JP2017081892A - Aerosol product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide aerosol products of hydrogen containing skin lotions which can effectively prevent the loss of dissolved hydrogen at the time of injection and maintain a refreshing feel even in a low alcohol formulation and which are excellent in moisture retention.SOLUTION: In an aerosol product 300, a lotion 301 is pressurized and filled in an aerosol container 302 together with an injection gas 303. A propellant gas 303 contains 1 volume% or more of hydrogen and the total content of hydrogen and inert gas is 90 volume% or more. The lotion 301 contains a hydrophilic organic component having IOB value of 1.7 or more to 6 or less within a range of 5 mass% or more to 30 mass% or less, and contains polyols as a hydrogen transpiration inhibiting component forming a part of the hydrophilic organic component at 2 mass% or more and 20 mass% or less, and wherein the content of the lower monovalent alcohol component (alcohol component) consisting of one or more selected from ethanol, methanol and propanol is less than the total content of the polyols or less than 10 mass%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an aerosol product in which lotion is filled with a hydrogen-containing propellant gas.

  In recent years, attempts have been made in the field of cosmetics to impart reducing properties by dissolving gaseous hydrogen, and to provide functions such as moisturizing skin, whitening, anti-aging (anti-aging), and patent applications have been filed (Patent Literature). 1-12). If you increase the viscosity of the base material of liquid cosmetics that retain dissolved hydrogen, such as beauty serums, emulsions, gels, and creams, the evaporation of hydrogen when applied to the skin, etc. will be suppressed, and the above moisturizing, whitening, anti-aging A greater effect can be produced with respect to the above (Patent Documents 8 to 12). For example, a milky lotion serves to moisturize the skin by supplementing the skin with a good balance of moisture and moisturizing ingredients, mainly oil.

  However, in order to promote the penetration of active ingredients such as emulsion into the skin, it is important that the state of the stratum corneum of the skin is sufficiently prepared prior to the use thereof. A lotion is used for this purpose. Lotion has a significantly low viscosity and low oil phase component content, so it does not have a long-lasting water retention capacity like milky lotion, but it removes dirt on the surface and quickly penetrates water quickly. Moisture and flexibility are given to the stratum corneum, and the permeation and sustaining effect of the skin-beautifying and moisturizing components from the subsequent emulsion is sufficiently extracted. In other words, it softens the skin that has been stiffened by replenishing moisture to the stratum corneum of the skin, and works to increase the penetration of the later-used emulsion and serum into the skin. And addition of gaseous hydrogen is also tried to such lotion (patent documents 1-7). By adding gaseous hydrogen to the skin lotion, the stratum corneum, which is prepared as a base, is retained in the reduction zone, allowing water to be replenished while reducing damage due to oxidation, and the ability of dissolved hydrogen to penetrate water into the skin. Because it improves, it is said that a more fresh and elastic skin condition can be realized, and the duration of the effect can be greatly extended.

  By the way, since gaseous hydrogen has low solubility in water and its specific gravity is the smallest among all gases, hydrogen dissolved in low-viscosity lotion rapidly evaporates when the liquid level is exposed to the atmosphere. As a result, when gaseous hydrogen is dissolved in the lotion by pressurization or stirring and bottling, the amount of free space in the bottle increases as the lotion is used. There is a problem that the concentration of dissolved hydrogen in the remaining lotion is greatly reduced. This problem is somewhat caused by storing the hydrogen-containing lotion in an aluminum pouch container having excellent barrier properties against gaseous hydrogen (for example, Patent Document 5), and expelling air from the pouch and plugging it every time it is used. However, due to the loss of luxury due to the poor appearance of the aluminum pouch container and the excessive flexibility of the container itself, there is also the inconvenience that the lotion will blow out if too much force is applied. , Almost not popular. In addition, in actual products, a form in which a single use portion is packaged in individual small-sized aluminum pouches is also found (for example, trade name: Aquadeto (minus 600 millivolts), URL: http: //www.m600mv .Co.jp / beautity.html) In addition to the increased packaging costs, the pouch-wrapped amount of course can only be used up once, and there is a problem that it cannot be flexibly adapted to the proper usage amount that varies among individuals. .

  By the way, a lotion has a rapid moisture penetration but also a rapid evaporation, and if it is applied to the face while being uniformly applied, a sufficient effect cannot be obtained even when the skin is finished with an emulsion or the like. As an application method, it is recommended to soak it in cotton and apply it to the skin. Recently, however, aerosol lotion that is easy to carry and easy to carry even without using cotton is available. It is becoming popular. This aerosol form has another important significance in the case of hydrogenated lotions. In other words, by containing hydrogen in the aerosol injection gas, the dissolved hydrogen concentration in the sealed container is maintained according to the hydrogen concentration in the filling gas, regardless of the remaining amount of the toner in the container. There are advantages you can do. Such aerosol products of hydrogen-containing lotion are disclosed in Patent Documents 1 to 3.

  Japanese Patent Laid-Open No. 2001-2560   JP 2015-37769 A   JP2015-86220A   Japanese Patent No. 4600809   JP 2014-227346 A   JP 2004-285036 A   Japanese Patent Laid-Open No. 2005-21876   JP 2007-308467 A   JP 2007-314496 A   JP 2008-279424 A   JP 2011-173083 A   Japanese Patent No. 5060032

Problems to be solved by the invention

  Evaporation of dissolved hydrogen in water is further accelerated when stirring or vibration is applied to the water. When using a lotion filled with aerosol, the lotion is vigorously stirred when injected at high pressure through the pores of the nozzle. There is a problem that many of them are evaporated and lost before reaching the skin. In particular, the formula of the skin lotion is a highly volatile lower monohydric alcohol component such as ethanol (hereinafter referred to simply as “alcohol component” in the present specification, unless otherwise specified, such as ethanol, propanol and methanol). In the case of containing monohydric alcohol), the loss of dissolved hydrogen when spraying lotion is further increased. This is a matter to be worried not only because of the loss of the above-mentioned effect due to the hydrogen addition, but also in that a lot of wasted hydrogen component is generated.

  In skin lotions, these alcohols are often added to sterilize and clean, improve the solubility of oil phase components, as well as to provide a refreshing sensation accompanying the volatilization of alcohol on the skin and an astringent (tightening) effect on the skin. . On the other hand, in recent years, excessive astringent action and degreasing by alcohol have been disliked, and there has been considerable demand for lotion formulations that do not use alcohol, but lotions that do not contain alcohol are often worried about stickiness. In particular, a lotion formulation containing a large amount of polyols such as glycerin and ethylene glycol as a moisturizing component tends to feel uncomfortable. On the other hand, lotion without adding moisturizing ingredients has low moisture retention after application, and it is not widely used as a commercial lotion because it has little moisturizing and softening effect on the stratum corneum, which is required as a base for emulsion application. It is rarely used in prescriptions.

  Examining the contents of the prior art related to aerosol products using hydrogen-filled gas in order, in Patent Document 1, what is filled is purified water to which catechin, an antioxidant, is added, instead of containing alcohol. Also, it does not contain any moisturizing ingredients and cannot be expected to function as a lotion as it is. Also in Patent Documents 2 and 3, the filler is simply purified water, which causes the same problem as the aerosol product of Patent Document 1. In addition, although the concept of “cosmetics” as a filler is described in the claims of Patent Document 2, no specific composition example of the cosmetics is disclosed at all, and therefore, particularly described in the previous paragraph. Further, it is impossible to read about the problem and the means for solving the problem of hydrogen transpiration at the time of injection accompanying the addition of alcohol and the increased stickiness caused by the addition of moisturizing ingredients.

  On the other hand, Patent Document 4 suggests the possibility of gaseous hydrogenation for both alcohol-added lotions and non-alcohol-containing lotions, but specific lotions disclosed in Reference Examples and Examples. All formulations include alcohol. And it is a normal bottle filled with lotion, and no measures are taken for preventing the transpiration of hydrogen after opening, and the adoption of an aerosol container is not mentioned. Naturally, there is no description or suggestion about the problem relating to the transpiration of dissolved hydrogen when spraying the skin lotion containing alcohol from the aerosol. Moreover, there is no disclosure of a specific formulation for the non-alcohol-containing lotion, and it is impossible to read about problems and solutions relating to a decrease in refreshing feeling in the non-alcohol-containing lotion and an increase in stickiness due to the addition of a moisturizing agent.

  The subject of this invention is providing the aerosol product of the hydrogen containing lotion which can prevent the dissolved hydrogen loss at the time of injection effectively, is excellent in moisture retention, and can maintain a refreshing feeling also in a low alcohol prescription.

Means for solving the problem

In order to solve the above-mentioned problems, the aerosol product of the present invention is an aerosol product obtained by pressurizing and filling lotion with a spray gas into an aerosol container,
The propellant gas contains 1% by volume or more of hydrogen, and the total content of hydrogen and inert gas is 90% by volume or more,
The lotion contains a hydrophilic organic component having an IOB value of 1.7 or more and 6 or less within a range of 5% by mass or more and 30% by mass or less, and polyols as hydrogen transpiration suppressing components that form part of the hydrophilic organic component. Whether the content of the lower monohydric alcohol component consisting of one or more selected from ethanol, methanol and propanol is less than the total content of the polyols. Or less than 10% by mass.

  In the present invention, the “inert gas” includes carbon dioxide gas as a concept in addition to nitrogen, argon, helium and neon, and one or a mixture of two or more thereof can be used.

  According to the configuration of the present invention, since the lotion is filled in the aerosol container together with the propellant gas containing 1.5% by volume or more of hydrogen, by injecting and using this, hydrogen is effective in the lotion. Can be dissolved. As a result, the stratum corneum of the skin that is prepared as a base by applying lotion is retained in the reduction region, and moisture penetration into the stratum corneum can be achieved while reducing damage due to oxidation. That is, the moisture and flexibility of the skin are improved as compared with the conventional lotion, and the penetration and sustaining action of the beautifying skin component and the moisturizing component from the subsequent emulsion can be more effectively extracted. In addition, by adding hydrogen to the aerosol injection gas, the dissolved hydrogen concentration in the sealed container is maintained according to the hydrogen concentration in the filling gas, regardless of the remaining amount of the toner in the container. it can.

  In the present invention, the lotion contains a hydrophilic organic component having an IOB value of 1.7 or more and 6 or less within a range of 5% by mass or more and 30% by mass or less. The IOB value is an abbreviation for Inorganic / Organic Balance (inorganic / organic ratio), and is a value corresponding to the ratio of the inorganic value of the compound to the organic value of the compound, and is an index indicating the degree of polarity of the organic compound It is. Specifically, it is expressed as IOB value = inorganic value / organic value. For each of the “inorganic value” and “organic value”, for example, “organic value” is 20 for one carbon atom in the molecule, and “inorganic value” is 100 for one hydroxyl group, "Inorganic value" and "organic value" corresponding to various atoms or functional groups are set, and "inorganic value" and "organic value" of all atoms and functional groups in organic compounds are integrated. Thus, the IOB value of the organic compound is calculated (see, for example, Yoshio Koda, “Organic Conceptual Diagram: Basics and Applications”, pages 11-17, published by Sankyo Publishing, 1984).

  When considering the affinity between lotion and skin keratin layer mainly composed of protein, fat and fat, and the penetration of moisture into the skin, the organic component to be added to the lotion has an IOB value of 1.7 or more and 6 or less. It is important to select a hydrophilic component. Ingredients with an IOB value of less than 1.7 have a strong oily tendency and a large emulsifying action, and ingredients with an IOB value of more than 6 are less effective in maintaining the affinity between water and the skin. This is because there is a possibility of hindering the rapid penetration of water. And in order to maintain the penetration | invasion of water | moisture content and moderate holding | maintenance power, setting the total content of the hydrophilic organic component which has IOB of said range in the range of 5 mass% or more and 30 mass% or less is possible. is necessary.

And, as a result of detailed investigations, the inventors of the present invention have carried out aerosol injection of lotion with a gas containing hydrogen, the composition of the hydrophilic organic component of the lotion, and the persistence of the dissolved hydrogen concentration after injection, In addition, the present inventors have found that there is the following correlation between the moisturizing feeling and its sustainability, as well as the body feeling when applied to the skin, such as a refreshing feeling.
(1) By containing an appropriate amount of polyol as a hydrophilic organic component, not only the moisture retention of the skin is improved, but also the transpiration of dissolved hydrogen during injection is effectively suppressed. That is, polyols function as a hydrogen transpiration suppression component during aerosol injection.
(2) When the skin lotion in which hydrogen is dissolved is applied to the skin, it feels smoother than the skin lotion in which hydrogen is not dissolved, and the amount of alcohol component added is small or not added. Even if it exists, the refreshing feeling at the time of skin application is enhanced.
(3) The lotion in which hydrogen is dissolved has a longer duration of moisture retention than the lotion in which hydrogen is not dissolved. As a result, coupled with the effect of (2), despite the high moisturizing property, discomfort such as stickiness is also suppressed, and the skin finish can be obtained very comfortably.
As long as the effect of (1) is within the proper composition range, the effect of (2) and (3) tends to become more pronounced as the amount of dissolved hydrogen after injection increases as the added amount of polyols increases. .

In the present invention, on the premise of the above, the total content of polyols as a hydrogen transpiration suppressing component in a lotion filled with aerosol is 3% by mass or more and 20% by mass or less, and imparting a refreshing feeling, sterilization / washing or skin The content of the lower monohydric alcohol component (especially ethanol) consisting of one or more selected from ethanol, methanol and propanol added for the purpose of tightening is less than the total content of the polyols, Or it sets to less than 10 mass%. Thereby, transpiration of dissolved hydrogen from the skin lotion at the time of aerosol injection can be effectively suppressed. The significance of this effect can be easily understood by considering it in two ways: when the alcohol that promotes the transpiration of dissolved hydrogen is contained in the lotion within the above range and when it is not contained.
A: When an alcohol component is added: Evaporation of the alcohol component at the time of injection tries to promote the transpiration of dissolved hydrogen, but this harmful effect is suppressed by the effect of adding polyols, and lotion is effective even after aerosol injection Can maintain a high dissolved hydrogen concentration. As a result, it is possible to achieve both cleaning, bactericidal effect and refreshing effect by adding an alcohol component.
B: When no alcohol component is added: The effect of suppressing the transpiration of dissolved hydrogen due to the addition of polyols is remarkably achieved, and the sticky feeling due to the addition of polyols is suppressed by a new refreshing sensation derived from the increase in dissolved hydrogen concentration. . As a result, while having very good moisturizing properties due to polyols and dissolved hydrogen, the sticky feeling peculiar to the lotion to which no alcohol component is added is suppressed by the refreshing feeling derived from dissolved hydrogen.

  In any case, the effects of maintaining the reducing properties of the skin with dissolved hydrogen, improving and sustaining the moisturizing property, and imparting a refreshing sensation are difficult to achieve due to differences in the action of alcohol components and polyols. It can be seen that there are advantages that can be achieved simultaneously. In A, the refreshing feeling and the improvement of the smooth feeling on the skin become more prominent. In B, the reducing ability is imparted to the skin as the dissolved hydrogen concentration increases, and the whitening and anti-aging effects derived therefrom. Etc. tend to become more prominent.

  In addition, if the total content of polyols is less than 3 masses, the transpiration of dissolved hydrogen during aerosol injection becomes significant, and sufficient effects peculiar to dissolved hydrogen cannot be obtained, or wasteful loss of hydrogen increases, which is uneconomical. This causes a problem of becoming 3 mass% or more. From the same viewpoint, it is more desirable that the total content of polyols is 1/2 or more of the total content of hydrophilic organic components. Further, the hydrophilic organic component desirably has an alcohol component (lower monohydric alcohol component) content of less than 80% of the total content of polyols.

  Moreover, when the total content of polyols exceeds 20% by mass, the feeling of stickiness to the skin becomes excessive, which may lead to discomfort. The total content of polyols is more desirably 5% by mass or more and 17% by mass or less. In addition, if the content of alcohol components (especially ethanol) exceeds the total content of polyols or exceeds 10% by mass, the transpiration of dissolved hydrogen during aerosol injection becomes significant, and the effects unique to dissolved hydrogen Cannot be obtained sufficiently, or wasteful loss of hydrogen is increased, resulting in uneconomical problems.

  The polyols that can be added to the skin lotion in the present invention include, for example, glycerin, polypropylene glycol / polyethylene glycol copolymer or alkyl ether thereof, polyethylene glycol or alkyl ether thereof, polyoxyalkylene dicarboxylic acid ester, 1,3-butylene glycol. , Dipropylene glycol, isoprene glycol, 1,2-pentane glycol, 1,2-hexane glycol, 2-methyl-1,3-propanol, ethyl carbitol, 1,2-butylene glycol, and polyoxyethylene methyl glucoside Although it is 1 type or 2 types or more chosen, it is not limited to these. Among these, glycerin is the component that is most excellent in the effect of suppressing dissolved hydrogen transpiration during aerosol injection. In order for the lotion to make the dissolved hydrogen transpiration suppression effect more prominent, it is desirable to contain, for example, glycerol as a polyol in a range of 1% by mass to 8% by mass.

When the aerosol container is equipped with a valve unit that injects while mixing the injection gas and the lotion, the lotion is injected as fine droplets, so the influence of dissolved hydrogen evaporation is particularly significant. The effect when the present invention is applied becomes more conspicuous. Then, by making the composition of the lotion and the injection gas within the range of the present invention, the filling pressure of the injection gas into the aerosol container is P (MPa), and the hydrogen volume content in the injection gas is U _H The concentration of dissolved hydrogen measured immediately after collecting 30 cc in a cylindrical container having an inner diameter of 5 cm while spraying lotion from the spray nozzle of the aerosol container is defined as C _H (ppm).
D _R ≡C _H /(1.61·U _H · 10P) (when (U _H · 10P) <1)
≡C _H /1.61 (when (U _H · 10P) ≧ 1)
Residual hydrogen ratio D _R to be represented by it is possible to secure not less than 0.55.
The ambient temperature is assumed to be room temperature (20 ° C.). In addition, the injection of the skin lotion from the nozzle is collected in a container through a capillary tube having an inner diameter of 1 mm and a length of 80 mm attached to the nozzle.

Described above meanings hydrogen residual rate D _R. When the hydrogen volume content obtained by analyzing the injection gas in the aerosol container is U _H and the filling pressure of the injection gas into the aerosol container is P (MPa), the partial pressure of hydrogen in the aerosol container is U _H · P (MPa), which is converted into a unit of atmospheric pressure, and since 1 atmospheric pressure (pressure felt by the skin lotion after injection) is 0.1 MPa, the hydrogen partial pressure is U _H · 10 P (atmospheric pressure). The saturation concentration of dissolved hydrogen in water at 1 atm because it is 1.61Ppm, equilibrium dissolved hydrogen concentration for lotion in the container with hydrogen partial pressure becomes 1.61 · U H · _10P. When the dissolved hydrogen concentration after the injection of the lotion (for example, it can be measured with a polarographic dissolved hydrogen meter) is C _H , the value of C _H /(1.61·U _H · 10P) is aerosol. It means the ratio of hydrogen that is considered to be dissolved in the lotion in the container and remains in the lotion even after injection. Of course, the hydrogen residual rate D _R are wasted less of hydrogen, also is a good higher from the viewpoint of effect can be enhanced due to dissolved hydrogen, by optimizing the composition of the lotion, better value, for example zero. It is sufficiently possible to secure 7 or more by adopting the present invention.

Depending on the concentration of the injection gas and the setting of the filling pressure, the hydrogen partial pressure in the container may exceed the normal pressure (0.1 MPa). In this case, hydrogen exceeding the solubility under normal pressure is dissolved in the lotion in the container, but when the pressure returns to the atmospheric pressure after being ejected from the nozzle, the hydrogen dissolved in supersaturation is quickly foamed. since transpiration, calculation of the denominator of the residual hydrogen percentage D _R, it is reasonable to use 1.61ppm a saturated concentration of dissolved hydrogen at atmospheric pressure.

  The hydrogen concentration of the propelling gas is preferably 1.5% by volume or more and 97% by volume or less. When the hydrogen concentration of the injection gas is less than 1.5% by volume, sufficient hydrogen does not remain in the lotion after injection, and the effect becomes insufficient. Further, in order to increase the hydrogen concentration of the propellant gas to 97% by volume or more, after the lotion is injected into the aerosol container, the atmosphere in the gas filling space on the upper side is exhausted to an extremely low pressure, or is discharged to the container. Therefore, it is necessary to perform the filling of the lotion and the gas in an atmosphere filled with an inert gas. The former causes transpiration of components accompanying the boiling of the cosmetic water in the container, and the latter makes it difficult to avoid an increase in equipment costs for forming the atmosphere. When the container is filled with lotion or gas in the atmosphere, atmospheric components remain in the container before the injection gas is filled. As a result, oxygen, nitrogen and argon derived from the atmosphere remain in the spray gas in the aerosol container after filling. In this respect, the hydrogen concentration of the injection gas is more desirably 96% or less, and further desirably 93% or less.

  If the inert gas component other than hydrogen in the propellant gas is nitrogen, or if there is a large amount of dissolved oxygen in the lotion, the oxygen or nitrogen concentration in the propellant gas is the amount of oxygen or nitrogen derived from the atmosphere. It does not match. However, the argon concentration reflects the atmospheric argon concentration unless argon is positively added from the outside, and is a measure for knowing the amount of air remaining in the container before the injection gas is charged. This residual air amount is preferably low in terms of reducing the oxygen concentration that becomes oxidizable by dissolution in water. If the space in the container is up to about 70% of its volume before being filled with the propellant gas, it can be evacuated without boiling of the lotion (the residual amount in the atmosphere is 30% of the space volume). In this state, for example, when an injection gas composed of hydrogen and nitrogen is filled and the internal pressure of the container is 1 MPa (10 atm), the argon concentration of the injection gas in the aerosol container can be reduced to 0.03% by volume. On the other hand, when the injection gas is filled without exhausting the space in the container and the internal pressure of the container is 0.5 MPa (5 atm), the argon concentration of the injection gas in the aerosol container is 0.20% by volume. When the argon concentration is higher than this, the pressure of the injection gas is insufficient, the amount of the lotion remaining without being finally injected into the container is increased, and waste is increased. In addition, when the amount of residual air in the aerosol container increases, the oxygen concentration of the injection gas increases, and the effect of dissolved hydrogen may be diminished. From the same viewpoint, the oxygen concentration in the injection gas is preferably 0.5 volume% or more and 4.5 volume% or less, and more preferably the oxygen concentration of the injection gas is 2 volume% or less.

It is desirable that pure hydrogen gas is adopted as the raw gas filled from the outside into the aerosol container as the injection gas from the viewpoint of increasing the dissolved hydrogen concentration in the skin water after the injection. At this time, in consideration of the influence of the residual air in the aerosol container, the hydrogen concentration of the injection gas in the aerosol container is preferably 80% by volume or more, more preferably 85% or more. At this time, the hydrogen residual rate D _R makeup water after injection can be ensured than 0.65, the D _R can be increased to about 0.8 by Regulation of the composition of the lotion.

On the other hand, when hydrogen gas having a low explosion lower limit concentration in the atmosphere is used as the injection gas, the hydrogen concentration of the injection gas is set to 1.5% by volume or more and 7% by volume or less, thereby reducing the incombustibility of the injection gas itself. It can be raised and handling becomes easy. And in particular even in the case of employing the low injection gas of such hydrogen content, by adopting the present invention, the hydrogen residual rate D _R makeup vertebral after injection to ensure a high value even 0.7 or higher it becomes possible, the D _R can be increased to about 0.95 by Regulation of the composition of the lotion. In this case, the raw gas filled in the aerosol container as the injection gas from the outside adopts a hydrogen concentration of 5.8% or less, desirably 4% or less, more desirably 3% or less from the viewpoint of nonflammability. It is desirable. Moreover, it is desirable that the hydrogen concentration of the propelling gas in the container is 1.7 vol% or more and 3 vol% or less.

  The viscosity of the skin lotion filled in the aerosol container is desirably adjusted to 500 mPa · s or less. When the viscosity exceeds this value, sprayability from the aerosol is deteriorated, skin extensibility may be impaired, or excessive stickiness may occur. The lower limit of the viscosity is not particularly limited, but in the case of an aqueous cosmetic, it is generally about 1 mPa · s unless the viscosity is positively imparted. The viscosity of the skin lotion (and hence the viscosity of the resulting hydrogen-containing liquid aqueous cosmetic) is desirably 100 mPa · s or less, more desirably 50 mPa · s or less. In the present specification, as the viscosity, a value measured at 25 ° C. by a B-type viscometer (Brookfield viscometer) with an LV4 rotor at a rotation speed of 60 rpm is used.

  In addition, the lotion may be filled in an aerosol container previously containing hydrogen. In this way, the lotion sprayed from the aerosol container has a higher concentration in addition to the dissolved contribution from hydrogen contained in the propellant gas, in addition to what was previously contained in the lotion before filling the container. Hydrogen can be contained in the water, and the effect of the dissolved hydrogen described above can be enhanced. In particular, if a part of hydrogen previously contained in the lotion is contained as fine bubbles having an average bubble diameter of 1 μm or less, preferably 500 nm or less, more hydrogen can be contained, and the lotion after injection This improves the persistence of the dissolved hydrogen concentration and further improves the permeability of the skin lotion to the skin.

Hereinafter, constituent components and components that can be added to the lotion that can be used in the present invention are listed below.
Water is a component that forms the base of a liquid composition, and RO water or ion exchange water is used.
An aqueous solvent can be blended as appropriate. As an aqueous solvent, it can be used combining 1 type (s) or 2 or more types of ethanol, propanol (especially isopropanol), and methanol.
Moisturizing component: polyols have already been described. In addition, sorbitol, xylitol, maltitol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, chitosan and the like can be added as moisturizing ingredients.

Thickener: cellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, methylcellulose, carboxymethylcellulose, quince seed, carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, Heparan sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, caronic acid, chitin, Chitosan, carboxymethyl chitin, agar, gum arabic, gelatin, hyaluronic acid, z Chin, mucopolysaccharides, Chuberosu polysaccharide body or the like.
Antibacterial preservatives: benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid esters (such as ethyl paraben and butyl paraben), hexachlorophene and the like.

  Organic acids: amino acids such as glycine, alanine, valine, leucine, serine, threonine, phenylalanine, tyrosine, aspartic acid, asparagine, glutamine, taurine, arginine, histidine and their salts. Acyl sarcosine acid (eg, lauroyl sarcosine sodium), glutathione, citric acid, malic acid, tartaric acid, lactic acid and the like.

  Various drugs: Vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B such as vitamin B12, vitamin B15 and its derivatives, ascorbic acid, phosphorus ascorbate Vitamin C such as acid ester (salt), ascorbic acid dipalmitate, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin E nicotinate, etc., vitamin D, vitamin H, pantothenic acid, Vitamins such as pantethine. Nicotinamide, benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, hinokitiol, mucidin, bisabolol, eucalyptol, thymol, inositol, saponins (psychosaponin, carrot saponin, loofah) Saponin, muclodisaponin, etc.), pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, cephalanthin, placenta extract, etc.

  Natural extract: Barefoot, Clara, Kouhone, Orange, Sage, Thyme, Yarrow, Zeniai, Senkyu, Assembly, Spruce, Spruce, Birch, Horsetail, Loofah, Maronie, Yukinoshita, Arnica, Lily, Mugwort, Peonies, Aloe, Chinesea Extracted from organic solvent, alcohol, polyhydric alcohol, water, aqueous alcohol, etc.

  In addition, IOB value is less than 1.5 for surfactants, sequestering agents, fats and oils, waxes, hydrocarbon oils, synthetic ester oils, silicone oils, higher fatty acids, higher alcohols, etc. As long as it contains a lot of ingredients and the viscosity does not exceed the range suitable for lotions, and the oily ingredients do not feel excessively sticky to the skin, they can be added as appropriate while carefully limiting the amount added. is there. Since specific examples of these components are well known, detailed listing is omitted.

Effect of the invention

  Since the details of the operation and effect of the present invention have already been described in the section of “Means for Solving the Problems”, they will not be repeated here.

  The perspective view which shows an example of the aerosol product of this invention   The longitudinal cross-sectional view which shows the principal part of the aerosol container in FIG.   The longitudinal cross-sectional view which expands and shows the injection valve of FIG.   The schematic diagram which shows an example of the apparatus which adds gaseous hydrogen to a lotion as a hydrogen fine bubble.   FIG. 5 is a cross-sectional view showing an example of a liquid processing nozzle used in the apparatus of FIG. 4.   The side surface enlarged view of FIG.   Sectional drawing which shows the detail of the processing core part of the liquid processing nozzle of FIG.   FIG. 7 is an enlarged view that substantially illustrates an arrangement form of screw members forming a collision portion in one throttle hole of FIG. 6.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a perspective view showing an embodiment of the aerosol product of the present invention. The aerosol product 300 is a product obtained by pressurizing and filling a lotion 301 with an injection gas 303 into an aerosol container 302. The propellant gas 303 contains 1% by volume or more of hydrogen (gaseous hydrogen), and the total content of hydrogen and inert gas is 90% by volume or more. The “inert gas” included in the propelling gas 303 includes carbon dioxide gas as a concept in addition to nitrogen, argon, helium, and neon, and is one or a mixture of two or more thereof. In this embodiment, nitrogen gas is used. Is used, and contains a small amount (for example, less than 0.20% by volume) of argon gas partially derived from the atmosphere. The hydrogen concentration of the injection gas 303 is desirably 1.5 volume% or more and 97 volume% or less, and the filling pressure to the aerosol container 302 is, for example, 0.4 MPa or more and 1 MPa or less.

  On the other hand, the skin lotion 301 contains a hydrophilic organic component having an IOB value of 1.7 or more and 6 or less within a range of 5% by mass or more and 30% by mass or less, and forms a part of the hydrophilic organic component. The content of the lower monohydric alcohol component (alcohol component) consisting of one or more selected from ethanol, methanol and propanol is 2 to 20% by mass. The total content is less than or less than 10% by mass. The total content of polyols is more preferably 1/2 or more of the total content of hydrophilic organic components, and the hydrophilic organic component has an alcohol content of 80% of the total content of polyols. It is more desirable to be less than. In this embodiment, ethanol is used as the alcohol component. Examples of components that can be employed as polyols are as described above. The ratio of the filling space of the lotion 301 and the injection gas 303 in the aerosol container 302 is, for example, about 40% to 70% in terms of the ratio of the lotion volume to the total space volume in the container.

Hereinafter, the details of the structure of the aerosol product 300 will be described.
As shown in FIG. 2, in the aerosol product 300, a mountain cup 308 in which the valve unit 306 is airtightly integrated is assembled in the opening of the container body 305 of the aerosol container 301, and a dip tube is formed from the lower end of the valve unit 306. 304 extends downward in the container, and its lower end is immersed in the skin lotion 302. When the nozzle 307 attached to the valve unit 306 is pressed, the valve is opened, and the hydrogen-containing liquid aqueous solution sucked up by the dip tube 304 while the injection gas for pressurizing the hydrogen-containing liquid aqueous cosmetic 302 flows into the valve unit 306 as well. The cosmetic 302 is injected from the injection nozzle 307 together with the injection gas.

  FIG. 2 shows details of the valve unit 306. The valve unit 306 includes a valve casing 312 whose inside is an injection preparation chamber 313, a valve cap 311 that covers the opening of the injection preparation chamber 313, and an injection control head 310c that has one end positioned inside the injection preparation chamber 313. A valve sliding body 310 having a sliding shaft portion 310a with the other end projecting outside the valve cap 311 and arranged in a clearance fit with a sliding hole 311a formed in the valve cap 311; An elastic biasing member (configured by a compression coil spring in the present embodiment) 314 is provided between the bottom of the valve casing 312 and the valve sliding body 310 in 313. As shown in FIG. 1, a push type injection nozzle 307 (FIG. 1) is fitted to the sliding shaft portion 310a.

  A cylindrical tube connector portion 312a whose inner surface communicates with the injection preparation chamber 313 is integrated with the bottom of the valve casing 312 in a protruding form, and one end of the dip tube 304 is fitted therein. The valve sliding body 310 is disposed so as to be movable back and forth in the axial direction between a closed position where the injection control head 310c closes the sliding hole 311a and an open position where the injection control head 310c retracts from the sliding hole 311a. Has been. The sliding shaft portion 310a is formed with an injection path 310b that opens in the end surface on the protruding side from the valve cap 311 and is closed by the bottom on the opposite side in the axial direction, and an end on the side close to the injection control head portion 310c. A radial flow control hole 310b extending from its outer peripheral surface to the inner peripheral surface of the injection path 310 is formed through the portion. When the valve slide body 310 is in the closed position, the flow control hole 310b is blocked by the inner peripheral surface of the slide hole 311a of the valve cap 311. When the valve slide body 310 is in the open position, the flow control hole 310b is closed with the slide hole 311a. The injection preparation chamber 313 and the injection path 310b communicate with each other through the flow control hole 310b.

  The valve sliding body 310 is normally biased so as to be in the closed position by the elastic biasing member 314. A tapered valve seat surface 311b is formed in the sliding opening 311a of the valve cap 311 so as to follow the end portion on the injection preparation chamber 313 side, and in the closed position, the sliding shaft portion of the injection control head 310c is formed here. A tapered valve sealing surface 310d formed at the end of the connection side with 310 is brought into close contact with each other, and the flow of the aerosol contents from the injection preparation chamber 313 side to the injection path 310b side is prevented.

  On the other hand, when the injection nozzle 307 in FIG. 1 is pressed, the valve sliding body 310 moves to the open position against the urging force of the elastic urging member 314, and the flow control hole 310b is detached from the sliding hole 311a. It moves to the large-diameter valve seat surface 311b side. Then, an annular gap communicating with the injection preparation chamber 313 is formed between the outer peripheral surface of the sliding shaft portion 310 and the valve seat surface. As shown in FIG. 2, the lotion 302 in the aerosol container 302 is pressurized by the jet gas 303. In this state, the lotion 302 is in the dip tube 304 → the jet preparation chamber 313 → the annular gap → circulation. It is injected out of the container from the injection hole 307a of the injection nozzle 307 of FIG. 1 through the control hole 310b → the injection path 310b.

  In the present embodiment, a gas flow hole 312b is formed so as to penetrate the wall portion of the valve casing 312. The compressed injection gas 303 flows into the injection preparation chamber 313 from the gas flow hole 312b, and the dip tube. 304 is mixed with the lotion 302 and injected from the injection nozzle 307 (FIG. 1) (however, the gas flow hole 312b can be omitted. In this case, only the lotion is injected from the injection nozzle 307. The Rukoto).

    In the lotion 302 thus sprayed, gaseous hydrogen of the spray gas 303 is dissolved, and when this is sprayed onto the skin and applied, the stratum corneum of the skin is retained in the reduced region, reducing the damage due to oxidation while the stratum corneum is reduced. Water penetration into the layer can be achieved. As a result, as will be described in detail in the examples described later, the moisture and flexibility of the skin are improved, and the penetration and sustaining action of the skin-beautifying and moisturizing components from the subsequent emulsion can be more effectively extracted. In addition, by adding hydrogen to the aerosol injection gas, the dissolved hydrogen concentration in the sealed container is maintained according to the hydrogen concentration in the filling gas, regardless of the remaining amount of the toner in the container. it can.

  Here, the lotion 302 contains a hydrophilic organic component having an IOB value of 1.7 or more and 6 or less within a range of 5% by mass or more and 30% by mass or less, and a total content of polyols as a hydrogen transpiration suppressing component. 3 mass% or more and 20 mass% or less, and the content of the alcohol component is set to be less than the total content of the polyols or less than 10 mass%. Thereby, the transpiration of dissolved hydrogen from the skin lotion 302 at the time of aerosol injection can be effectively suppressed.

  The addition of the alcohol component to the skin lotion 302 is optional, but when the alcohol component is added, the evaporation of the alcohol component at the time of injection tends to promote the evaporation of dissolved hydrogen, but the polyols dissolve the dissolved hydrogen. Since it has a transpiration suppressing action that remains in the liquid, the lotion can maintain an effective dissolved hydrogen concentration even after aerosol injection. As a result, it is possible to achieve both cleaning, bactericidal effect and refreshing effect by adding an alcohol component. On the other hand, when the alcohol component is not added, the effect of suppressing the transpiration of dissolved hydrogen due to the addition of polyols is remarkably achieved, and the sticky feeling due to the addition of polyols is suppressed by the refreshing feeling derived from the improvement of the dissolved hydrogen concentration. As a result, while having very good moisturizing properties due to polyols and dissolved hydrogen, the sticky feeling peculiar to the lotion to which no alcohol component is added is suppressed by the refreshing feeling derived from dissolved hydrogen.

And as in the above embodiment, when the jet gas 303 and the lotion 302 are mixed and jetted, the lotion is jetted as fine droplets, so that the evaporation of dissolved hydrogen is particularly likely to occur. By making the composition as described above, the effect of suppressing the dissolved hydrogen transpiration becomes more remarkable. For example, a capillary tube having an inner diameter of about 1 mm and a length of about 80 mm is inserted into the injection hole 307a of the injection nozzle 307, and 30 cc is collected in a cylindrical container having an inner diameter of 5 cm while spraying the skin lotion 302 through the capillary tube, and immediately measured. When the dissolved hydrogen concentration is C _H (ppm), the filling pressure of the injection gas 303 into the aerosol container 301 is P (MPa), the hydrogen volume content in the injection gas is U _H ,
D _R ≡C _H /(1.61·U _H · 10P) (when (U _H · 10P) <1)
≡C _H /1.61 (when (U _H · 10P) ≧ 1)
Residual hydrogen ratio D _R to be represented by it is possible to secure not less than 0.55.

Next, a method for manufacturing the aerosol product 300 as described above will be described.
That is, in FIG. 2, with the mountain cup 308 not attached, the aerosol container 301 is filled with lotion 302, and then the assembly of the mountain cup 308 is assembled with the valve unit 306 and the dip tube 304. Is inserted into the container main body 305 and covered with the opening, and the outer peripheral edges of both are crimped and sealed. In this state, the space formed above the liquid level of the lotion 302 in the aerosol container 1 is filled with residual atmosphere. Next, a gas filling connector (not shown) is connected to the sliding shaft portion 310 of the valve unit 306 protruding from the mountain cup 308, and a cylinder or the like connected to the gas filling connector is compressed while pushing down the sliding shaft portion 310 in this state. The raw gas of the injection gas is filled from the gas source to the set filling pressure. As a result, the aerosol container 301 is filled with an air-fuel mixture of the raw gas and the residual atmosphere as an injection gas.

  In addition, after filling the cosmetic container 302 with the aerosol container 301, the upper space of the cosmetic liquid 302 can be evacuated to about 0.3 MPa, for example, with the mountain cap 308 not attached. As a result, the amount of residual air mixed into the propellant gas 303 can be reduced, and in particular, the influence of oxygen that becomes oxidizing can be reduced.

As the raw gas to be filled, it is desirable to use pure hydrogen gas from the viewpoint of increasing the dissolved hydrogen concentration in the skin lotion after injection. For example, when the filling pressure of the injection gas 303 is 0.5 MPa and decompression exhaust before filling is not performed, the hydrogen concentration of the injection gas 303 in the aerosol container 301 is only about 80% by volume, and the filling pressure is 0. If the pressure is increased to 0.7 MPa, the hydrogen concentration becomes 85% by volume and 90% by volume at 10 MPa. At this time, the concentrations of argon derived from the residual air are 0.20% by volume, 0.14% by volume and 0.09% by volume, respectively, and the oxygen concentration is 4.2% by volume, 3.0% by volume and 2%, respectively. .1% by volume. On the other hand, when reduced pressure exhaust before filling is performed and the exhaust level is 0.4 MPa, the hydrogen concentration of the injection gas 303 is 92% by volume, 94% by volume, and 96% by volume, and the argon concentration is 0.07% by volume. 0.05% by volume and 0.03% by volume, and the oxygen concentration is 1.68% by volume, 1.20% by volume and 0.84% by volume. At this time, the hydrogen residual rate _{D R} in lotion 302 after injection can be ensured 0.65 or more, it is possible to increase the _{D R} to about 0.8 by Regulation of the composition of the lotion 302.

On the other hand, when hydrogen gas having a low explosion lower limit concentration in the atmosphere is used as the injection gas 303, the hydrogen concentration of the injection gas 303 is set to 1.5% by volume or more and 7% by volume or less so that the injection gas itself does not burn. Can be improved and handling becomes easy. Even when adopting a low propellant gas having a hydrogen content, the hydrogen residual rate D _R makeup vertebral after injection can secure high values also at least 0.7, optimization of the composition of the lotion 302 the _{D R} can be increased to about 0.95 by like. In this case, as the propellant gas, the raw gas filled from the outside into the aerosol container should employ a hydrogen concentration of 5.8% or less, desirably 4% or less, more desirably 3% or less from the viewpoint of nonflammability. Is desirable.

  Next, the skin lotion 302 may be filled with an aerosol container 301 containing hydrogen in advance. In this configuration, the lotion 302 sprayed from the aerosol container 301 is added with hydrogen contained in the lotion before filling the container 301 in addition to the one dissolved in hydrogen contained in the propellant gas 303. Hydrogen can be included in the concentration. The hydrogen to be contained may be dissolved by, for example, pressure dissolution, but if a part of the hydrogen to be contained is contained as fine bubbles having an average bubble diameter of 1 μm or less, preferably 500 nm or less, more hydrogen is contained. In addition, the persistence of the dissolved hydrogen concentration of the lotion 302 after injection can be improved, and the penetration of the lotion 302 into the skin can be further improved. Hereinafter, an example of a method for incorporating hydrogen into the lotion in the form of such fine bubbles will be described.

  FIG. 4 conceptually shows an example of an apparatus for producing a lotion containing hydrogen fine bubbles. In the apparatus 500, the skin lotion 502 as a raw material is stored in the tank 501 in a state where the viscosity is adjusted to 500 mPa · s or less (desirably 100 mPa · s or less, more desirably 50 mPa · s or less), In the middle of the circulation pipe 51 extending from the tank 501, a gas introduction part 219 composed of an ejector or the like, a liquid feed pump 505, and the liquid processing nozzle 1 are provided in this order. Hydrogen gas is supplied to the gas introduction part 219 from a hydrogen cylinder 420 as a hydrogen gas supply source via a pressure reducing valve 411 and a gas supply tube 412. As a hydrogen gas supply source, in addition to a hydrogen cylinder, an electrolytic hydrogen generator or a hydrogen storage alloy that reversibly adsorbs and desorbs hydrogen is used as a hydrogen gas storage unit, and hydrogen desorption from the hydrogen storage alloy by heating is performed. A hydrogen alloy canister that releases hydrogen gas may be used. The liquid feed pump 505 is constituted by a vane pump or a vortex pump suitable for liquid-liquid mixed phase liquid feed, and it is particularly desirable to use a vane pump.

  FIG. 5 shows a cross section of the liquid processing nozzle, and FIG. 6 shows an enlarged side surface of the liquid inlet side from the axial direction. The liquid processing nozzle 1 includes a nozzle body 2 in which a liquid channel 3 is formed. The nozzle body 2 is formed in a cylindrical shape, and a liquid passage having a circular cross section is formed in the direction of the central axis O thereof. The nozzle body 2 includes a partition wall 8 that divides the liquid flow path 3 into an inflow chamber 6 on the liquid inlet 4 side and an outflow chamber 7 on the liquid outlet 5 side, and an inflow chamber 6 and an outflow chamber formed through the partition wall 8. A processing core portion CORE is formed that includes a plurality of throttle holes 9 that communicate with each other through different paths and a collision portion 10 that protrudes from the inner surface of the throttle hole 9. In FIG. 6, two throttle holes 2 having the same inner diameter are formed in the partition wall portion 8 so as to be axial objects with respect to the central axis O. Each inner peripheral surface of the inflow chamber 6 and the outflow chamber 7 is a tapered surface 14 that decreases in diameter toward the processing core portion CORE.

  FIG. 8 is an enlarged view of one of them, and the collision portion 10 is formed so that a plurality of circumferential ridges 11 and valleys 12 serving as high flow velocity portions are alternately arranged on the outer peripheral surface. . In this embodiment, the collision part 10 is a screw member (hereinafter, also referred to as “screw member 10”) whose leg end side protrudes into the flow path, and as a result, a plurality of ridges 11 formed in the collision part. Are integrally formed in a spiral shape. In addition, a peak part and a trough part may be closely integrated in the axial direction of a collision part, without integrating in a spiral shape and closing in the circumferential direction.

As shown in FIG. 6, the collision unit 10 surrounds the central axis of each throttle hole 9 in the projection onto a plane orthogonal to the axis O of the nozzle body 2 in each of the plurality of throttle holes 9 in the processing core unit CORE. Four are arranged in a cross shape. As shown in FIG. 8, in each throttle hole 9, a main flow region 21 is formed between the screw member 10 and the inner peripheral surface of the throttle hole 9. A liquid circulation gap 15 is formed at the center position of the cross formed by the four collision portions 10. The front end surfaces of the four collision portions 10 forming the liquid flow gap 15 are formed flat, and the liquid flow gap 15 is formed in a square shape in the above-described projection. The inner diameter D of the throttle hole 9 (liquid flow path) is set to 2.5 mm or more and 7 mm or less (preferably 2.9 mm or more and 5.5 mm or less), and a liquid circulation area composed of the main circulation area 21 and the liquid circulation gap 15 is set. The total flow sectional area St is set to 2.5 mm ² or more and 35 mm ² or less (preferably 4 mm ² or more and 13 mm ² or less).

  FIG. 7 is an enlarged view of the processing core unit CORE. Each set of collision portions formed in the throttle hole 9 is formed by four screw members that are screwed so that the tip protrudes into the throttle hole 9 from the wall outer peripheral surface side of the nozzle body 2. As shown by a broken line in FIG. 6, the screw member 10 is screwed into a screw hole 19 penetratingly formed in the wall portion of the nozzle body 2, and supports the lower surface of the screw head at a midway position in the screw thrust direction of each screw hole 19. For this purpose, a stepped surface 19r is formed. The formation position of the stepped surface 19r is such that when the screw member 10 is screwed in, the length of the screw leg portion protruding into the throttle hole 9 (that is, the portion serving as the collision portion) forms the liquid flow gap 15. It has been adjusted to be appropriate. In addition, when the flow rate of the lotion flowing through the liquid processing nozzle 1 can be reduced as in the case of small lot production, only one throttle hole 9 may be provided, and two screw members that are opposed to each other in the diameter direction are also provided. It is good only as well.

  As shown in FIG. 5, in order to avoid the interference of the screw members 10 between the plurality of throttle holes 9, the set of four screw members 10 incorporated in each throttle hole 9 has an axial direction between the throttle holes 9. Are arranged at positions shifted from each other. In FIG. 7, the plurality of screw members 10 </ b> A, 10 </ b> B, 10 </ b> C, 10 </ b> D in the same throttle hole 9 are arranged at positions shifted from each other in the axial direction (flow direction) of the throttle hole 9. . Specifically, in each throttle hole 9, screw member pairs 10A, 10B and 10C, 10D arranged at positions orthogonal to each other on the same plane are different from each other in the flow direction (in FIG. The holes 9 are arranged at positions A and B on the downstream side, and the positions of the lower throttle holes are arranged at positions C and D on the upstream side. In the projection onto the plane orthogonal to the central axis O in FIG. 5, the four screw members 10A and 10B at the positions A and B and the four screw members 10C and 10D at the positions C and D respectively form a cross shape. Will be arranged as follows.

  A process for producing a lotion containing hydrogen fine bubbles using the apparatus 550 of FIG. 4 will be described. That is, when the skin lotion 502 as a raw material is charged into the tank 501 and the liquid feeding pump 505 is operated, the lotion from the tank 501 is supplied with hydrogen gas from the hydrogen cylinder 420 at the gas introduction unit 219 and mixed phase flow. And sucked into the liquid feed pump 505. When the flow rate of hydrogen gas for forming a multiphase flow is Q1, and the flow rate of the lotion is Q2, the dynamic pressure on the liquid inlet side of the liquid treatment nozzle 1 is 0.1 MPa or more and 0.5 MPa or less (preferably 0.2 MPa or more 0.4 MPa or less), and the flow rate ratio Q1 / Q2 of the hydrogen gas to the lotion is set to be 0.01 or more and 0.2 or less (preferably 0.03 or more and 0.1 or less).

  Since hydrogen gas is entrained in the stirring flow in the pump inside the liquid feed pump 505, the hydrogen gas phase is preliminarily crushed into bubbles of about 50 to 1000 μm and supplied to the liquid processing nozzle 1 on the downstream side of the pump. Further, the dissolution efficiency of hydrogen gas and the efficiency of crushing into fine bubbles of 1 μm or less are further enhanced. In this state, the multiphase flow is dissolved in the hydrogen gas and pulverized into fine bubbles by the liquid processing nozzle 1, and returns to the tank 502. Thereafter, while the water 502 in the tank is circulated, the hydrogen gas is continuously dissolved and pulverized into fine bubbles, so that the concentration of hydrogen fine bubbles is increased.

  The operation in the liquid processing nozzle 1 of FIG. 5 is as follows. The multiphase flow is first squeezed collectively by the taper portion 13, further distributed to the individual throttle holes 9, and individually squeezed by the liquid flow region composed of the main flow region 21 and the liquid flow gap 15, and the screw member Pass through this while colliding with 10. When passing through the outer peripheral surface of the screw member 10, the flow forms a high speed region at the thread valley and a low speed region at the peak. Then, the high-speed region of the valley portion becomes a negative pressure region by Bernoulli's theorem, and bubbles are generated by cavitation, that is, by the reduced pressure deposition of a pre-dissolved gas such as air.

  Since a plurality of valleys are formed on the outer periphery of the screw member 10 and a plurality of screw members 10 are arranged in the throttle hole 9, this reduced pressure precipitation occurs simultaneously and frequently in the valleys in the throttle hole 9. It will be. Then, when the liquid flow collides with the screw member 10, reduced pressure precipitation in the valley portion occurs violently, and further, this is entrained in the vortex generated when detouring downstream of the screw member 10 and vigorously stirred. In the vicinity of the impingement part 10 and in the immediately downstream region, a remarkable strong stirring region containing an infinite number of micro vortices is formed. The decompression area where the bubbles are deposited is limited to the vicinity of the valley bottom around the collision part, and the high-speed liquid flow passes through the area almost instantaneously. You don't have to worry about getting caught up and growing too much. Then, the lotion supplied to the liquid treatment nozzle 1 is mixed with bubbles of hydrogen gas preliminarily pulverized by the pump 505 to form a mixed phase flow. By being involved in the strong stirring region SM downstream of 10, the mixing with the lotion proceeds remarkably, and the microbubbles can be made extremely efficiently.

  Further, in the liquid processing nozzle 1, a plurality of constricted portions are formed in the partition wall portion 8, and the flow path sections before and after the constriction portion are concentrated in the inflow chamber 6 or the outflow chamber 7 defined by the partition wall portion 8. Therefore, the section where the flow path branches into a plurality of systems is only the throttle hole 9 formed in the partition wall 8. As a result, a decrease in flow velocity or non-uniformity in the throttle hole 9 is suppressed, and so-called drift in which hydrogen gas is biased to a part of the throttle hole 9 can be reliably prevented. That is, it is possible to achieve both a sufficient cavitation effect and a sufficient flow rate by forming a plurality of throttle holes 9 having the collision portion 10, and the drift between the plurality of throttle holes 9 is effectively suppressed, The generation of fine bubbles based on the cavitation effect can be continued stably.

  The lotion containing hydrogen fine bubbles thus obtained has an average diameter of fine bubbles measured by a laser diffraction particle size meter of about 100 nm to 800 nm, and a dissolved hydrogen concentration measured by a polarographic type dissolved hydrogen meter is 0.8 ppm or more. It can be increased to about 2.5 ppm or less (when the hydrogen fine bubbles are contained in a large amount, the hydrogen concentration indication value of the dissolved hydrogen meter may be supersaturated).

Hereinafter, the test conducted to confirm the effect of the present invention and the result thereof will be described.
(Experimental example 1)
As the lotion, those having various compositions shown in Tables 1 and 2 were prepared.

After weighing 80 cc of each of the above-mentioned lotions and injecting it into the container body of the aerosol container having an internal volume of 133 cc illustrated in FIGS. A sample was used.
(1) After pre-evacuating the gas filling space in the container to 0.5 MPa, the mountain cup was caulked and sealed, and filled with a nitrogen-2 volume% hydrogen mixed gas as a raw gas at a pressure of 0.7 MPa.
(2) The inside gas-filled space was preliminarily evacuated to 0.5 MPa, and then the mountain cup was caulked and sealed, and filled at a pressure of 0.7 MPa using a nitrogen-5% by volume hydrogen mixed gas as the raw gas.
(3) The container-filled gas filling space was sealed by caulking the mountain cup without preliminary vacuum evacuation, and was filled at a pressure of 0.7 MPa using pure hydrogen gas as the raw gas.
(4: Comparative Example) A mountain cup was caulked and sealed without preliminarily evacuating the gas filling space in the container, and it was filled with pure nitrogen gas as a raw gas at a pressure of 0.7 MPa.
Tables 1 and 2 show the composition analysis results by gas chromatography of the injected gas in the aerosol container.

Each aerosol product sample is inserted into a cylindrical container having an inner diameter of 5 cm while spraying a lotion through the capillary tube by inserting a capillary tube having an inner diameter of about 1 mm and a length of about 80 mm into the injection hole 307a of the injection nozzle 307 in FIG. 30 cc was collected. Then, using a polarographic dissolved hydrogen meter with measuring the dissolved hydrogen concentration C _H shortly after and 2 hours after injection _(ppm), was calculated residual hydrogen ratio D _R immediately after injection in accordance calculation formula described above.

Moreover, the skin toner of each aerosol product sample was used by 10 female subjects aged 20 to 60, and the following items were evaluated.
-Refreshing feeling: The operation of spraying 1 cc of skin lotion on the face and rubbing the skin lotion into the skin by hand was repeated twice at intervals of 1 minute to obtain an answer as to whether or not a remarkable refreshing feeling or smooth feeling was obtained. “◎” for 9 or more subjects who felt a refreshing or smooth feeling, “○” for 7 to 8 subjects, “△” for 4-6 people, and 3 or less subjects Was evaluated as “×”.
・ Moisturizing feeling: The operation of spraying 1 cc of skin lotion onto the face and rubbing the skin lotion into the skin by hand is repeated 3 times at 1 minute intervals. Is the skin moisturizing feeling (moist feeling) obtained after 5 minutes and 2 hours? We asked for an answer about whether or not. “◎” when the number of subjects who feel that the moisturizing feeling is remarkable is 9 or more, “○” when 7 to 8 people, “△” when 4 to 6 people, “×” when 3 or less people ".
・ Improvement of skin tension after one month: We asked for answers on skin elasticity, gloss, and wrinkle elimination when the same operation as moisturizing feeling evaluation was continued for one month. “◎” if there are 9 or more subjects who felt a clear effect on at least one of skin elasticity, luster and wrinkle resolution, “○” if 7 to 8 subjects, and 4 to 6 cases The case where “Δ” was 3 or less was evaluated as “X”.
The above results are shown in Tables 1 and 2.

Examples 1 to 4 in Table 1 show the results for lotions having a relatively large content of ethanol (alcohol component) and a relatively large total content of polyols. In the lotion compositions of Examples 1 to 3 having an ethanol content of 10% or less and less than the polyol content, of course, the hydrogen concentration in the propellant gas is 2% by volume or 5%. even when vol% and less, dissolved hydrogen concentration before and after 0.2ppm immediately after injection, high hydrogen residual rate _{D R} is also from 0.82 to 0.92 immediately after injection, after 2 hours and maintained approximately half Thus, it can be seen that the dissolved hydrogen concentration persists well. And although it contains many ethanol, it turns out that the moisturizing property after two-hour progress is favorable, the improvement effect of skin tone is also remarkable, and a refreshing feeling is also favorable. On the other hand, it can also be seen that the sample using nitrogen gas as the propellant gas is clearly inferior in the effect of maintaining the moisturizing feeling and improving the skin tone compared to the case where the propellant gas containing hydrogen is used. Moreover, about the sample of Example 1 and Example 2 with few addition amounts of ethanol, a refreshing feeling is also lacking, and it can be read that the addition of hydrogen has a clear effect on the improvement of the refreshing feeling. In other words, although the samples of Examples 1 to 3 have a high content of polyols that tend to cause stickiness, a sufficient refreshing feeling can be realized with a small amount of alcohol component due to the hydrogen content. It can be said that. On the other hand, about Example 4 in which alcohol content exceeds 10 mass%, the moisturizing feeling according to Example 1- Example 3 and the skin improvement effect can be achieved by making the addition amount of polyols considerably large. Yes. However, in the lotion of Comparative Example 1 in which the addition amount of polyols is kept small, the alcohol component evaporates remarkably, and even if the hydrogen content of the propellant gas is considerably increased, the dissolved hydrogen residual rate, sustainability, or moisturizing feeling It turns out that it is inferior to the improvement effect of skin tone.

  Next, Examples 5 to 9 in Table 2 show the results for lotions having a composition containing no ethanol (alcohol component) or having a relatively small content. Examples 6 and 7 are examples of compositions that do not contain ethanol at all. In Example 6 having a high polyol content, the refreshing feeling is somewhat sacrificed when the hydrogen content of the propellant gas is small. , Residual hydrogen residual rate and persistence, moisture retention, and skin-strengthening effect are extremely good, and by increasing the hydrogen content, the refreshing feeling can be improved to a level that is almost satisfactory. I understand that. This is particularly clear when compared with the result of nitrogen gas filling in which no hydrogen is added to the propellant gas, and it is clear that hydrogen addition is significant in the refreshing effect. In Example 7, the amount of polyol added is relatively small, but by adding a large amount of glycerin, ethanol was added a little to impart a refreshing feeling, but in Examples 6 and 7, It can be seen that comparable dissolved hydrogen residual ratio and persistence, moisture retention, and skin-strengthening effect can be achieved. On the other hand, the comparative example 2 is a result at the time of carrying out aerosol filling of purified water, and compared with Examples 6-9 which do not add polyols, it is clearly inferior to the residual rate and sustainability of dissolved hydrogen. In addition, it can be seen that the results of inferior moisturizing property and skin-strengthening effect are poor even when the amount of dissolved hydrogen is considerably high.

(Example 2)
In the apparatus 500 of FIG. 4, 180 L of lotion having the same composition as Table 1 and Table 2 in Experimental Example 1 (except for Comparative Example 2 in Table 2 using purified water) is charged into the tank 501, respectively. Circulation was performed while adding hydrogen under the conditions (liquid temperature 20 ° C.). The pump used was a vane pump TVP-MS1803 manufactured by Toshin Technical Co., Ltd. Moreover, the thing of the form shown in FIGS. 5-8 was used for the liquid processing nozzle 1. FIG. The material of the nozzle body 2 is ABS resin, the inner diameter of the liquid inlet 4 and the liquid outlet 5 is φ14 mm, and the lengths of the inflow chamber 6 and the outflow chamber 7 in the flow direction are 30 mm. With respect to the core part CORE, the number of formed throttle holes 9 is two in the arrangement shown in FIG. 3, the inner diameter d of the throttle hole 9 is φ4.6 mm, and the thickness of the partition wall part 8 is 7.0. The inner peripheral surfaces of the inflow chamber 6 and the outflow chamber 7 were each formed as a continuous tapered surface extending from the inner peripheral edge of the liquid inlet 4 and the liquid outlet 5 to the outer peripheral edge on the corresponding side of the partition wall portion 8. The collision portion 10 is formed by a screw member having a flat tip end surface, specifically, a M1.4 JIS coarse pitch pan head screw (made of SUS304 stainless steel), and has a flow cross-sectional area. Is about 10 mm ² for each aperture 9.

  The concentration of dissolved hydrogen in each lotion after the circulation is over 1.6 ppm, and by a laser diffraction particle size meter, a considerable amount of hydrogen fine bubbles having an average particle diameter of 100 to 400 nm is present in any lotion. It was confirmed that it was formed. Using these lotions, aerosol samples were prepared in the same manner as in Experimental Example 1, and the same evaluation was performed. Tables 4 and 5 show the results. In addition, Examples 11 to 14 and Comparative Example 3 in Table 4 use lotions having the same composition as Examples 1 to 4 and Comparative Example 1 in Table 1 before hydrogenation. Examples in Table 5 16-19 use the lotion of the same composition as Examples 6-9 of Table 2 before hydrogenation.

  Since each lotion before filling contains dissolved hydrogen and fine-bubble hydrogen, the amount of dissolved hydrogen and persistence after spraying, the moisturizing feeling, and the effect of improving skin tension are compared with Experimental Example 1 for each sample. It can be seen that it is greatly improved. However, it can be seen that the effect of the sample of Comparative Example 3 in which the amount of ethanol added is still insufficient.

300 aerosol product 301 aerosol container 302 lotion 303 spray gas 306 valve unit 307 spray nozzle

Claims (11)

An aerosol product in which lotion is pressurized and filled into an aerosol container together with a propellant gas,
The propellant gas contains 1% by volume or more of hydrogen, and the total content of hydrogen and inert gas is 90% by volume or more,
The skin lotion contains a hydrophilic organic component having an IOB value of 1.7 or more and 6 or less within a range of 5% by mass or more and 30% by mass or less, and serves as a hydrogen transpiration suppressing component that forms part of the hydrophilic organic component. The content of the lower monohydric alcohol component comprising the polyols in the range of 3 to 20% by mass and comprising one or more selected from ethanol, methanol and propanol is more than the total content of the polyols. Aerosol product characterized by being less or less than 10% by weight.   The aerosol product according to claim 1, wherein the lotion has a total content of the polyols of ½ or more of a total content of the hydrophilic organic components.   The aerosol product according to claim 2, wherein the hydrophilic organic component has a lower monohydric alcohol component content of less than 80% of the total content of the polyols.   The aerosol product according to claim 3, wherein the lotion contains glycerin as the polyol in a range of 1% by mass to 8% by mass.   The aerosol product according to any one of claims 1 to 4, wherein the aerosol container includes a valve unit that injects the injection gas and the lotion while mixing. A cylinder having an inner diameter of 5 cm while injecting the skin lotion from the spray nozzle of the aerosol container while setting the filling pressure of the spray gas into the aerosol container to P (MPa), the hydrogen volume content in the spray gas to U _H The dissolved hydrogen concentration measured immediately after collecting 30 cc in a cylindrical container is C _H (ppm).
D _R ≡C _H /(1.61·U _H · 10P) (when (U _H · 10P) <1)
≡C _H /1.61 (when (U _H · 10P) ≧ 1)
Aerosol products according to claim 5, wherein residual hydrogen ratio D _R is 0.55 or more, represented by.   The aerosol product according to claim 6, wherein the hydrogen concentration of the propellant gas is 1.5 vol% or more and 97 vol% or less, and the argon concentration is 0.03 vol% or more and 0.20 vol% or less.   The aerosol product according to claim 7, wherein the oxygen concentration of the injection gas is 0.5 volume% or more and 4.5 volume% or less.   The aerosol product according to claim 8, wherein the oxygen concentration of the injection gas is 2% by volume or less. The injection concentration of hydrogen gas is not less 80% by volume or more, aerosol product according to any one of claims 7 to 9 wherein the residual hydrogen ratio D _R is 0.65 to 0.8. The hydrogen concentration in the injection gas is not more than 7 vol% 1.5 vol%, to any one of claims 7 to 9 wherein the residual hydrogen ratio D _R is 0.7 to 0.95 The aerosol product described.

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