JP5537978B2 - Fixed-quantity aerosol products - Google Patents

Description

  The present invention relates to a metered injection type aerosol product.

  In recent years, aerosol products have been used for various applications, and various aerosol products have been developed according to the applications. One example is a quantitative injection type aerosol product that injects a predetermined amount of contents in one injection operation, and such an aerosol product is used in, for example, fragrances and insecticides (Patent Documents). 1 and 2).

JP 2005-272012 A JP 2001-335083 A

However, such a fixed-injection type aerosol product having an aerosol valve having a fixed-injection function has a predetermined injection amount after the product is opened or not used for a long time. May be smaller. It has been found by the applicant's earnest examination that this is because the aerosol composition once introduced into the housing of the valve returns to the container body over time and decreases.
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a quantitative injection type aerosol product in which the injection amount is constant regardless of the operation.

An aerosol product of a quantitative injection type according to the present invention comprises an aerosol container and an aerosol composition filled in the aerosol container, and the aerosol container has a quantitative injection mechanism for injecting a predetermined amount of the aerosol composition. The aerosol composition is a metered-injection aerosol product comprising: an aerosol composition comprising a stock solution, a liquefied gas, and a low-solubility compressed gas, and an Ostwald absorption coefficient for the solvent of the low-solubility compressed gas is 0.3 or less , the pressure of the aerosol container is, 0.05 to 0.3 MPa higher than the saturation vapor pressure of the liquefied gas, when the operation of opening the aerosol valve, a predetermined amount per one time of the aerosol composition is injected It is characterized by 0.2 to 1.0 ml.
In the present invention, the low-solubility compressed gas means a low-solubility gas in a stock solution or a liquefied gas, and is appropriately determined according to the stock solution or the liquefied gas.

  In such a quantitative injection type aerosol product, the housing of the aerosol valve includes an introduction passage that does not directly communicate with the gas phase portion in the aerosol container, but communicates with the liquid phase portion in the aerosol container, The quantitative injection mechanism is preferably a mechanism that closes or partially closes the introduction passage by opening an aerosol valve. Moreover, a ball is mentioned as closing or partially closing the introduction passage.

  Furthermore, it is preferable to use such a fixed injection type aerosol product, in which the compressed gas is air. Further, the saturated vapor pressure of the liquefied gas at 25 ° C. is 0.2 to 0.6 MPa, and the liquefied gas is preferably contained in the aerosol composition in an amount of 50 to 90 Vol%.

In the quantitative injection type aerosol product of the present invention, the aerosol composition contains a stock solution, a liquefied gas, and a low solubility compressed gas, and the Ostwald absorption coefficient of the low solubility compressed gas with respect to the solvent is 0.3 or less, When the pressure in the aerosol container is 0.05 to 0.3 MPa higher than the saturated vapor pressure of the liquefied gas and the aerosol valve is opened, the predetermined amount per time the aerosol composition is injected is 0.00. Since it is 2 to 1.0 ml, the pressure in the aerosol container (gas phase portion) is slightly higher than the pressure in the housing of the aerosol valve. Therefore, the stock solution and the liquefied gas filled in the housing are unlikely to return to the aerosol container, and a certain amount of the aerosol composition is injected even when operated after standing for a long time.

The metered injection type aerosol product of the present invention, wherein the aerosol valve housing does not directly communicate with the gas phase part in the aerosol container, and has an introduction passage communicating with the liquid phase part in the aerosol container, When the metering injection mechanism is a mechanism for closing or partially closing the introduction passage by opening the aerosol valve, only the liquid aerosol composition introduced from the introduction passage is accumulated in the housing of the aerosol valve. . That is, the low-solubility compressed gas surely remains in the gas phase portion in the aerosol container. Therefore, the difference between the pressure in the gas phase (compressed gas + saturated vapor pressure of liquefied gas) and the pressure in the housing (saturated vapor pressure of liquefied gas) can be maintained for a longer period.
Further, when the saturated vapor pressure at 25 ° C. of the liquefied gas is 0.2 to 0.6 MPa, and the liquefied gas is contained in the aerosol composition in an amount of 50 to 90 vol%, the aerosol is highly safe and highly effective. A product is obtained.

It is a section side view showing one embodiment of the aerosol product of the present invention. It is an enlarged view of the aerosol valve of FIG. It is an enlarged view which shows the state immediately after injection of the aerosol valve | bulb of FIG.

Next, the quantitative injection type aerosol product of the present invention will be described with reference to the drawings.
The aerosol product 10 shown in FIG. 1 is composed of a fixed injection type aerosol container 11 and an aerosol composition 12 (gas phase part A and liquid phase part B) filled therein.

The aerosol container 11 includes a pressure-resistant container main body 13 and a fixed-quantity injection type aerosol valve 14 attached to the opening. The container main body 13 and the aerosol valve 14 are each provided in one aerosol valve 14. It is configured to communicate only with the introduction passage 15.
The container body 13 is made of metal and is a general one provided with a bottom portion 13a, a trunk portion 13b, a shoulder portion 13c, and a bead portion 13d.

  As shown in FIG. 2, the aerosol valve 14 includes a cylindrical housing 21, a stem 22 accommodated in the housing so as to be movable up and down, a spring 23 that constantly biases the stem upward, and a stem of the stem. A stem rubber 24 that closes the hole, a mounting cup 25 that covers the upper portion of the housing 21 and is fixed to the container body 13, a cylindrical metering housing 26 that is attached to the lower end of the housing, and a vertically movable housing are accommodated in the metering housing. And a dip tube 28 attached to the lower end of the metering housing. In addition, a cylindrical bush 29 is provided between the housing 21 and the metering housing 26 so that when the ball 27 reaches the upper end of the metering housing 26, the introduction passage 15 is reliably closed by the ball 27. (See FIG. 3).

Returning to FIG. 2, the housing 21 has an upper end that is open and an upper cylindrical portion 21 a that accommodates the stem 22, a lower end that is open and a lower cylindrical portion 21 b that accommodates the bush 29, and The upper cylinder part 21a and the lower cylinder part 21b are communicated with each other through a communication hole 21d formed at the center of the partition wall 21c. The housing 21 does not include a hole that directly communicates with the gas phase portion in the aerosol container.
The stem 22 has a bottomed cylindrical shape, is open at the upper end, and has a stem hole 22a on the side surface.
The spring 23 is provided between the lower end of the stem 22 and the partition wall 21 c of the housing 21.
The stem rubber 24 has a ring shape that closes the stem hole 22 a and is sandwiched between the upper end opening of the housing 21 and the mounting cup 25.

The mounting cup 25 includes a mounting portion 25a fixed to the bead portion, a central housing holding portion 25b, and a connecting portion 25c that connects the mounting portion 25a and the housing holding portion 25b. Is formed with a central hole that allows the stem 22 to protrude.
The fixed amount housing 26 includes a housing mounting portion 26a that receives the lower cylindrical portion 21b of the housing, a ball accommodating portion 26b that accommodates the ball 27, and a cylindrical coupling portion 26c to which the dip tube 28 is coupled. The diameter of the ball housing portion 26 b is configured to be larger than the ball 27.
The bush 29 includes an insertion portion 29a inserted into the lower cylindrical portion 21b of the housing and a lower end opening portion 29b that receives the ball 27, and an inner surface of the lower end opening portion 29b is tapered so as to expand downward. Yes. The lower end opening 29b receives the ball 27 and closes the introduction passage 15.

The introduction passage 15 includes a housing 21, a bush 29, a metering housing 26, and a dip tube 28. By performing an injection operation of the aerosol product 10 (an operation of pushing an injection member (not shown) attached to the stem downward), the aerosol valve 14 is opened, and the ball housing portion 26b of the metering housing is opened from within the housing 21. The aerosol composition is injected from the opening of the stem. At the same time, the ball 27 contacts the lower end opening 29b of the bush 29, and the introduction passage 15 is closed (see FIG. 3). Thereby, the fixed amount aerosol composition stored in the housing 21 to the ball housing portion 26b of the fixed amount housing is injected. Its volume is 0.2 to 1.0 ml, in particular 0.3 to 0.7 ml. On the other hand, when the aerosol valve 14 is closed, the ball 27 moves below the ball housing portion 26b, and at the same time, the closing of the introduction passage 15 (lower end opening 29b) is also released. As a result, the liquid (raw liquid and liquefied gas liquid) in the aerosol container is stored again in the housing 21 and in the ball housing portion 26b of the metering housing.
In order to make it easier for the ball to return to its original position after injection, a cut may be made in the lower end opening of the bush to provide a passage between the ball and the passage between the lower tube portion of the housing and the bush. May be provided. In this case, even if the ball 27 closes the lower end opening 29, the introduction passage 15 is not completely blocked. However, by making the cross-sectional area of the cut or passage smaller than the cross-sectional area of the other part of the introduction passage 15, the injection (quantitative injection) when the stored aerosol composition is injected and the subsequent injection There is a difference in the injection amount. By confirming this change, the operator can recognize that the quantitative injection has been performed. The quantitative injection mechanism used in the present invention includes a mechanism capable of recognizing that a fixed amount of the aerosol composition has been injected.

The aerosol composition 12 is composed of a stock solution, a liquefied gas, and a low solubility compressed gas.
The stock solution is obtained by dissolving an active ingredient in a solvent, becomes a fine mist when sprayed into the atmosphere, adheres to an object, and exhibits the effectiveness of the active ingredient. Further, a surfactant or the like is appropriately blended according to the use and purpose.

Examples of the active ingredient include insecticides, repellents, acaricides, fungicides for fungi and fungi, antibacterial agents and fungicides, stabilizers, fragrances, excipients and the like.
Examples of the insecticidal component include transfluthrin, methfluthrin, profluthrin, imiprothrin, phthalthrin, phenothrin, permethrin, ciphenothrin, cypermethrin, resmethrin, allethrin, praretrin, framethrin, etofenprox and other pyrethroid compounds, silafluophene, etc. These are silicon compounds, organophosphorus compounds such as fenitrothion, and carbamate compounds such as propoxle. Of these, pyrethroid compounds are preferred from the viewpoint of insecticidal efficacy and safety.
Examples of the repellent include dibutyl sebacate and N, N-diethyl-m-toluamide, and examples of the acaricide include methyl 5-chloro-2-trifluoromethanesulfonamide benzoate, phenyl salicylate, 3- Examples thereof include iodo-2-propynylbutyl carbamate, and examples of the fungicide, antibacterial agent and fungicide include 2-mercaptobenzothiazole, 2- (4-thiazolyl) benzimidazole, triphorine, 3-methyl-4- Examples thereof include isopropylphenol and ortho-phenylphenol.
The active ingredient is contained in an amount of 0.01 to 80.0% by weight based on the whole stock solution. If it is less than 0.01% by weight, it is difficult to obtain a desired effect, while if it exceeds 80.0% by weight, the stability of the aerosol composition tends to be lowered.

Examples of the solvent include alcohol solvents such as ethanol and isopropanol, glycol solvents such as propylene glycol and dipropylene glycol, glycol ether solvents such as diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether, and higher grades such as isopropyl myristate. And hydrocarbon solvents such as fatty acid ester solvents, kerosene, and liquid paraffin. The solvent is appropriately determined depending on the active ingredient, and the stock solution is prepared by adding the active ingredient to the solvent.
The stock solution is preferably 10 to 50% by volume in the aerosol composition, more preferably 20 to 40% by volume. When the amount is less than 10% by volume, the amount of spray particles decreases, and the effectiveness tends to be weak. On the other hand, when the amount exceeds 50% by volume, the mist becomes rough, and when sprayed into a space, the effect tends to drop and it is difficult to maintain the effect.

The liquefied gas is a liquid having a vapor pressure in the aerosol container, and when injected into the atmosphere, it changes to a gas and makes the stock solution into a fine mist.
Examples of the liquefied gas include liquefied petroleum gas, dimethyl ether, and a mixed gas of liquefied petroleum gas and dimethyl ether. The saturated vapor pressure at 25 ° C. of the liquefied gas is preferably 0.2 to 0.6 MPa, and more preferably 0.3 to 0.5 MPa. When the saturated vapor pressure is less than 0.2 MPa, the reach distance of the spray particles tends to be short, and when it exceeds 0.6 MPa, the pressure in the aerosol container is increased due to the temperature rise and the safety is lowered.
The liquefied gas is preferably contained in the aerosol composition in an amount of 50 to 90% by volume, and more preferably 60 to 80% by volume. If it is less than 50% by volume, the fog becomes rough, and when sprayed into the space, it is easy to fall and the effect is difficult to sustain. On the other hand, if it exceeds 90% by volume, the amount of spray particles decreases, and the efficacy tends to be weak.

The low-solubility compressed gas is a compressed gas having low solubility in the stock solution and the liquefied gas, and the pressure in the aerosol container is 0.05 to 0.3 MPa, particularly 0.07 to 0.2 MPa higher than the saturated vapor pressure of the liquefied gas. To do. Thus, the liquid volume of the aerosol composition introduced into the housing can be maintained by making the pressure in the gas phase part of the aerosol container higher than the saturated vapor pressure of the liquefied gas.
Examples of the low-solubility compressed gas include those having an Ostwald absorption coefficient of 0.3 or less with respect to the solvent used, such as nitrogen gas, oxygen gas, and compressed air. For example, when ethanol is used as the solvent, nitrogen gas is 0.143, oxygen gas is 0.220, and air is 0.158 (air is an actual measurement value). When the Ostwald absorption coefficient exceeds 0.3, the amount of dissolution increases, and the pressure in the container increases at high temperatures, which may reduce safety. However, the gas is not particularly limited as long as it is a gas exhibiting the low solubility described above with respect to the solvent of the stock solution and the liquefied gas.
The low-solubility compressed gas may be filled with a stock solution and a liquefied gas in a container, and after filling the valve so as to reach a predetermined pressure from the stem of the valve. The air in the container may be compressed by filling the liquefied gas without vacuuming, and crimping the valve.

  Since the aerosol valve housing 21 of the aerosol product 10 is not in direct communication with the gas phase portion A in the aerosol container 11, the aerosol valve housing 21 is liquid (raw liquid and liquefied gas as components of the liquid phase portion B). Filled by. That is, the pressure in the housing 21 is smaller than the pressure in the aerosol container 11 by the amount of compressed gas. Therefore, the liquid in the housing 21 of the aerosol valve is always pressed upward by the gas phase part A in the aerosol container via the liquid phase part B in the aerosol container 11 to reduce the liquid in the housing 21. To prevent.

In the present invention, a compressed gas is introduced into the aerosol composition, and the pressure in the gas phase in the aerosol container is made larger than the pressure in the housing of the aerosol valve, whereby the liquid in the housing 21 (raw liquid and liquefied gas liquid). Is prevented, and the injection amount is stabilized, particularly the initial injection amount is stabilized.
In the embodiment of FIG. 1, the one in which the introduction passage from the liquid phase portion of the aerosol container into the housing of the aerosol valve is closed with a ball is disclosed. However, as shown in FIG. 10 or FIG. 11 of Patent Document 1 and FIG. 1 of Patent Document 2, the introduction passage may be closed with a stem.

Moreover, although the fixed quantity injection mechanism which can recognize that a fixed quantity aerosol composition was injected, such as making a cut in the lower end opening part 26 of the bush of FIG. 2, was demonstrated, as shown in FIG. By using a quantitative injection type aerosol container that can recognize that a predetermined amount of the aerosol composition has been injected by changing the injection amount by narrowing the area of the introduction passage (partially closed) May be.
Further, as shown in FIG. 1 of Patent Document 1, an aerosol container in which the cross-sectional area of the introduction passage (or introduction hole) is smaller than the cross-sectional area of the injection passage, and a predetermined amount of aerosol composition stored in the aerosol valve is stored. You may use the fixed-quantity injection type aerosol container which can recognize that the fixed-quantity aerosol composition was injected by changing the injection quantity (momentum) of injection (quantitative injection) of a thing, and subsequent injection.

"Example 1"
The aerosol container 11 of FIG. 1 was prepared. A stock solution was prepared by blending 5% by weight of transfluthrin with 95% by weight of ethanol. Next, the above-mentioned stock solution and liquefied petroleum gas (saturated vapor pressure at 25 ° C. of 0.4 MPa) were filled in an aerosol container having an atmospheric pressure inside such that the liquid volume ratio was 3: 7. The pressure in this aerosol container at 25 ° C. was 0.5 MPa.

"Example 2"
The aerosol container 11 shown in FIG. 1 is prepared, and the same undiluted solution and liquefied petroleum gas (saturated vapor pressure at 25 ° C. at 0.4 ° C.) as in Example 1 are contained in an aerosol container having an atmospheric pressure inside at a liquid volume ratio of 3: 7 and filled with nitrogen gas. The pressure at 25 ° C. in the aerosol container was 0.55 MPa.

"Example 3"
The aerosol container 11 of FIG. 1 is prepared, and after filling the same stock solution as in Example 1, the space is vacuumed and depressurized, filled with liquefied petroleum gas (saturated vapor pressure at 25 ° C. is 0.4 MPa), and further nitrogen Filled with gas. The liquid volume ratio between the stock solution and the liquefied petroleum gas is 3: 7. The pressure in this aerosol container at 25 ° C. was 0.7 MPa.

"Comparative Example 1"
The aerosol container 11 of FIG. 1 was prepared, and after filling the same stock solution as in Example 1, the space was vacuumed and decompressed, and liquefied petroleum gas (saturated vapor pressure at 25 ° C. was 0.4 MPa) was filled. The liquid volume ratio between the stock solution and the liquefied petroleum gas is 3: 7. The pressure in this aerosol container at 25 ° C. was 0.4 MPa.
"Comparative Example 2"
The aerosol container 11 of FIG. 1 was prepared, and after filling the same stock solution as in Example 1, the space was vacuumed and decompressed, and liquefied petroleum gas (saturated vapor pressure at 25 ° C. was 0.2 MPa) was filled. The liquid volume ratio between the stock solution and the liquefied petroleum gas is 3: 7. The pressure at 25 ° C. in the aerosol container was 0.22 MPa.
“Comparative Example 3”
The aerosol container 11 of FIG. 1 was prepared, and after filling the same stock solution as in Example 1, the space was vacuumed and decompressed, and liquefied petroleum gas (saturated vapor pressure at 25 ° C. was 0.6 MPa) was filled. The liquid volume ratio between the stock solution and the liquefied petroleum gas is 3: 7. The pressure at 25 ° C. in the aerosol container was 0.58 MPa.

  The aerosol products of Examples 1 to 3 and Comparative Examples 1 to 3 were stored in a constant temperature water bath at 25 ° C., and the injection amount after 1 hour, the injection amount after 7 days, and the injection amount after 18 days were measured. The measurement results are shown in Table 1 below. In addition, the gas pressure in Table 1 indicates the saturated vapor pressure (MPa) at 25 ° C. of the liquefied gas, and the product pressure indicates the pressure (MPa) in the aerosol container.

  As is clear from Table 1, the injection amounts of Examples 1 to 3 showed stable numerical values. On the other hand, in Comparative Examples 1 to 3, a decrease in the injection amount was observed with a storage period of 7 days.

A Gas phase part B Liquid phase part 10 Aerosol product 11 Aerosol container 12 Aerosol composition 13 Container body 13a Bottom part 13b Body part 13c Shoulder part 13d Bead part 14 Constant injection type aerosol valve 15 Introduction passage 21 Housing 21a Upper cylinder part 21b Bottom Tube portion 21c Bulkhead 21d Communication hole 22 Stem 22a Stem hole 23 Spring 24 Stem rubber 25 Mounting cup 25a Mount portion 25b Housing holding portion 25c Connecting portion 26 Fixed housing 26a Housing mounting portion 26b Ball housing portion 26c Connecting portion 27 Ball 28 Dip tube 29 Bush 29a Insert 29b Lower end opening

Claims (5)

This is a metered-injection type aerosol product comprising an aerosol container and an aerosol composition filled in the aerosol container, the aerosol container having an aerosol valve having a quantitative injection mechanism for injecting a predetermined amount of the aerosol composition. And
The aerosol composition comprises a stock solution, a liquefied gas and a low solubility compressed gas;
Ostwald absorption coefficient for the solvent of the low solubility compressed gas is 0.3 or less,
The pressure in the aerosol container is 0.05 to 0.3 MPa higher than the saturated vapor pressure of the liquefied gas,
When the operation of opening the aerosol valve, the predetermined amount per time the aerosol composition is injected is 0.2 to 1.0 ml,
A fixed-injection aerosol product. The aerosol valve housing does not directly communicate with the gas phase part in the aerosol container, but has an introduction passage communicating with the liquid phase part in the aerosol container,
The metered injection type aerosol product according to claim 1, wherein the metered injection mechanism is a mechanism for closing or partially closing the introduction passage by opening an aerosol valve. 3. A metered dose aerosol product according to claim 2, wherein the introduction passage is closed by a ball. The metered injection type aerosol product according to claim 1, wherein the compressed gas is air. The liquefied gas has a saturated vapor pressure at 25 ° C. of 0.2 to 0.6 MPa,
The quantitative injection type aerosol product according to claim 1, wherein the liquefied gas is contained in an aerosol composition in an amount of 50 to 90 Vol%.