in this all-injection-type aerosol product 1, since the push button 6 is fixed to a fixed position by the lock mechanism 20, the pressing state of the stem 4 is maintained. As a result, while the valve mechanism of the spray can 2 is in an open state, the injection is continued until the contents stored in the spray can 2 disappear, and the injection ends when the gas pressure by the propellant disappears. Therefore, in this all-injection-type aerosol product 1, the contents accommodated in the spray can 2 can be ejected in a full amount by a single pressing operation.

<Effect>
The total injection type aerosol product of the present invention combines (A) component with a solvent (B) having a specific boiling point and a propellant (C) containing dimethyl ether, and B / C is within a specific range. Therefore, the uniformity of the dispersion of the component (A) in the entire processing space is improved, the component (A) is uniformly adhered to the surface to be treated, and an excellent antimicrobial effect (antibacterial, sterilizing, antifungal, antifungal Etc.) is obtained. For example, an excellent antifungal effect is exerted even on a treatment surface that is difficult to reach such as a ceiling of a bathroom or a high part of a wall surface.
The following can be considered as the reason why the above-mentioned effect can be obtained. First, when (C) component contains dimethyl ether, a jet power improves and (A) component can fully be spread | dispersed. In addition, since the boiling point of the component (B) is 70 ° C. or higher, the droplet containing the component (A) adheres well to the processing target surface after the contents are jetted, and then spreads to the processing target surface. Cheap. In addition, when the boiling point of the component (B) is 200 ° C. or less, the solvent is appropriately volatilized after adhesion, and the droplets are thickened, so that it is difficult for the droplets to flow down from the surface to be treated.

In the present invention, when the component (D) is used in combination with the components (A) to (C), the effect of suppressing microorganisms is further improved. Moreover, the sustainability of the microbial control effect is also improved.
In the present invention, when the (E) component is used in combination with the (A) to (C) components or the (A) to (D) components, the microorganism suppressing effect is further improved. In addition, it is possible to improve the sustainability of the microorganism suppressing effect in a high humidity environment such as a bathroom.

The all-injection-type aerosol product of the present invention is used for the treatment of a space where antimicrobial effects such as antibacterial, sterilizing, antifungal and antifungal are required.
The processing target of the all-injection aerosol product of the present invention is not particularly limited, and examples include a bathroom, a washroom, a kitchen, a toilet, a living room, and a closet.
From the viewpoint of the usefulness of the present invention, the all-injection aerosol product of the present invention is suitable for mold prevention in the bathroom.

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.
The raw materials used in the following examples are shown below.

<Raw materials>
A-1: Silver-supported zeolite inorganic antibacterial agent (trade name: Zeomic AJ10N, manufactured by Sinanen Zeomic Co., Ltd.).
A-2: Silver-supported silica / alumina inorganic antibacterial agent (trade name: ATOMY BALL- (UA), manufactured by JGC Catalysts & Chemicals Co., Ltd.).
A-3: Zinc-supported titanium oxide inorganic deodorant (trade name: ATOMY BALL- (TZ-R), manufactured by JGC Catalysts & Chemicals Co., Ltd.).

B-1: Ethanol (special reagent grade, Junsei Chemical Co., Ltd., boiling point: 78.37 ° C.).
B-2: Propylene glycol (special grade reagent, Junsei Chemical Co., Ltd., boiling point: 188.2 ° C.).
B-3: Isoparaffin hydrocarbon (trade name: Isopar H, manufactured by Exxon Chemical Co., Ltd., boiling point: 179 to 188 ° C. (catalog)).
B-4: n-pentane (reagent grade 1, manufactured by Junsei Chemical Co., Ltd., boiling point: 36.07 ° C.).
B-5: Tetraethylene glycol dimethyl ether (trade name: Hisolv MTEM, manufactured by Toho Chemical Industry Co., Ltd., boiling point: 275 ° C.).

C-1: Dimethyl ether (Mitsubishi Gas Chemical Co., Ltd.).
C-2: Liquefied petroleum gas (vapor pressure at 20 ° C .: 0.15 MPa).
C-3: Compressed nitrogen (filled so that the internal pressure at 25 ° C. becomes 0.8 MPa).

D-1: Monooleate (trade name: Emazole O-10V, manufactured by Kao Corporation, HLB = 9).
D-2: monolaurate (trade name: Emazole L-10V, manufactured by Kao Corporation, HLB = 8.6).
D-3: Glyceryl monocaprylate (trade name: MG-80, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB = 3.2).
D-4: Polyoxyethylene monooleate (ethylene oxide average 20 mol adduct, trade name: Emazole O-120V, manufactured by Kao Corporation, HLB = 1.5).
D-5: Dilauric acid glycol (trade name: EG-di-L, manufactured by Nippon Emulsion Co., Ltd., HLB = 2).
D-6: Polyoxyethylene lauryl ether (ethylene oxide average 30 mol adduct, trade name: Laureth-30, manufactured by Nippon Emulsion Co., Ltd., HLB = 16).

E-1: Acrylic copolymer (trade name: Julimer AT-210, copolymer of acrylic ester and acrylic acid, pure content of 30% by mass, aqueous solution), manufactured by Toagosei Co., Ltd., water at 20 ° C. Solubility in: 30 g or more / 100 mL).
E-2: Polyvinylpyrrolidone (trade name: K-30, manufactured by Nippon Shokubai Co., Ltd., solubility in water at 20 ° C .: 1 g or more / 100 mL).

<Examples 1 to 25 and Comparative Examples 1 to 9>
In the following procedure, the entire amount injection type aerosol product shown in FIG. 1 in which the contents of the composition (unit: mass%) shown in Tables 1 to 3 were filled in a container with the treatment amount (g) shown in Tables 1 to 3 were used. A full-injection aerosol product having the same structure as in No. 1 was produced.
Among the components shown in Tables 1 to 3, components other than the component (C) (propellant) were mixed to prepare a chemical solution. This chemical solution is put into a spray can 2 equipped with a valve mechanism (“Valsan Pro EX non-smoke fog type (for 6-10 tatami mat)” (trade name, manufactured by Lion Co., Ltd.)). After the components were pressure-filled and sealed, the nozzle cap 3 shown in FIG. 1 was attached to obtain a full-injection aerosol product.
About the comparative example 7 which used C-3 (compressed nitrogen) as (C) component, it filled so that the (A) component and (B) component in processing amount might become the same quantity as Example 1, and 25 degreeC Compressed nitrogen was charged so that the internal pressure at 0.8 MPa was 0.8 MPa.
The following evaluation was performed using the obtained all-injection aerosol product.
Examples 1 to 11, 17, 19 to 22, and 24 to 25 are reference examples.

[1. Evaluation of fungicidal effect]
(Evaluation method)
First, as shown in FIG. 4, two places (in the middle) of the ceiling surface of the sealable evaluation room (height from the floor surface to the ceiling surface: about 2 m) having the same volume as the 1818 type (for meter module) bathroom. At one of the four corners), test glass slides (slide glass inoculated with bacteria) 41 and 42 prepared by the following method ^{* 1} were attached with the surface inoculated with the bacteria facing the floor side. .
Next, a full-injection aerosol product 43 (a full-injection aerosol product manufactured in each example) was placed on the central floor in the evaluation room, and the contents were injected.
After 90 minutes from the injection of the contents, the air in the evaluation chamber was exhausted, and the slide glasses 41 and 42 were collected.
The bacterial solution collected from the slide glasses 41 and 42 by the following method ^{* 2} is appropriately diluted with physiological saline so as to have a measurable concentration, and then smeared on a potato dextrose agar medium at 25 ° C. After culturing for 5 days, the number of colonies formed was counted visually. The number of viable bacteria was determined from the measured number of colonies and the dilution rate of the bacterial solution, and the value was defined as the “number of bacteria after treatment”.
Separately, a bacterial solution collected from an untreated test glass slide was appropriately diluted with physiological saline so as to obtain a measurable concentration, and smeared on a potato dextrose agar medium at 25 ° C. for 5 days. After culturing, the number of colonies formed was visually counted. The number of viable bacteria was determined from the measured number of colonies and the dilution rate of the bacterial solution, and the value was defined as “the number of untreated bacteria”.
From the above results, the fungicidal efficacy and the uniformity of the fungicidal effect were evaluated according to the following evaluation criteria.

(* 1: How to make a test slide glass)
Cladospodium cladosporoides HMC1064 (bathroom isolate) cultured on a potato dextrose agar (Difco) slant medium at 25 ° C. for 1 week was sterilized in a 0.05% Tween 80 (Kanto Chemical) aqueous solution at about 106 CFU / mL. A spore solution was prepared. Next, 0.1 mL of the spore solution was inoculated on a slide glass (manufactured by Matsunami Glass Industrial Co., Ltd., white edge polishing No. 2, 76 × 26 mm), left to stand overnight at room temperature, and then dried and fixed.

(* 2: Method for collecting bacteria from slide glass)
Place slide glass (Matsunami Glass Kogyo Co., Ltd., white edge polishing No. 2, 76 × 26 mm) and SCDLP medium (Nihon Pharmaceutical Co., Ltd.) 10 mL into a sterile plastic petri dish (As One Co.) The mixture was stirred with Nissui Pharmaceutical Co., Ltd., and the bacteria were extracted from the slide glass.

(Evaluation criteria)
{The fungicidal effect: the center of the ceiling}
About the slide glass 41 installed in the center of the ceiling surface, the calculated number of bacteria is converted into a common logarithm (log), and the value obtained by subtracting the number of treated bacteria from the number of untreated bacteria (log (untreated number of bacteria) − log (the number of bacteria after treatment)) was determined, and the value was defined as the fungicidal efficacy. From that value, the fungicidal effect was determined according to the following criteria. The results are shown in Tables 1-3.
<Criteria>
A: The fungicidal effect is 4 or more.
○: The fungicidal efficacy is 2 or more and less than 4.
Δ: The fungicidal efficacy is 1 or more and less than 2.
X: The fungicidal efficacy is less than 1.

{Uniformity of fungicidal effect: Difference between the center and corner of the ceiling}
For the slide glass 42 installed at the corner of the ceiling surface, log (untreated number of bacteria) −log (number of treated bacteria) was determined in the same manner as described above, and the value was used as the fungicidal effect.
The difference between the fungicidal efficacy at the center of the ceiling and the fungicidal efficacy at the ceiling corner (difference between the center and the corner) was calculated, and the uniformity of the fungicidal effect was determined from the value based on the following criteria. The results are shown in Tables 1-3.
<Criteria>
A: The difference between the center and the corner is less than 1.
○: The difference between the center and the corner is 1 or more and less than 2.
Δ: The difference between the center and the corner is 2 or more and less than 3.
X: The difference between the center and the corner is 3 or more.

[2. Evaluation of sustainability of fungicidal effect]
(Evaluation method)
First, as shown in FIG. 5, slide in the center of the ceiling surface of a sealable evaluation room (height from the floor surface to the ceiling surface: about 2 m) having the same volume as the 1818 type (for meter module) bathroom. Glass 51 (manufactured by Matsunami Glass Industrial Co., Ltd., white edge polishing No. 2, 76 × 26 mm) 51 was attached.
Next, the total amount injection type aerosol product 33 (the total amount injection type aerosol product manufactured in each example) was placed on the central floor surface in the evaluation room, and the contents were injected.
After 90 minutes from the injection of the contents, the air in the evaluation chamber was exhausted, and the slide glass 51 was collected.
The slide glass 51 was placed in a 500 mL beaker containing about 500 mL of tap water (amount in which the entire slide glass was immersed), left standing for 30 seconds, and then taken out and dried at room temperature.
Cladospodium cladosporeoids HMC1064 (bathroom isolate) cultured on a potato dextrose agar (Difco) slant medium at 25 ° C. for 1 week was diluted to 50% and sterilized using a potato dextrose liquid medium of about 102 CFU / mL. A spore solution was prepared and inoculated into the slide glass 51 by 0.1 mL.
The slide glass 51 is covered with a film cut to 12.1 cm × 1 cm (film described in JIS Z 2801 (antibacterial test method / antibacterial effect of antibacterial processed products)) so as to cover the spore solution, and 25 ° C. The cells were cultured for 7 days under conditions of relative humidity of 98% or higher.
After the culture, the bacteria were collected from the slide glass 51, smeared on a potato dextrose agar medium, and the number of colonies after culturing at 25 ° C. for 5 days was counted.
The same operation was performed on an untreated slide glass, and the bacteria were collected, smeared on a potato dextrose agar medium, and the number of colonies after culturing at 25 ° C. for 5 days was counted.
From the above results, the sustainability of the fungicidal effect was evaluated according to the following evaluation criteria.

(Evaluation criteria)
The number of colonies formed from the bacteria recovered from the slide glass 51 (the slide glass sprayed with the contents) relative to the number of colonies formed from the bacteria recovered from the untreated slide glass (the number of untreated colonies) The ratio of the number of colonies after) was calculated according to the following formula, and the value was defined as the rate of reduction of the fungicidal effect. Based on the value, the sustainability of the fungicidal effect was determined according to the following criteria. The results are shown in Tables 1-3.
Antifungal effect reduction rate = number of colonies after treatment / number of untreated colonies × 100 (%)
<Criteria>
○: The mold-proof effect reduction rate is less than 70%.
(Triangle | delta): The antifungal effect fall rate is 70% or more and less than 90%.
X: The mold-proof effect fall rate is 90% or more.

As shown in the above results, all of the aerosol injection products of Examples 1 to 25 had a good fungicidal effect, high uniformity of the fungicidal effect, and good sustainability of the fungicidal effect. In particular, the sustainability of the antifungal effect was excellent when a nonionic surfactant having a HLB of 2 to 16 or a water-soluble polymer compound was blended.
On the other hand, Comparative Examples 1 to 3 not containing the component (A) had a low fungicidal effect and a low durability of the fungicidal effect.
In Comparative Example 4 using a solvent having a boiling point of 36.07 ° C., the fungicidal effect at the ceiling corner was low. In addition, the antifungal effect was low.
In Comparative Example 5 using a solvent having a boiling point of 275 ° C., the fungicidal effect at the ceiling corner was low, and the uniformity of the fungicidal effect was low.
In Comparative Example 6 using liquefied petroleum gas as the propellant, the fungicidal effect at the ceiling corner was low, and the uniformity of the fungicidal effect was low. In addition, the antifungal effect was low.
In Comparative Example 7 using compressed nitrogen as a propellant, the fungicidal effect was low. In addition, the antifungal effect was low.
In Comparative Example 8 where B / C was 1.12, the fungicidal effect at the ceiling corner was low, and the uniformity of the fungicidal effect was low. In addition, the antifungal effect was low.
In Comparative Example 9 where B / C was 0.08, the uniformity of the fungicidal effect was low.

1 Full-injection aerosol product 2 Spray can 3 Nozzle cap 4 Stem 5 Cap body 6 Push button 7 Injection nozzle 8 Shoulder cover

Claims (3)

A full-injection aerosol product filled with contents in a container,
The content is an inorganic agent (A) having a transition metal, a solvent (B) having a boiling point of 70 to 200 ° C., a propellant (C) containing dimethyl ether, and a nonionic property having an HLB of 2 or more and less than 16. A surfactant (D) ,
A mass injection type aerosol product, wherein a mass ratio (B / C) of the solvent (B) to the propellant (C) is 0.1 to 1.0. The all-injection aerosol product according to claim 1, wherein the content further contains a water-soluble polymer compound (E). The all-injection type aerosol product according to claim 1 or 2 , which is used for mold prevention in a bathroom.

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