JP5971844B2 - Aerosol composition - Google Patents

Description

  The present invention relates to an aerosol composition containing an aqueous stock solution and a liquefied gas, and capable of forming a diamond dust frozen body of water in the aqueous stock solution by the heat of vaporization of the liquefied gas at the time of discharge.

  Conventionally, an aerosol composition intended to cool a discharged body such as a human body by the heat of vaporization of a liquefied gas is known, and a frozen body of water in an aqueous stock solution is formed by the heat of vaporization of the liquefied gas at the time of discharge. There is known an aerosol composition that cools a discharge target.

For example, Patent Document 1 discloses a discharge product comprising an aqueous stock solution containing a surfactant and a liquefied gas (aerosol propellant) containing liquefied petroleum gas as a main component, and the liquefied gas is emulsified in the aqueous stock solution. Describes aerosol compositions that form frozen or snow-like frozen bodies.
Patent Document 2 discloses an aerosol comprising a stock solution containing a lower alcohol having 1 to 3 carbon atoms and a linear monocarboxylic acid having 10 to 22 carbon atoms and a liquefied gas, and the discharged material forms a sorbet-like frozen body. A composition is described.
Patent Document 3 describes an aerosol composition comprising a stock solution containing a lower alcohol having 1 to 3 carbon atoms and a nonionic surfactant and a liquefied gas, and the discharged material forms a sorbet-like frozen body. .
Patent Document 4 describes an aerosol composition comprising a stock solution containing a lower alcohol having 1 to 3 carbon atoms and a higher alcohol having 12 or more carbon atoms and a liquefied gas, and the discharged material forms a sorbet-like frozen body. Yes.
Patent Document 5 describes an aerosol composition comprising dimethyl ether, water, and 0 to 5% by weight of an alcohol having 2 to 3 carbon atoms, and forming a frozen body of water and dimethyl ether by heat of vaporization of dimethyl ether. .

Japanese Patent No. 2960445 Japanese Patent Laid-Open No. 11-60471 Japanese Patent Laid-Open No. 10-287553 JP-A-9-212415 Japanese Patent No. 4402348

Known aerosol compositions include surfactants and emulsification aids that are liquid or solid at room temperature other than water contained in the aqueous stock solution when a frozen body of water in the aqueous stock solution is formed by the heat of vaporization of the liquefied gas. Oils and fats, water-soluble polymers, etc. remain in the frozen body. If the amount is large, when the frozen body is melted, it remains as a liquid or solid.
Therefore, when discharged directly onto the skin, etc., the feeling of use is reduced due to stickiness or solid residual feeling, and even when discharged onto a cloth, the liquid or solid remaining components remain attached to the cloth, etc. There was a problem that it took time and effort to remove.

In addition, these aerosol compositions are used to cool the user or cool the body temperature when the physical condition is poor, especially in a high temperature environment such as summer, that is, at a temperature of 25 ° C. or more, under a hot sun, etc. It is important to be able to be used effectively even at a temperature of 40 ° C. or higher. Since it is difficult to sufficiently emulsify, there is a problem that the component ratio of the aerosol composition to be discharged is not constant, and the formation of the frozen body is insufficient.
In addition, when the amount of components such as surfactants, emulsification aids, fats and oils, and water-soluble polymers is reduced, there is a problem that a uniform frozen body cannot be obtained under a high temperature environment.
Furthermore, the form of the frozen body formed when a known aerosol composition is discharged is a lump, sherbet, or snow, and is in the form of a diamond dust composed of finer ice particles (with a crystal diameter of approximately There was no material that could be formed into an aggregate of 0.2 mm or less.

  Therefore, the present invention solves the above-described problems, and suppresses components remaining in a liquid or solid when a frozen body is melted, and suppresses a decrease in feeling of use due to stickiness or a solid residual feeling. An aerosol composition that facilitates the removal, mixing of aqueous stock solution and liquefied gas, and easy emulsification, and enables formation of a frozen body that is a uniform diamond dust-like aggregate even in a high-temperature environment. The purpose is to provide.

  The present invention is an aerosol composition comprising an aqueous stock solution and a liquefied gas and forming a frozen body upon discharge, wherein the aqueous stock solution comprises 95% by weight or more of water and a monohydric alcohol having 2 to 3 carbon atoms. , Containing a surfactant and an emulsification aid and not containing oils, water-soluble polymers and alcohols having 4 or more carbon atoms, and the monohydric alcohol having 2 to 3 carbon atoms is 3% by weight of the aqueous stock solution. %, And the liquefied gas is composed of liquefied petroleum gas and dimethyl ether, and the weight blending ratio of the aqueous stock solution and liquefied gas is 50/50 to 10/90. .

The aqueous stock solution preferably contains 0.01% by weight or more of a surfactant, 0.1% by weight or more of an emulsifying aid, and 0 to 0.3% by weight of a preservative, and water and a monohydric alcohol having 2 to 3 carbon atoms. More preferably, the total content is 99% by weight or less.
The liquefied gas is preferably 30% by weight or more of dimethyl ether, with the balance being liquefied petroleum gas.

According to the aerosol composition of the present invention, the aqueous stock solution contains 95% by weight or more of water and a monohydric alcohol having 2 to 3 carbon atoms, thereby reducing the components remaining when the frozen body is melted and remaining. By not containing fats and oils that are difficult to remove and water-soluble polymers, it is possible to suppress the deterioration of the feeling of use due to stickiness or solid residual feeling, and to facilitate the removal. .
In addition, a frozen body can be formed into fine diamond dust by containing a monohydric alcohol having 2 to 3 carbon atoms, and the frozen body can be formed by setting the monohydric alcohol having 2 to 3 carbon atoms to 3% by weight or more. Can be more surely made into a fine diamond dust-like aggregate.
If the monohydric alcohol having 2 to 3 carbon atoms is less than 3% by weight of the aqueous stock solution, depending on the outside air temperature at the time of discharge, the water finely divided by discharge is combined when frozen, and snow with large particles In some cases, it may be in the form of a frozen body, a sherbet, or a block.
Further, the aqueous stock solution contains a surfactant and an emulsification aid, the liquefied gas is composed of liquefied petroleum gas and dimethyl ether, and the weight blending ratio of the aqueous stock solution and liquefied gas is 50/50 to 10/90. In addition, it is easy to mix and emulsify the aqueous stock solution and the liquefied gas, and it is possible to reliably form a frozen body that is a uniform diamond dust aggregate even in a high temperature environment.

Mixing and emulsification of aqueous stock solution and liquefied gas is easier because the aqueous stock solution contains 0.01% by weight or more of surfactant, 0.1% by weight or more of emulsification aid, and 0 to 0.3% by weight of preservative. It becomes.
Because the liquefied gas is 30% by weight or more of dimethyl ether and the remainder is made of liquefied petroleum gas, even if the ratio of the aqueous stock solution is increased, the formation of a frozen body that is a uniform diamond dust-like aggregate even in a high temperature environment Is possible.
Mixing and emulsifying the aqueous stock solution and the liquefied gas is not hindered by adjusting the aqueous stock solution to 99% by weight or less in combination with water and a monohydric alcohol having 2 to 3 carbon atoms.

  The present invention is an aerosol composition comprising an aqueous stock solution and a liquefied gas and forming a frozen body upon discharge, wherein the aqueous stock solution comprises 95% by weight or more of water and a monohydric alcohol having 2 to 3 carbon atoms, It contains a surfactant and an emulsification aid, does not contain fats and oils, water-soluble polymers and alcohols having 4 or more carbon atoms, and monohydric alcohol having 2 to 3 carbon atoms is 3% by weight or more of the aqueous stock solution. The liquefied gas is composed of liquefied petroleum gas and dimethyl ether, and the weight ratio of the aqueous stock solution and the liquefied gas is 50/50 to 10/90.

  The aerosol composition of the present invention is prepared by, for example, filling a pressure resistant container with an aqueous stock solution, then filling a liquefied gas, then fixing a valve, and shaking the aerosol container to emulsify the aqueous stock solution and the liquefied gas. can do.

For example, purified water or ion exchange water is used as the water.
The combined amount of water and a monohydric alcohol having 2 to 3 carbon atoms is 95% by weight or more in the aqueous stock solution, and preferably 99% by weight or less.
When the combined amount of water and a monohydric alcohol having 2 to 3 carbon atoms is less than 95% by weight, when the frozen body formed by the discharged material is melted, the remaining water or carbon number in the liquid or solid state Components other than the monohydric alcohols of 2 to 3 lead to a decrease in the feeling of use due to stickiness, a solid residual feeling, and the like, and the removal thereof takes time.
Moreover, even if the blending amount of the water of the aqueous stock solution and the monohydric alcohol having 2 to 3 carbon atoms is 95% by weight or more, if oils and fats and water-soluble polymers are contained, the frozen body is dissolved. They remain, resulting in a decrease in the feeling of use due to stickiness, a solid residual feeling, and the like, and the removal thereof takes time.
The blending amount of the monohydric alcohol having 2 to 3 carbon atoms is 3% by weight or more of the aqueous stock solution, and when it is less than 3% by weight, it is frozen into a lump, sherbet or snow when discharged, and is fine A frozen body that is an aggregate of diamond dust cannot be obtained.

  The surfactant and the emulsification aid are uniformly mixed and emulsified with the aqueous stock solution and the liquefied gas in the aerosol container, and the heat of vaporization of the liquefied gas is uniformly transmitted to the discharged material, so that a uniform diamond dust aggregate Is formulated for the purpose of forming a frozen body.

  Examples of the surfactant include polyoxyethylene sorbitan fatty acid esters such as mono coconut oil fatty acid POE sorbitan, monostearic acid POE sorbitan, monooleic acid POE sorbitan; POE · POP cetyl ether, POE · POP decyl tetradecyl ether, etc. Polyoxyethylene polyoxypropylene alkyl ether; polyoxyethylene glycerin fatty acid ester such as POE glyceryl monostearate; polyoxyethylene lanolin alcohol such as POE lanolin alcohol; polyoxyethylene hydrogenated castor oil such as POE hydrogenated castor oil; POE cetyl ether , POE stearyl ether, POE oleyl ether, POE lauryl ether, POE behenyl ether, POE octyldodecyl ether Polyoxyethylene alkyl ethers such as POE isocetyl ether and POE isostearyl ether; polyethylene glycol fatty acid esters such as polyethylene glycol monostearate; hexaglyceryl monolaurate, hexaglyceryl monomyristate, pentaglyceryl monolaurate, monomyristic acid Pentaglyceryl, pentaglyceryl monooleate, pentaglyceryl monostearate, decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monostearate, decaglyceryl monoisostearate, decaglyceryl monooleate, decaglyceryl monolinoleate, etc. Polyglycerin fatty acid ester; polyoxyethylene glyceride such as POE glyceryl monooleate Polyoxyethylene sorbitan fatty acid esters such as monopalmitic acid POE sorbitan, monostearic acid POE sorbitan, monoisostearic acid POE sorbitan, monooleic acid POE sorbitan; monolauric acid POE sorbitol, tetrastearic acid POE sorbit, tetraoleic acid Examples thereof include polyoxyethylene sorbite fatty acid esters such as POE sorbit; HLB such as 10-19, preferably 11-18. When HLB is larger than 19, the liquefied gas tends to be difficult to emulsify.

The blending amount of the surfactant is preferably 0.01% by weight or more in the aqueous stock solution.
When the surfactant content is less than 0.01% by weight in the aqueous stock solution, the aqueous stock solution and the liquefied gas are difficult to emulsify, forming a frozen body that is a diamond dust-like aggregate with a uniform discharge. Hard to do.
In addition, since the water in the aqueous stock solution and the monohydric alcohol having 2 to 3 carbon atoms are combined in an amount of 95% by weight or more, the surfactant is less than 5% by weight, and there is little residue, and the deterioration of the feeling in use can be suppressed.

  The emulsification aid is composed of a powder that makes it easy to emulsify an aqueous stock solution and a liquefied gas, and the powder acts as an active ingredient, and is also used as a carrier that supports other active ingredients, an adhesive, and the like. .

  Examples of the emulsification aid include talc, zinc oxide, kaolin, mica, magnesium carbonate, calcium carbonate, zinc silicate, magnesium silicate, aluminum silicate, calcium silicate, silica, zeolite, ceramic powder, boron nitride and the like. Can be given.

The blending amount of the emulsification aid is preferably 0.1% by weight or more, more preferably 0.4% by weight in the aqueous stock solution.
When the blending amount of the emulsification aid is less than 0.1% by weight, it is difficult to obtain the effect of blending the emulsification aid.
In addition, since the mixture of water and monohydric alcohol having 2 to 3 carbon atoms in the aqueous stock solution is 95% by weight or more, the emulsification aid is less than 5% by weight and is clogged with the discharge holes of the valve and the discharge member during discharge. Even when stored for a long period of time, the emulsification aid is hardened at the bottom of the container and does not hinder uniform discharge.

The liquefied gas is a liquid in an aerosol container and is emulsified with an aqueous stock solution to form an emulsion.
When discharged into the atmosphere, the liquefied gas is vaporized, and the discharged material is cooled by the heat of vaporization to form a diamond dust frozen body mainly composed of an aqueous stock solution.

The liquefied gas is composed of liquefied petroleum gas which is propane, normal butane, isobutane or a mixture thereof, and dimethyl ether.
By mixing dimethyl ether, even if the total amount of water and monohydric alcohol having 2 to 3 carbon atoms in the aqueous stock solution is 95% by weight or more, the aqueous stock solution is reliably cooled by the heat of vaporization at the time of discharge. A frozen body that is an aggregate of diamond dust can be formed.
Further, it is preferable to contain 30% by weight or more of dimethyl ether in the liquefied gas, which increases the heat of vaporization at the time of discharge, and increases the blending ratio of the aqueous stock solution when blending the aqueous stock solution and the liquefied gas. By increasing the absolute amount of water in the aerosol container, it becomes possible to obtain a frozen body that is a large amount of diamond dust aggregate.

The weight blending ratio of the aqueous stock solution and the liquefied gas is 50/50 to 10/90, preferably 45/55 to 15/85.
When the weight ratio of the aqueous stock solution and the liquefied gas is greater than 50/50, heat of vaporization for freezing the aqueous stock solution by the liquefied gas cannot be obtained.
On the other hand, when the ratio is smaller than 10/90, it is difficult to emulsify the liquefied gas, the emulsification tends to be unstable, the amount of the frozen body obtained is reduced, and the pressure is increased and vaporized when filled in the container. Since the amount of liquefied gas increases, the odor becomes stronger and the risk of ignition increases, which increases the trouble in use.

The aqueous undiluted solution may contain a small amount of active ingredients such as fragrances, preservatives, and medicinal ingredients as necessary to improve the feeling of use or maintain the quality.
Further, in order to adjust the pressure in the aerosol container, a compressed gas such as carbon dioxide, nitrogen gas, nitrous oxide gas, compressed air, or oxygen gas may be used as a pressurizing agent.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these.
In each example and comparative example, an aluminum stock solution and a liquefied gas as a propellant were filled in an aluminum pressure vessel (φ45 × 157), an aerosol valve was fixed to the opening of the pressure vessel, and the pressure vessel was shaken up and down. An aqueous composition, liquefied petroleum gas (LPG) and dimethyl ether (DME) were emulsified to produce an aerosol composition.
An aerosol valve having a stem hole of φ0.4 and a housing under tap of φ2.0 was used, and a discharge member having a discharge hole of φ1.2 was used.
In addition, since evaluation of the following emulsification state needs visual observation in a pressure vessel, the glass-made transparent pressure vessel was used.
The components of the aqueous undiluted solution and the liquefied gas were as follows, and the components having different component ratios were evaluated as examples and comparative examples.

<Aqueous stock solution>
Water: Purified water Ethanol: 99 degree synthetic unmodified alcohol Surfactant: Polyoxyethylene polyoxypropylene cetyl ether [20E. O] [8P. O] (Brand name: NIKKOL PBC-44)
Emulsification aid: Talc (trade name: Crown Talc)
Preservative: Methylparapen (trade name: Platens M)

Tables 1 to 3 show the evaluation results for each example and comparative example.
The evaluation was performed as follows with respect to the emulsified state, the discharged material temperature, the discharged material state, the freeze holding time, the crystal state, and the residual feeling.
<Emulsified state>
After the glass pressure vessel filled with each component was allowed to stand for 1 hour under a constant temperature condition, the emulsified state was visually confirmed by shaking the pressure vessel at 60 times / minute under the same temperature condition.
What was emulsified within 1 minute of shaking time was “◎”, what was emulsified in 1 to 3 minutes was “◯”, and what was not emulsified in 3 minutes was “x”.
The temperature conditions were three conditions of 25 ° C, 5 ° C, and 45 ° C.
<Discharge temperature>
The pressure-resistant container filled with each component was allowed to stand at 25 ° C. for 1 hour, then shaken at 60 times / minute for 3 minutes, further left for 1 hour, and then shaken at 60 times / minute for 10 seconds. The product was discharged from a position 10 cm perpendicular to a paper waste (pulp 100%, sheet size 380 × 330 mm), and the temperature was measured by a thermocouple placed on the paper waste.
<Discharged state>
The pressure-resistant container filled with each component was allowed to stand at 25 ° C. for 1 hour, then shaken at 60 times / minute for 3 minutes, further left for 1 hour, and then shaken at 60 times / minute for 10 seconds. 1 g of the material was discharged, and the state of the discharged material was observed.
A sample in which the discharged product was frozen was indicated as “◯”, and a sample in which the discharged material was not frozen and foamed or the water phase was in a mist state as “×”.

<Freeze retention time>
The pressure-resistant container filled with each component was allowed to stand at 25 ° C. for 1 hour, then shaken at 60 times / minute for 3 minutes, further allowed to stand for 1 hour, and then shaken at 60 times / minute for 10 seconds. A frozen body is formed by discharging 5 g of contents from a position 10 cm perpendicular to the waste (100% pulp, sheet size 380 × 330 mm), and immediately after that, the paper waste is left in a constant temperature room at 40 ° C. The state of the frozen body formed was observed.
When the time until the frozen material on the paper waste melts was 1 minute or more, “◯” was given, and when it was less than 1 minute, “X” was given.
<Crystal state>
The pressure-resistant container filled with each component was allowed to stand at 25 ° C. for 1 hour, then shaken at 60 times / minute for 3 minutes, further allowed to stand for 1 hour, and then shaken at 60 times / minute for 10 seconds. A frozen body was formed by discharging 5 g of contents from a position 10 cm perpendicular to the waste (100% pulp, sheet size 380 × 330 mm), and the size of the crystals was measured with a microscope (VHX-100).
When the crystal size is 30 μm to 200 μm in diameter (diamond dust shape), “◯”, when it is larger (snow hail: diameter 5 mm, misty snow: diameter 1 mm, hail: diameter 5 mm to 50 mm) × ”.
<Residual feeling>
The pressure-resistant container filled with each component was allowed to stand at 25 ° C. for 1 hour, then shaken at 60 times / minute for 3 minutes, further left for 1 hour, and then shaken at 60 times / minute for 10 seconds. 1 g of the object was discharged toward the back of the hand, and the touch when the discharged object remaining after melting was touched was observed.
A sample having no stickiness or the like was defined as “◯”, and a sample having a stickiness was “×”.

Table 1 shows an aqueous stock solution: liquefied gas (propellant) = 20: 80.

Table 2 shows aqueous stock solution: liquefied gas (propellant) = 30: 70.

Table 3 shows aqueous stock solution: liquefied gas (propellant) = 40: 60.

As described above, the aerosol composition of the present invention (Examples 1 to 6, 11 to 16, 21 to 26) has no problem in emulsification of the aqueous stock solution and the liquefied gas.
In addition, the discharged matter becomes a frozen body that is a uniform diamond dust aggregate, and the freezing and holding time thereof is sufficiently secured.
On the other hand, in the composition containing no dimethyl ether (Comparative Examples 1, 11, and 21) and the composition containing no dimethyl ether and 2% ethanol (Comparative Examples 2, 12, and 22), a frozen body was formed. The discharged material is not frozen in the form of diamond dust, and the holding time of the frozen body is not sufficient.
In addition, in the aqueous stock solution, 90% by weight of water and 3.5% by weight of ethanol, for a total of 93.5% by weight (Comparative Examples 3, 13, and 23), a diamond dust-like frozen body was formed. The sticky sensation due to the residual surfactant and emulsification aid after the frozen body was melted was remarkable.
Furthermore, 95.85% by weight of water in the aqueous stock solution and 3.5% by weight of ethanol for a total of 99.35% by weight (Comparative Examples 24 and 25) The emulsion was insufficiently emulsified, the discharge state was uneven, a sufficient frozen body could not be obtained, and the freezing time was not sufficient.

As described above, according to the aerosol composition of the present invention, the discharged product becomes a frozen body that is a uniform diamond dust-like aggregate even after being left in a high-temperature environment, and has excellent adhesion and is continuously cooled. Possible aerosol compositions can be obtained.
In addition, when the frozen body is melted, there are very few components that remain in liquid or solid form, which suppresses a decrease in feeling of use due to stickiness or solid residual feeling, and even when it is attached to a cloth, it is extremely easy to remove. Become.

Claims (4)

An aerosol composition comprising an aqueous stock solution and a liquefied gas and forming a frozen body upon discharge,
The aqueous stock solution contains 95% by weight or more of water and a monohydric alcohol having 2 to 3 carbon atoms, a surfactant and an emulsifying aid, and contains oils and fats, water-soluble polymers and alcohols having 4 or more carbon atoms. Not including
The monohydric alcohol having 2 to 3 carbon atoms is 3% by weight or more of the aqueous stock solution;
The liquefied gas consists of liquefied petroleum gas and dimethyl ether,
An aerosol composition, wherein the weight ratio of the aqueous stock solution and the liquefied gas is 50/50 to 10/90.   The aerosol composition according to claim 1, wherein the aqueous stock solution contains 0.01% by weight or more of a surfactant, 0.1% by weight or more of an emulsification aid, and 0 to 0.3% by weight of a preservative. .   The aerosol composition according to claim 1 or 2, wherein the liquefied gas is 30% by weight or more of dimethyl ether and the balance is liquefied petroleum gas.   The aerosol composition according to any one of claims 1 to 3, wherein the aqueous stock solution contains 99% by weight or less of water and a monohydric alcohol having 2 to 3 carbon atoms.