JP2007031397A - Aerosol preparation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aerosol preparation enabling compressed gas to be filled therein at high pressure and high concentration with slight change in jet properties as the pressure drop of a compressed gas propellant is suppressed even if contents are jetted. <P>SOLUTION: The aerosol preparation with compressed gas as propellant is provided. In this aerosol preparation, a gas-permeable container in which a temperature-dependent gas-reserving medium is sealed up is held in an aerosol container. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aerosol formulation using a compressed gas as a propellant.

As compared with an aerosol using a liquefied gas such as LPG, an aerosol using a compressed gas as an injection gas has a problem that the injection pressure rapidly decreases and the injection characteristics change as the contents are injected. As a method for solving this, there are a method of filling by increasing the initial pressure at the time of filling, and a method of reducing the filling rate of the contents to suppress the drop of the injection pressure. However, if the initial pressure is increased, even within the normally used temperature range of 40 ° C., the pressure regulated by the High Pressure Gas Safety Law may exceed 1.0 Mpa, and the pressure resistance range of the container may be exceeded. There is. Moreover, if it is attempted to suppress the change in the injection characteristics by lowering the filling rate of the contents, there is a problem that the injection capacity when used is reduced.
As a solution to the problem caused by a decrease in the injection pressure of compressed gas, for example, Envirospray (Patent Document 1) having an inflatable bladder that generates pressure by gas generation reaction when the contents are injected is known. However, this envirospray has a complicated apparatus and has a problem that it is difficult to apply to a compressed gas other than carbon dioxide because it uses a reaction between carbonate and acid.

Aerosol preparations using compressed gas as a propellant are widely used in the food field, cosmetic field, pharmaceutical field and the like. For example, in the food sector, whipped cream using compressed gas such as nitrous oxide gas, fillings and spreads such as butter and margarine, mist spray and foam spray using carbon dioxide gas; fried food using nitrogen gas A food filled in an aerosol container such as a liquid spray of oil or a mousse spray is known, but none of them considered the pressure drop (Patent Document 2). There is disclosed a double-structure aerosol container in which a propellant and contents are separated and housed, and containing an adsorbent having a specific surface area and pore diameter in a certain range (Patent Document) 3). However, even though the adsorbent contained in the aerosol container can prevent the pressure drop of the propellant, there is no idea to control the pressure, and in a system with moisture, activated carbon adsorbs moisture and releases carbon dioxide. Therefore, it could not be used.
Japanese Patent Laid-Open No. 58-112979 JP 2004-201506 A Japanese Patent Laid-Open No. 2005-8204

  An object of the present invention is to provide an aerosol preparation capable of filling a compressed gas with a high pressure and a high concentration, in which the pressure drop of the compressed gas propellant is suppressed even when the contents are injected, and the change in the injection characteristics is small.

  Therefore, the present inventors searched for an aerosol preparation that can suppress an increase in internal pressure even at a high temperature such as 40 ° C., can be filled with compressed gas at a high pressure, and can be manufactured more easily. In a liquid state, a compressed gas can be dissolved and dissolved at a higher concentration than water, and a temperature-dependent gas storage medium that hardly dissolves a compressed gas in a solid state is enclosed in a gas permeable container. Then, when held in the aerosol container, even if the compressed gas is filled at a high concentration at a high pressure, since the compressed gas is dissolved at a high concentration in the gas storage medium at a high temperature, the increase in the internal pressure is small, It has been found that it is possible to suppress a decrease in injection pressure caused by injecting the contents.

  That is, this invention provides the aerosol formulation which hold | maintains the gas-permeable container which enclosed the temperature-dependent gas storage medium in the aerosol container in the aerosol formulation which uses compressed gas as a propellant.

  Although the aerosol formulation of the present invention is filled with compressed gas at a high pressure and high concentration, the increase in internal pressure at a high temperature is small, and even when the contents are injected, the decrease in the injection pressure is suppressed. Little change in characteristics.

  Examples of the compressed gas used in the aerosol preparation of the present invention include carbon dioxide gas, nitrogen gas, nitrous oxide gas, and air. These propellants may be used as a mixed gas as appropriate. As the compressed gas, carbon dioxide gas, nitrous oxide gas, particularly carbon dioxide gas is preferable.

  The aerosol preparation of the present invention is filled so that the initial filling pressure of the compressed gas is 1.5 to 0.40 Mpa, further 1.0 to 0.5 Mpa, particularly 1.0 to 0.7 Mpa at 25 ° C. Preferably it is done. Within this range, even if the contents are injected, there is little change in the injection characteristics, and an aerosol preparation with a stable preparation effect can be obtained.

  The temperature-dependent gas storage medium used in the present invention is temperature-dependent in gas storage, and when the medium is in a liquid or gel state, the compressed gas is dissolved at least twice as much as that of water at the same temperature. However, when the medium is in a solid state such as a crystal, the compressed gas is hardly dissolved. The solubility of the compressed gas when the medium is in a liquid state is preferably at least 3 times the mass of water at the same temperature.

  The temperature-dependent gas storage medium has a melting point of 0 to 40 ° C., more preferably 5 to 40 ° C., particularly 10 to 35 ° C., and at least a part of the temperature-dependent gas storage medium is in a liquid state in a temperature range in which an aerosol preparation is normally used. The compressed gas is preferably excellent in storage and release properties. That is, the gas storage medium dissolves the compressed gas in a liquid state at a temperature equal to or higher than the melting point, but becomes a solid state at a low temperature equal to or lower than the melting point and releases the compressed gas almost without dissolving. Therefore, since the gas storage medium becomes higher than the melting point at a high temperature and changes to a liquid state, it becomes possible to dissolve more compressed gas. Dissolves and suppresses increase in internal pressure. On the other hand, if a large amount of compressed gas is dissolved in the gas storage medium in the liquid state, the compressed gas stored in the gas storage medium is easily released and the internal pressure is reduced even if the internal pressure is reduced by injection and use. Maintained. Moreover, even if temperature falls and internal pressure falls, the solid-state part of a gas storage medium increases, A carbon dioxide gas is discharge | released and the pressure in an aerosol container can be maintained.

  Examples of gas storage media include glycerin fatty acid esters (oils and fats) such as olive oil, soybean oil, cottonseed oil, corn oil, rapeseed oil, beef tallow and palm olein; capric acid, caprylic acid, palmitooleic acid, oleic acid, palmitic acid, Higher fatty acids such as isostearic acid and stearic acid; aliphatic higher alcohols such as lauryl alcohol, oleyl alcohol, and isostearyl alcohol; alcohol fatty acid esters such as methyl laurate, isopropyl myristate, isopropyl palmitate, oleyl oleate, and methyl stearate Polyhydric alcohols such as polyethylene glycol (PEG; average molecular weight 300-1500) and polypropylene glycol (PPG; average molecular weight 500-40000); glycerin, polyglycerin, butanediol, sucrose, etc. Or polyol and consisting fatty polyol fatty acid esters, polyoxyethylene chain and a polyoxypropylene chain and those having an ether bond, and the like. In particular, as the gas storage medium, fats and oils, fatty acids, polypropylene glycol, and polyethylene glycol are preferable. Particularly, fats and oils such as palm olein having a melting point of 10 to 35 ° C., capric acid, oleic acid, polyethylene glycol (PEG 400, PEG 600, PEG 1000). Etc. are preferred. In addition, as for carbon number of a fatty acid and aliphatic higher alcohol here, 8-24 are preferable.

  A gas storage medium can be used individually or as a mixture of 2 or more types. In this case, you may mix and use 2 or more types from which melting | fusing point differs. Above the melting point of the high-melting point gas storage medium, all the gas storage medium becomes liquid and can store a large amount of compressed gas, so it is possible to suppress an increase in internal pressure, and below the melting point of the low-melting point gas storage medium, Since all the gas storage media are in a solid state, the compressed gas is released and the decrease in internal pressure due to the low temperature is suppressed. For example, when a gas storage medium having a melting point of less than 40 ° C. and a gas storage medium having a melting point of 40 ° C. or higher are used as a mixture, the liquid gas storage medium part dissolves the compressed gas at a temperature lower than 40 ° C. A gas storage medium having a melting point coexisting at 40 ° C. or higher becomes a reservoir and becomes a liquid at 40 ° C. or higher, which further dissolves the compressed gas. Therefore, an increase in pressure in the aerosol container at a high temperature can be suppressed. Further, for example, when a gas storage medium having a melting point of about 10 ° C. (for example, 10 to 15 ° C.) and a medium having a melting point of 30 to 40 ° C. are combined, It melts and becomes liquid, dissolves the compressed gas and suppresses the increase in internal pressure. Since the gas storage medium having a low melting point is liquid at 10 to 30 ° C., it functions as a gas reservoir for compressed gas, and at a low temperature of 10 ° C. or less Since all of them are in a solid state, the stored compressed gas is released, and the phenomenon that the amount of dissolved gas in the content itself increases and the injection pressure decreases can be suppressed. Therefore, in addition to being able to be filled with a large amount of compressed gas, it is possible to simultaneously suppress an increase in internal pressure at a high temperature and a decrease in internal pressure at a low temperature.

When the gas storage medium is liquid and difficult to handle in the gas permeable container, it may be adsorbed on another substance or gelled. Examples of the adsorbing material include inorganic porous carriers such as silica gel and zeolite. Examples of the gelling agent include an oil gelling agent obtained by introducing a fatty acid chain into cellulose or polyol, and a derivative of hardened castor oil.
When two or more types of gas storage media are mixed and used, the mixture may be enclosed in the same gas permeable container, or each may be enclosed in separate gas permeable containers.

The gas permeable container used in the present invention is a container which has at least a part of a film or sheet part or an elastomer part that can transmit compressed gas as a propellant and does not allow liquid to permeate. By enclosing the gas storage medium in such a gas permeable container, when the pressure in the aerosol container of the aerosol formulation is reduced, the compressed gas dissolved in the gas storage medium in the gas permeable container is permeated. If the pressure in the aerosol container is adjusted and the pressure in the aerosol container increases at high temperatures, the compressed gas is taken into the gas storage medium in the gas permeable container and dissolved, and the pressure in the aerosol container is An internal pressure holding adjustment function for adjusting the pressure is produced. Here, the gas permeability is the permeability of the target carbon dioxide gas or nitrous oxide gas, but from a resin and a resin film of 500 cc / m ² · day · atm (25 ° C.) (ASTM D-1434) or higher. It is also preferable that

The film or sheet used in the gas permeable container is a high molecular compound, for example, polyamide such as nylon 12 or nylon 11, polyvinyl chloride, polycarbonate, polystyrene, polytetrafluoroethylene, polyolefin such as polyethylene, polypropylene or polybutadiene; Polyethylene terephthalate; polyvinyl acetate; ethyl cellulose; elastomers such as silicon rubber and styrene butylene copolymer. Preferable materials include polyolefins such as polyethylene and polypropylene, polystyrene and the like. Polyolefin is more preferable, and polyethylene is particularly preferable from the viewpoint of heat-fusibility and cost.
The polymer compound film or sheet may be a single layer or may be a laminated layer. The thickness of the polymer compound film is preferably 10 μm to 500 μm, particularly 40 μm to 200 μm. However, when adjusting as a gas permeable container, processing of heat sealing or the like is performed. It is preferable in terms of easiness and durability against volume change accompanying gas permeation.

  The material of the gas permeable container other than the gas permeable film or sheet is not particularly limited as long as it is a gas impermeable substance. For example, plastic, metal, glass or the like may be used, or aluminum foil or the like may be used. A laminated film or the like may be used. The gas permeable container is preferably a gas permeable film or sheet as a whole from the viewpoint of the transmission efficiency of the compressed gas.

  The shape of the gas permeable container is not particularly limited as long as the surface area of the container is large and the compressed gas permeation efficiency is good. For example, a pillow, a box-shaped one using a gas permeable film for a part thereof, etc. It is done. Those embedded in an elastomer such as styrene and polyolefin (propylene / butylene) copolymer can also be used. In terms of aerosol productivity, a valve in which a mechanism of such a gas permeable container is attached to a part of the valve may be used. In these shapes, a pillow is particularly preferable from the viewpoint of easy response to pressure changes, and it can be manufactured inexpensively and easily by filling with a gas storage medium and sealing with a heat seal or the like.

  The gas permeable container holds the gas storage medium at a ratio of preferably 20 to 80% by volume, more preferably 40 to 60% by volume with respect to the volume in the container so as to cope with expansion due to a rapid pressure change. It is preferable to do so.

  Further, the ratio of the gas storage medium to the aerosol container is 3 to 40% by volume of the aerosol container, and further 5 to 15 from the viewpoints of head space at the time of gas filling, ensuring operability, and not reducing the filling rate of contents. It is preferable that it is volume%.

  In the case where the aerosol container of the aerosol formulation is a double container having an inner bag, the gas permeable container is held in the compressed gas filling portion outside the inner bag filled with the injection contents. In this case, it is preferable to fill a gas permeable container filled with a gas storage medium of 5 to 70% by volume, further 5 to 40% by volume of the volume of the compressed gas filling part which is a space outside the inner bag. Further, the gas storage medium may be directly filled between the inner bag and the aerosol container (outer cylinder can). When the pressure falls within this range, when the internal pressure is reduced by injection, the compressed gas can be easily supplied from the gas permeable container, and the internal pressure is excellently maintained. If the volume is 5% by volume or less, the amount of compressed gas stored is small, and the internal pressure may not be sufficiently maintained.

In the gas permeable container, in addition to the gas storage medium, it is preferable that a physical gas adsorbing substance, for example, a porous body that physically adsorbs the compressed gas, coexists so that the dissolved amount of the compressed gas can be further increased. Examples of the physical gas adsorbing substance include porous bodies such as activated carbon, silica gel, and zeolite. This physical gas adsorbing material is preferably used in an amount of 5 to 70 parts, more preferably 10 to 50 parts, and particularly preferably 10 to 30 parts with respect to 100 parts of the gas storage medium. The physical gas adsorbing substance can be used in other shapes such as powder form to granular form of several tens μm to several mm, a columnar shape, a plate shape and the like. In addition, as measured by the BET method, the surface area was 600 to 3000 m ² / g, the pore volume was 0.2 to 3.0 mL / g, the surface area was 800 to 1300 m ² / g, and the pore volume was 0.3. A value of ˜1.0 mL / g is preferable from the viewpoint of an increase in adsorption amount and availability.

If the physical gas adsorbent contains moisture in the contents to be filled, it is difficult for the compressed gas to adsorb by adsorbing moisture into the pores, and the physical gas adsorbent itself has already adsorbed moisture. Therefore, it is preferable to obtain a stable amount of compressed gas adsorption by preliminarily mixing with a highly hydrophobic liquid such as fats and oils after drying under high temperature and reduced pressure as a pretreatment. As the oils and fats, it is preferable to use the gas storage medium described above.
More preferably, when the surface of the physical gas adsorbing substance is hydrophobized with a hydrophobic coupling agent, the oil and fat permeation into the pores increases, so that the agent is easy to use.

As the aerosol container, any pressure container can be used, and materials such as metal, glass and plastic can be used. However, when the gasser shaker method or the like is used as the filling method, aluminum impact cans, DI cans, -Monoblock cans are preferred.
When the aerosol container is a double container provided with an inner bag filled with the contents, the inner bag is preferably made of polyethylene, polypropylene or the like in order to ensure gas permeability to some extent.

Since the aerosol formulation of the present invention has a small pressure drop of the compressed gas, it can be used in various fields with little change in the spray pattern when the contents are jetted and a reduction in the foam specific volume of the foam spray. For example, in the food field, whipped creams; fillings such as butter and margarine; spreads; aerosol preparations such as liquid sprays of sautéed oil, mousse sprays, and the like. In the cosmetics field, foams, gels, mousses, liquids, mist sprays, lotions, emulsions, hair preparations, hair preparations, and other aerosol preparations. In the pharmaceutical field, topical disinfection and analgesia. , Foam-like, gel-like, or mousse-type aerosol preparations for preventing stagnation.
When the aerosol formulation of the present invention is used for these products, it is preferable to obtain a product having stable product properties such as foam specific volume, etc., in which changes in jetting properties accompanying pressure drop during use are suppressed.

Example 1 Foam cleaning material of the present invention 1
A cleaning composition was prepared according to Formula 1 described in Table 1, and 210 g of this cleaning composition was filled in an aerosol can (aluminum DI can of φ60 mm × 135 mm) having an internal volume of 350 mL. A container filled with a polyethylene film (thickness 40 μm) pillow (inner size 3 cm × 5 cm) and carbon dioxide gas storage medium 5 g of PEG 1000 (melting point 35 to 37 ° C.) is held in an aerosol can, and the final equilibrium pressure is 0 A foam-like cleaning material was manufactured by filling carbon dioxide gas so as to be 9 Mpa.

Invention product 2
Instead of PEG1000 of the product 1 of the present invention, 15 g of fatty acid mixed with 10 g of oleic acid (melting point: 4 to 8 ° C.) and 7 g of capric acid (melting point: 30 to 32 ° C.) was used as a gas storage medium under the same conditions. The gas was charged to a final equilibrium pressure of 0.9 Mpa.

Comparative product 1
Under the same conditions as in the product 1 of the present invention, only 220 mL of the detergent composition was filled in an aerosol can, and carbon dioxide gas was filled so that the final equilibrium pressure was 0.9 Mpa.

Comparison product 2
Under the same conditions as in the product 1 of the present invention, only 210 mL of the detergent composition was filled in an aerosol can, and carbon dioxide gas was filled so that the final equilibrium pressure was 0.83 Mpa.

  Foam ratio when jetting 10g of internal pressure after leaving the foam-like cleaning materials of the present invention products 1 and 2 and comparative products 1 and 2 to stand at 40 ° C for 1 week, and adjusting the temperature to 25 ° C. The volume was measured. Subsequently, it was left to stand in an environment of 25 ° C., and 10 g was sprayed once a day. The internal pressure after a total of 20 injections and the foam specific volume during the 20th injection were measured.

  Foam specific volume measurement method: Foam was sprayed into a 20 mL hemispherical container, and after setting up, the weight was measured to determine the specific volume.

  The feel of the foam: 5 expert panelists spray the foam on the inside of the upper arm to the size of a ping-pong ball, and the feel when the foam is pushed out with a finger is heavy (1 point), slightly heavy (2 points), slightly light (3 points) and light (4 points) were evaluated in 4 stages, and the average value was evaluated.

The results are shown in Table 2.

  The aerosol formulation of the present invention had a high foam specific volume even when sprayed 20 times, and was safe without exceeding 1.0 Mpa even at high temperatures.

Example 2 Foamed gel lotion of the present invention 3
A gel composition was prepared according to Formula 2 described in Table 3, and a double container having an inner bag was filled. A double container having an inner bag made of polyethylene having an inner volume of 138 mL was used as an outer cylinder can (φ40 mm × 156 mm, aluminum DI can having an inner volume of 176 mL). After filling the outer can with 20 g of fatty acid mainly composed of lauric acid as a carbon dioxide gas storage medium (Table 4 fatty acid composition: melting point about 32 to 36 ° C.), the inner bag is inserted and carbon dioxide is filled at 25 ° C. The bag was filled with 130 g of gel composition. At this time, the final filling pressure of carbon dioxide gas was 0.88 Mpa.

Comparison product 3
130 g of the gel composition used in the product 3 of the present invention was filled in the inner body of a double container, and carbon dioxide was filled with carbon dioxide so that the final filling pressure was 0.88 Mpa.

  The foamed cosmetics of the present invention product 3 and comparative product 3 were measured for the internal pressure after standing at 40 ° C. for 1 week, the internal pressure after adjusting the temperature to 25 ° C., and the foam specific volume when 5 g was injected. . Subsequently, it was left to stand in an environment of 25 ° C., and 5 g was sprayed once a day. The internal pressure after a total of 20 injections and the foam specific volume during the 20th injection were measured. Table 5 shows the results of the evaluation.

  The aerosol formulation of the present invention has a small decrease in the specific volume of the foam and does not exceed 1.0 Mpa even when the pressure is maintained at a high temperature. In addition, the feel of the foam is heavy in both the inventive example 3 and the comparative product 3, but the extensibility (ease of spreading) of the gel foam is a level in which the inventive product 3 has better extensibility than the comparative product 3. Was maintained until after 20 injections.

Claims (6)

  An aerosol formulation in which a compressed gas is used as a propellant and a gas permeable container enclosing a temperature-dependent gas storage medium is held in the aerosol container.   The aerosol preparation according to claim 1, wherein the compressed gas is carbon dioxide gas or nitrous oxide gas.   The aerosol formulation according to claim 1 or 2, wherein the melting point of the temperature-dependent gas storage medium is 0 to 40 ° C.   The temperature-dependent gas storage medium is one or more selected from the group consisting of fats and oils, higher fatty acids, aliphatic higher alcohols, alcohol fatty acid esters, polyhydric alcohols, polyol fatty acid esters, polypropylene glycol and polyethylene glycol. The aerosol formulation of any one of Claims 1-3.   The aerosol preparation according to any one of claims 1 to 4, wherein a physical gas adsorbing substance is further allowed to coexist in the gas permeable container.   The aerosol according to any one of claims 1 to 5, wherein the aerosol container is a double aerosol container, and the gas permeable container is held in a compressed gas filling portion outside the inner bag filled with the injection contents. Formulation.