JPH0873839A - Aerosol product using compressed gas and production of the aerosol product - Google Patents

Abstract

PURPOSE: To obtain the subject product consisting of a specific constitution, CO2 and an undissolvable compressed gas as propellants, capable of favorably retaining its spraying status to the last by making the best use of the advantages of both the CO2 as the dissolvable compressed gas and the undissolvable compressed gas. CONSTITUTION: (A) A stock solution, i.e., an aqueous solution or an alcoholic aqueous solution, containing an active ingredient or surfactant, (B) a carbonate or bicarbonate (pref. sodium carbonate or sodium bicarbonate) and (C) an organic or inorganic acid (pref. citric acid or hydrochloric acid), are put into an aerosol vessel followed by sealing and then pressurizing the vessel with an undissolvable compressed gas (e.g. N2 , helium), thus obtaining the objective product. Specifically, this product is obtained by the following procedure: either of the component B or C is incorporated, in advance, in the component A, and the other is then incorporated in the form of e.g. a water-soluble capsule in the component A. It is recommended that the undissolvable compressed gas be filled immediately after sealing the vessel. It is preferable that the pressure of the gas inside the vessel is adjusted to 3.5-7.8kg/cm<2> at normal temperatures.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aerosol product which uses a compressed gas as a propellant and a method for producing the same.

[0002]

2. Description of the Related Art Some aerosol products use a liquefied gas and a compressed gas as a propellant.
As the liquefied gas, propane, butane, isobutane, dimethyl ether, etc. are used alone or as a mixture, and although the injection characteristics are good, they are all flammable.
In the manufacturing process, it is necessary to have appropriate equipment and management system that handles flammable high-pressure gas, and as a precaution for using the product, the product is marked with flammability and fire caution, and sufficient caution should be taken for transportation and storage. is necessary. As the compressed gas, carbon dioxide, nitrogen, oxygen, air, helium, argon or the like is used as a propellant. In this case, unlike the case of liquefied gas, there is a drawback of pressure drop. That is, when carbon dioxide is used as the compressed gas and a water-soluble base is used, carbon dioxide is a constant amount of carbon dioxide in the water-soluble base under a constant pressure according to Henry's law of gas dissolution. Dissolve in. Due to this dissolved gas, the initial injection state of the product is good, but the injection state deteriorates from the middle stage to the final stage. This is because as the content liquid decreases, the volume of the gas portion in the container increases, the internal pressure of the container decreases according to Boyle's law, and as the pressure decreases, carbon dioxide gas evaporates and drops from the water-soluble base. Since a part of the pressure is replenished, the amount of dissolved gas in the water-soluble base is reduced as a result, and the injection state is deteriorated in combination with the pressure drop.

When nitrogen gas is used as the compressed gas, unlike carbon dioxide gas, the amount of gas dissolved in the liquid is small.
For example, the dissolved amount of water of the nitrogen gas is 20 ° C., it was 0.016 ml / MLH ₂ O at 1 atm, dissolved amount of water of carbon dioxide 20 ° C., is 0.88 ml / MLH ₂ O at 1 atm. Therefore, when filling the water-soluble base and pressurizing only with nitrogen gas to make a product, the product is in a poor injection state, as can be judged from the gas insolubility in the liquid, and the valve structure to improve this is The button structure was devised to require a fine liquid passage and a spray mechanism. For this reason, it is costly and there is an instability of the spray state caused by the fine structure. At the same time, since it behaves in accordance with Boyle's law as an advantage of the insoluble compressed gas, it is easy to fill the gas and accurately predicts the decrease in pressure with the consumption of the content liquid when designing. I was able to do something.

As described above, by using the soluble compressed gas and / or the insoluble compressed gas, which are safer than the liquefied gas, as a propellant for an aerosol product, two compressed gas components are prepared by a conventional method. In the filling process, depending on the pressure filling method, the filling is performed using two pressure filling heads, one for every one of the two components, that is, a total of two pressure filling heads. When the soluble compressed gas and the insoluble compressed gas are combined, the soluble compressed gas is first filled and then the insoluble compressed gas is filled. At the time of filling, the filling pressure is set as high as possible while considering the pressure resistance of the can. This is of course to increase the filling speed. Normally, the pressure is set to about 15 to 20 kg / cm ² G, so that the pressure resistance of the can is filled to the limit, and the liquid in the can is absorbed so as to be filled. In order to accelerate the gas absorption depending on the content liquid, technologies such as vibrating the can and devising the mechanism of the aerosol valve to accelerate the gas passage speed have been introduced. At the same time, it takes a considerable amount of time until the equilibrium pressure is reached by absorbing carbon dioxide into the content liquid. It is necessary to take a few minutes of idle time before pressure-filling carbon dioxide gas at least and then filling nitrogen gas. This means that it is not possible to fill the two components of compressed gas in a continuous process in a series of filling devices. It is uneconomical to construct a line that fills the compressed gas of the second component with an idle time of several minutes, because it costs a lot in terms of location and investment. As another method, it is possible to mix two components of compressed gas in advance and pressurize, but in the case of carbon dioxide gas and nitrogen gas, physicochemical properties Is. This causes problems in the filling process. That is, during filling, there is a depressurization step from the cylinder in which the mixed gas is stored as a raw material to the filling device via the pipe, the pressure reducing valve, and the like. At this time, there is a disadvantage that the carbon dioxide gas is liquefied by cooling due to the adiabatic expansion and the component ratio of the mixed gas is changed. Further, the quality control of the mixed gas of the compressed gas as the raw material gas is complicated and difficult, and the control of the gas amount of the filled aerosol product becomes very difficult. More than,
This is a big problem when filling two components as compressed gas by the conventional method.

[0005]

Therefore, an object of the present invention is to make up for each of the above disadvantages of the soluble compressed gas (eg, carbon dioxide gas) and the insoluble compressed gas (eg, nitrogen gas), and to provide advantages. The present invention proposes better aerosol products and foamy aerosol products by utilizing the above. Further, the object of the present invention is to provide a method for producing an aerosol product using the two-component compressed gas proposed here, which can be easily and simply devised with a more rational method than the conventional method. Is proposed.

[0006]

The object of the present invention can be achieved by the following constitutions (1) to (3). (1) Using an aqueous solution containing an active ingredient, an aqueous solution containing a surfactant, or an alcoholic aqueous solution as a stock solution, a stock solution, a predetermined amount of carbonate or hydrogen carbonate, and a predetermined amount of an organic acid in an aerosol container, or An aerosol product characterized by containing and sealing an inorganic acid and pressurizing with a non-soluble compressed gas. (2) A liquid obtained by adding a hydrocarbon oil having a carbon number of 5 or more to an aqueous liquid containing a surfactant is used as a stock solution, and a stock solution, a predetermined amount of carbonate or hydrogen carbonate, and a predetermined amount of organic solution are contained in an aerosol container. A foamy aerosol product, characterized by containing and sealing an acid or an inorganic acid and pressurizing with a non-soluble compressed gas. (3) When a stock solution, a predetermined amount of a carbonate group or a carbonate group of hydrogen carbonate, and a predetermined amount of an acid group of an organic acid or an inorganic acid are stored in an aerosol can, either the carbonate group or the acid group is previously prepared as a stock solution. The method for producing an aerosol product according to claim 1 or 2, wherein the other group is charged as a water-soluble capsule or the like and sealed.

The present invention comprises a stock solution, a carbonate or a hydrogen carbonate (carbonate group) and an organic acid or an inorganic acid (acid group).
By accommodating and sealing, and pressurizing with a compression-insoluble gas, an aerosol product with a good injection state can be obtained until the end, and by making it a system that generates carbon dioxide gas from a carbonic acid group and an acid group, Manufacture of an aerosol product capable of easily and simply filling two components of a compressible gas (for example, carbon dioxide gas) and a non-soluble compressed gas (for example, compressed insoluble gas) (for example, nitrogen gas). A method can be provided. In addition, depending on the type of aerosol product, even if a gas that is insoluble in compression is not used, carbon dioxide gas is generated from the carbonate or hydrogen carbonate and the organic acid or inorganic acid in the aerosol can until the end. It is possible to provide an aerosol product having a good jetting state and a method for manufacturing an aerosol product which can be easily and conveniently carried out. When the pH of the mixed solution is adjusted to be substantially neutral, the predetermined amounts of the carbonic acid group and the acid group are preferable as calculated by the chemical equation. When a water-soluble capsule in which an organic acid or an inorganic acid is encapsulated is added, even if it is added to a solution in which a carbonate or a hydrogen carbonate is dissolved, a reaction does not occur immediately and the sealing work is facilitated. In some cases, an organic acid or an inorganic acid can be used in the form of powder. In the present invention, the stock solution is not particularly limited, but it is preferable that the stock solution constitutes an aerosol product such as an aqueous solution containing an active ingredient, an aqueous solution containing a surfactant, or an alcoholic aqueous solution. Also,
In the present invention, the stock solution is a stock solution that constitutes a foam-like aerosol product in which a water-soluble hydrocarbon oil containing a surfactant and having 5 or more carbon atoms, preferably 5 to 7, is added. Further, the components such as the above-mentioned active ingredient, surfactant, alcoholic aqueous solution and the like are not particularly limited and may be any as long as they are used in aerosol products.

The present invention will be described in detail below. First, carbon dioxide gas is generated in the aerosol container. That is, the carbonate or hydrogen carbonate is dissolved in an aqueous solution containing various active ingredients, an emulsion solution, or an alcoholic aqueous solution, and this is stored in an aerosol container, to which a predetermined amount of an organic acid or an inorganic acid is added, If it is sealed, a certain amount of carbon dioxide gas will be generated. In the present invention, the predetermined amount means an amount calculated and determined by a chemical equation from the amount of carbon dioxide gas to be generated. The generation of carbon dioxide gas will be described by taking sodium hydrogen carbonate as a hydrogen carbonate and citric acid as an organic acid. Sodium hydrogen carbonate has the chemical formula NaHC
O ₃ and citric acid is C ₆ H ₈ O ₇ .H ₂ O. As is well known, the reaction of these two in an aqueous solution produces 1 mol of citric acid and 3 mol of NaHCO ₃ to generate 3 mol of carbon dioxide gas, 1 mol of sodium citrate and 3 mol of water.
That is, when expressed by a chemical reaction formula, formula [1] is obtained.

[0009]

Embedded image

The respective molecular weights are citric acid = 210.14 NaHCO ₃ = 84.02 CO ₂ = 44, and NaH required depending on the amount of carbon dioxide gas to be generated.
The amounts of CO ₃ and citric acid can be calculated.
On the other hand, the amount of carbon dioxide dissolved in an aqueous solution has been accurately grasped by various studies. For example, according to the book “Soft Drinks” (Editing Committee of Soft Drinks published by Korin), the carbon dioxide absorption coefficient at each pressure is described for a sucrose aqueous solution at a temperature of 25 ° C. (768 to 76).
Page 9).

[0011]

[Table 1]

Here, the carbon dioxide gas mass C is obtained by C = (V) × (absorption coefficient) × 1.976 (gr / l) ... Equation (2). However, V = volume of solution (l) Now, take an aerosol container (full volume 156 ml), and put into it the stock solution of Example (1) (that is, aqueous solution containing active ingredient) 9
The amount of carbon dioxide gas required when filling 0 ml and filling carbon dioxide gas according to the present invention to an internal pressure of 5.0 kg / cm ² is calculated by the formula (2) as follows. From Table 1, the absorption coefficient of carbon dioxide is at 25 ° C., the absorption coefficient is 4.43, and the mass of carbon dioxide in the solution is (C ₁ ).

[0013]

[Formula 1]

C ₁ = 0.787 gr Carbon dioxide gas occupying 66 ml of head space is also 5 kg / c
Since the pressure of m ² is shown, the carbon dioxide gas mass in this space is (C ₂ gr)

[0015]

[Formula 2]

C ₂ = 0.760 gr The total weight of carbon dioxide in the aerosol container is C = C ₁ + C ₂ = 1.547 (gr) According to the above chemical reaction formula [1], 3 mol of NaHCO 3 is used.
_{Since 3} mol of carbon dioxide gas is generated from ₃ and 1 mol of citric acid, the above-mentioned 1.547 gr of CO ₂ can be obtained.

[0017]

[Formula 3]

[0018]

[Formula 4]

From NaHCO ₃ ...... 2.954 gr …… [Formula 3], each amount of citric acid ………… 2.462 gr …… [Formula 4] is required. Each of these amounts is a predetermined amount. According to the present example (described later), the result of the internal pressure of 5 kg / cm ² was obtained by the formulation of the aerosol container (full amount 156 ml), the aqueous solution 90 ml NaHCO _{3 3} gr citric acid 2.5 gr. That is, take 90 ml of the above aqueous solution and add 3 g of NaH
Add CO ₃ and stir. This was filled in an aerosol container, 2.5 gr of citric acid wrapped in wafer paper was added, and the aerosol valve was crimped. After 7 minutes, 5 kg
An internal pressure of / cm ² (room temperature) was obtained.

In the above pressure generation step, when a predetermined amount of NaHCO ₃ is dissolved in a stock solution such as an aqueous solution containing various active ingredients, and when a predetermined amount of citric acid is added thereto, the citric acid is directly dissolved in the solution. If the liquid is thrown into the container, a reaction immediately occurs, a foaming phenomenon occurs, and the content liquid overflows from the mouth of the container, so that the valve cannot be crimped. Therefore, it is preferable to wrap a certain amount of citric acid with a water-soluble resin-Ex polyvinyl alcohol film, water-soluble fiber, etc., and add it in the form of a capsule. As a method to make capsules,
A certain amount of tablets is compressed and the outer periphery is coated with a water-soluble resin so that spherical porous powder (silica) is infiltrated. If necessary, coat the outer periphery, put in a hemispherical hollow capsule molded in a water-soluble range, and bond two pieces together. In addition, it is important to adjust the pH of the aqueous solution to near neutral before dissolving carbonate or hydrogen carbonate in an aqueous solution containing various active ingredients in order to properly manage the amount of carbon dioxide gas generated. In the present invention, the pH is 5 to 8, preferably pH 6.0.
It is 7.9. As a pH adjusting method, an organic acid or an inorganic acid (eg, citric acid, tartaric acid, hydrochloric acid, etc.) is used as an adjusting agent on the acidic side, while triethanolamine, caustic soda, or caustic potassium is used as an adjusting agent on the alkaline side. , Diethanolamine, aqueous ammonia, borax, monoethanolamine, etc. are used.

As described above, a soluble compressed gas can be generated in the aerosol container. In the present invention, an insoluble compressed gas is filled in the aerosol container. This is because when only the soluble compressed gas is the propellant, the pressure in the can decreases as the space volume increases as the aerosol content is consumed, and at the same time, the gas dissolved in the content Partly evaporates. As a result, the state at the time of spraying (for example, spray state, spray pattern,
The state of bubbles and jetting force) change to the worse. When the insoluble compressed gas is filled, the soluble compressed gas can be prevented from being re-evaporated in the aerosol container, the drop in the can internal pressure can be prevented, and the state at the time of injection can be maintained in a good state. However, there are cases where the product can be used relatively well until the end by injection using only carbon dioxide. In that case, it is possible to use the generation of carbon dioxide gas according to the present invention to commercialize the product and to use no insoluble compressed gas. However, theoretically, it is considered preferable to use an insoluble compressed gas together. It is economical to use only carbon dioxide.

Nitrogen gas is a typical example of the insoluble compressed gas. The nitrogen gas can be filled by the pressure filling method or the under cup method which is conventionally used in the industry. However, since there is a pressure for generating carbon dioxide gas in the step of filling first, the filling pressure of nitrogen gas is a pressure that matches the final set pressure and the carbon dioxide gas pressure. According to the experiment, it can be considered that [nitrogen filling setting pressure] = [final setting pressure] − [carbon dioxide gas pressure]. That is, the pressure of the aerosol product is 25 ° C, 7
When you want to kg / cm ^2, when the pressure of carbon dioxide filled in the manner described Matasaki is 5 kg / cm ² [a nitrogen-filled set pressure] = [7] - [5] = 2 kg / cm ² ( at
25 ℃) is good. As a practical matter, the carbon dioxide gas previously filled was 5 kg.
Filling with nitrogen after showing / cm ² is problematic in terms of pressure and is also disadvantageous in terms of management, so immediately after the end of the injection of the two components for carbon dioxide generation and the end of the sealing work It is filled with nitrogen gas, and this is also the reason for the action and effect described later. Here, “immediately after the sealing work is completed” means immediately after the sealing work is completed, and specifically, 0 seconds to
Shows between 5 seconds.

Next, the carbon dioxide gas generation process will be described in detail. The generation of carbon dioxide gas is as shown in the above chemical reaction formula [I]. Similar to the experiment described above, the carbon dioxide gas generation test was performed using the following size materials. That is, the capacity of the container was 156 ml, the aqueous solution was 90 ml, the headspace was 66 ml, and the amounts of NaHCO ₃ and citric acid were calculated according to the amount calculation of the reaction formula and varied to obtain the graph shown in FIG. 1.
That is, the pressure generation in the can can be well controlled by controlling the amounts of NaHCO ₃ and citric acid. When carbon dioxide is pressure-filled by the conventional method, carbon dioxide absorption coefficient of the content liquid, absorption rate, filling speed, filling pressure, can pressure resistance, aerosol valve mechanism, content liquid temperature,
In consideration of various factors such as carbon dioxide temperature, it is necessary to adjust the conditions for filling each time. According to the present invention, the addition of NaHCO ₃ is (a) dissolved in an aqueous solution at a certain percentage (a) preliminarily weighed to form a water-soluble capsule (c) liquid filling as an aqueous solution of a certain concentration, etc. Among them, an appropriate method can be adopted, and for citric acid, the same methods as (a), (b) and (c) can be adopted, and a rational and simple process can be selected by combining these. By performing (a), it can be performed as a batch work. That is, an aqueous solution or the like containing the active ingredient may be stored in a large tank, and predetermined NaHCO ₃ may be added to this and mixed and stirred. However, this work may cause problems such as shortening the storage period of the aqueous solution, so it is necessary to investigate in advance. Since the work of (a) is an adding work at the time of filling, it is easy to automate. However, the problem of long-term storage of capsules (alteration,
Moisture absorption). (C) is rational because it can be carried out as a batch work, but liquid quantity control during filling work must be strictly performed. It is preferable that NaHCO ₃ is used by the method (a), and citric acid is encapsulated by the method (a). If the reverse is performed, it is not impossible, but it is not preferable as a process. That is, when citric acid is placed in an aqueous solution [method (a)] and filled in a can, and NaHCO ₃ is added thereto (method (a)], normal pressure is generated, but citric acid is added. The pH of the aqueous solution is temporarily lowered to about 3 and there is concern about the effect of this on the entire aqueous solution. However, in this case, p of the finished product by adding NaHCO ₃
H is at 6.7 and is normal.

The carbonates, hydrogencarbonates, organic acids and inorganic acids that can be used in the present invention are not particularly limited, but those shown below are preferable. As the carbonate, sodium carbonate (Na
HCO ₃ ), calcium carbonate (CaCO ₃ ), magnesium carbonate (MgCO ₃ ), rubidium carbonate (Rb ₂ CO)
₃ ), potassium carbonate (K ₂ CO ₃ ), cesium carbonate (C
s ₂ CO ₃ ). Examples of the hydrogen carbonate include sodium hydrogen carbonate (NaHCO ₃ ), potassium hydrogen carbonate (KHCO ₃ ), ammonium hydrogen carbonate (NH ₄ HCO ₃ ).
₃ ) and lithium hydrogen carbonate (LiHCO ₃ ). Examples of the organic acid include citric acid, acetic acid and tartaric acid, and examples of the inorganic acid include hydrochloric acid and sulfuric acid.

Next, the step of filling the insoluble compressed gas will be described in detail. As for the step of filling the insoluble compressed gas, for example, nitrogen gas, it can be filled by the conventional pressure filling method as described above. However, it is generally necessary to consider various factors such as the pressure inside the can, the filling speed, the filling pressure, the pressure resistance of the can, the aerosol valve mechanism, and the gas temperature, and it is difficult to fill carbon dioxide next to carbon dioxide. However, according to the present invention, nitrogen gas filling is performed immediately after charging the components for generating carbon dioxide gas and sealing the container. Therefore, the pressure in the can is close to the atmospheric pressure, and the pressure in the can depending on the nitrogen component is Since the setting can be relatively low pressure, the filling work is stable and easy. As the compression insoluble gas used in the present invention,
Nitrogen, helium, argon, neon, oxygen can be used. The internal pressure of the aerosol container is 8 kg / at a temperature of 35 ° C according to the general high pressure gas safety regulation, Article 12 and 27, and the safety regulations of industrial articles, Article 8 and 67.
It is regulated to be less than or equal to cm ² , and it is necessary to comply with it. Preferably in order to maintain the injection state of the product well for it seems better to design at normal temperature to ^{3.5kg / cm 2 ~7.8kg / cm 2} .

The compressed gas of the present invention and those other than the present invention were comparatively tested and evaluated below. (Comparative Experiment) FIG. 2 shows an AL container (full volume 156 ml), purified water 90 ml, NaHCO _{3 3} g and citric acid 2.5 g as shown in the following (a) to (c), and left for 1 day to consume the contents. The accompanying pressure reduction was tested. The results are summarized in the graph shown in FIG. (A) 2 components (Nightly pressure-filled with nitrogen 2 kg after sealing the container)
/ cm ² was intended) (b) reaction products ((A) and sealed by adding the same as the NaHCO ₃ and citric acid, nitrogen shall not filled) (c) pressured article (putting purified water 90ml crimp (Pressurized to 5 kg / cm ² by the conventional method) (Do not use NaHCO ₃ and citric acid: Evaporate liquefied carbon dioxide to reduce the pressure, and use an aerosol gas filling machine to fill the aerosol pipe with pressure (pressure filling method)) For each of the products (a), (a), and (c), the relationship between the remaining amount of liquid in the can (0 to 100%) and the pressure in the can is shown. According to this pressured product (c) is Kan'nai pressure after 1 day after filling has dropped from 5 kg / cm ² to 4.3 kg / cm ^2. If the content liquid exceeds 20%, the pressure drops drastically. In comparison, the reaction product (a) does not change in pressure even after 1 day. This is probably because the carbon dioxide gas was formed by reacting in a homogeneous system of the content liquid, and the gas was sufficiently saturated from the beginning. Also, the pressure drop due to the decrease of the content liquid is substantially uniform. The two-component product (a) was pressurized with nitrogen immediately after sealing the container, so that the initial pressure was 7.3 kg / cm ² even after 1 day. In this case, the internal pressure is 2 kg even if the liquid in the container becomes zero.
/ cm ² or more, and the normal injection ability was maintained. The present invention proposes a pressurizing method with two components, but it is considered that a product containing only carbon dioxide gas such as the product (a) according to the present experiment can be implemented as a part of the present invention.

Next, when the same test products as those in (a), (b) and (c) above are made and the internal volume is sprayed, the sprayed liquid is collected in a beaker and evaporated from there. The amount of evaporation was measured. The results are shown in [Fig. 3]. It can be inferred that this evaporation amount (percentage) is a number proportional to the amount of carbon dioxide gas contained in the content liquid. According to this result, (a) product ... The evaporation rate of carbon dioxide is almost constant and stable. (B) Product: The evaporation rate is relatively stable. (C) Product: The evaporation rate is large initially, and as the content liquid decreases, the evaporation rate decreases. Also, as shown in the bottom of the table, the spray condition is (a) product ... good spray condition until the end (ii) product ... good spray condition up to about 10% remaining amount (c) product ... about 30% remaining amount As mentioned above, the propellants of aerosol products are currently LPG and D.
The majority are MEs or blends thereof, both of which are flammable gases. That is, careful attention and control are required at each stage of manufacturing equipment, manufacturing control, distribution, storage, and consumption. According to the present invention, since it uses a non-combustible, safe and harmless compressed gas (for example, nitrogen gas, carbon dioxide gas) as a component, it becomes much safer. At the same time, water-soluble stock solutions, emulsion solutions, etc. are the main stock solutions, so they can be comprehensively manufactured as non-combustible products.

Since carbon dioxide has a bacteriostatic action, it is said that the one pressurized with this is free from microbial contamination. At the same time, the pH of the aqueous liquid changes depending on the pressure applied. That is, it is said that the pH of water becomes 4 or less at a pressure of 3.5 kg / cm ² or more. It is not good for the quality of the product that the undiluted aqueous solution of the aerosol undergoes an abnormal drop in pH due to carbon dioxide. For this reason, pressurization due to carbon dioxide should be kept low (example: 2
kg / cm ² ) This plan is optimal for reducing the drop in pH and for making nitrogen gas play the role of a propellant for injection. As described above, filling the two components of the compressed gas (soluble and insoluble) requires a large space in the conventional method and is economically disadvantageous because the amount of investment is large. According to the present invention, very economical, safe and accurate production is possible. Further, when only one component of carbon dioxide gas is required, high pressure gas manufacturing equipment, piping, etc. are not required, which enables simple, safe and economical production.

[0029]

【Example】

(Example 1) Formulated liquid (lotion) 1,3 butylene glycol 2% by weight oleyl alcohol 0.1 〃 POE (20) sorbitan monolaurate 0.5 〃 ethanol 10.0 〃 suitable amount paraben suitable amount purification 86.9% by weight of water Aluminum can for aerosol (capacity 156 ml)
90 ml, and ₃ g of NaHCO ₃ is weighed and added thereto. Separately, prepare a capsule in which 2.5 g of citric acid was taken and packed with a film of polyvinyl alcohol, put it in, immediately crimp the valve, and immediately after that, fill with nitrogen gas at 2 kg / cm ² G (pressure filling). ) After 10 minutes, the product showed a pressure in the can of 7 kg / cm ² at 25 ° C., and showed a good spraying condition when spraying with the top button attached. The internal pressure of the can after injection of the entire amount in a good state of the internal volume showed a residual pressure of 2 kg / cm ² .

(Example 2) Preparation liquid (alcohol for disinfection / sterilization) Propylene glycol 1.0% by weight Irgasan 0.5 〃 Ethyl alcohol 95% 72.0 〃 Purified water 26.5 〃 Can (capacity 156 ml)
90 ml, and 2.5 g of NaHCO ₃ is weighed and added thereto. When preparing the preparation liquid, 92.5 g of a mixture which has been mixed and dissolved in advance at this ratio may be put in the container. A capsule containing 2.1 g of citric acid wrapped in a water-soluble film was put into this, and immediately after crimping the valve, nitrogen gas was charged under pressure of 3 kg / cm ² . After about 10 minutes, the product internal pressure is 7.
It shows 1 kg / cm ² and shows a good injection state. Further, the entire amount could be injected in a good injection state, and the pressure inside the can when the content liquid was exhausted was 2 kg / cm ² .

(Example 3) Preparation liquid (lotion) Hyaluronic acid 0.5% liquid 0.5% by weight Oleyl alcohol 0.2 〃〃 Seaweed extract 0.1 〃 〃 Purified water 99.2 〃〃 Above preparation liquid 90 ml was put in the same container as in Example 1, 4 g of NaHCO ₃ was added thereto, a water-soluble capsule containing 3.3 g of citric acid was added, and the valve was crimped. The product shows an internal pressure of 6.7 kg / cm ² after 10 minutes, and the injection state is also good.

(Example 4) Preparation liquid (mousse for hair) Propylparaben 0.1% by weight Methylparaben 0.1 〃〃 UV inhibitor 0.3〃〃 Ethanol 99% 10.0〃〃 Perfume 0.1〃 〃 Purified water 78.7 〃 〃 Polyoxyethylene cetyl ether 1.2 〃 〃 Butyl methacrylate copolymer 7.0 〃 〃 Dipropylene glycol 1.5 〃 〃 Silicone 1.0 〃 〃 90ml to 156ml capacity)
Put in. Add ₂ gr of NaHCO ₃ to it. Alternatively, 92 gr of a mixed solution mixed in this ratio may be added. A water-soluble capsule containing 1.7 gr of citric acid and 5 gr of isopentane were put into this, the valve was immediately crimped, and immediately after that, nitrogen gas was pressurized and filled so that the inner pressure became 3 kg / cm ² . The product exhibits an internal pressure of 6.6 kg / cm ² after 10 minutes, and when it is sprayed with an adapter (spout), a good foam is sprayed, and the foam lasts well for 2 minutes or longer. In this case, as shown in the written chemical formula, the generation of carbon dioxide gas and sodium citrate Occurs. This substance is useful as a raw material for cosmetics and is widely used in makeup cosmetics, basic cosmetics and the like. Described on page 140 of the Cosmetic Raw Material Dictionary (Nikko Chemicals).

[0033]

EFFECTS OF THE INVENTION The present invention has the following effects as will be understood from what has been described in the above embodiments. An aqueous solution, an emulsion solution, or an aqueous alcohol solution containing various active ingredients is filled with hydrogen carbonate and an organic acid or an inorganic acid, and at the same time, the insoluble compressed gas is filled under pressure. It is possible to rationally produce an aerosol product having two components of soluble compressed gas. An aerosol product having such two components could not be mass-produced by a conventional production method. The compressed gas pressurized aerosol product proposed in the present invention was developed under a novel idea that combines the advantages of a soluble compressed gas with the advantages of an insoluble compressed gas. Soluble compressed gas has the property of dissolving in the content liquid, and when sprayed from an aerosol container, the melted gas body expands rapidly and is subdivided to subdivide the content at the same time, showing a good atomized state. As the gas is injected and decreases, the pressure decreases with the increase of the space (head space), and the gas infiltrated in the liquid evaporates to compensate for this.
As a result, the amount of gas in the liquid is reduced and the atomized state tends to deteriorate. On the other hand, since the insoluble compressed gas does not dissolve in the content liquid, there is no expansion or subdivision effect at the time of injection, but since it is not injected outside the container with the liquid when the content liquid is injected, the amount of gas initially filled It continues to work effectively as a propellant without losing any. In the present invention, by combining the above two components, the evaporation of the soluble compressed gas to the head space is suppressed to maintain a good effect at the time of injection, and at the same time, the characteristic of the insoluble gas is utilized to reduce the pressure in the can. Properly maintaining the effect of subdividing the jetting liquid on the basis of pressure. Depending on the properties of the product, the insoluble compressed gas may be unnecessary, and in that case, the product can be produced only by the carbon dioxide gas generated by the present invention. Also, in the case of filling only with carbon dioxide, when using the conventional pressure filling method, 1) the problem of reliquefaction in the pipe for feeding carbon dioxide, 2) filling the carbon dioxide with a certain constant pressure (for example, 20 kg).
/ Cm ² ) or more, and it is necessary to shake the aerosol can for a certain period of time (for example, 20 to 30) before gas saturation.
However, according to the present invention, this problem can be solved.

[Brief description of drawings]

FIG. 1 is a graph showing the results obtained by changing the amounts of NaHCO ₃ and citric acid according to the amount calculation of the reaction formula.

[Fig. 2] (A) to (C) are filled and left for 1 day,
5 is a graph showing the results of testing the pressure decrease with the consumption of contents.

[FIG. 3] The evaporation amount of a gas body that collects the injected liquid in a beaker and evaporates from it when the same test product as in (a), (a), and (c) is made and the internal volume is injected. It is a graph which shows the result of having measured.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B65D 83/34 83/36 C01B 31/20 A // A61K 7/00 S

Claims (3)

[Claims] 1. An aqueous solution containing an active ingredient, an aqueous solution containing a surfactant, or an alcoholic aqueous solution as a stock solution, into a aerosol container, a stock solution, a predetermined amount of a carbonate or hydrogen carbonate, and a predetermined amount of an organic solution. An aerosol product, characterized by containing an acid or an inorganic acid, sealing it, and pressurizing it with a non-soluble compressed gas. 2. An undiluted solution prepared by adding a hydrocarbon oil having a carbon number of 5 or more to an aqueous solution containing a surfactant as an undiluted solution, a predetermined amount of carbonate or hydrogen carbonate, and a predetermined amount. A foamy aerosol product, characterized by containing the organic acid or the inorganic acid as described in 1 above, sealing it, and pressurizing it with a non-soluble compressed gas. 3. When accommodating a stock solution, a predetermined amount of a carbonate group or a carbonate group of hydrogen carbonate, and a predetermined amount of an acid group of an organic acid or an inorganic acid in an aerosol can, either the carbonate group or the acid group is previously stored. Pour into the stock solution and another 1
The method for producing an aerosol product according to claim 1 or 2, wherein the other group is charged as a water-soluble capsule or the like and sealed.