JP7453798B2 - Effervescent compositions and ejectable products - Google Patents

Description

FIELD OF THE INVENTION This invention relates to foamable compositions and ejectable products. More specifically, the present invention relates to a foamable composition and a discharged product that are maintained at a low pressure within a container body, are easily discharged at a constant pressure, and have excellent foaming properties when discharged.

Dispensable products filled with foamable compositions have been developed in the past. A typical foaming composition consists of an aqueous stock solution and a liquefied gas, and the liquefied gas is emulsified in the aqueous stock solution and is discharged to the outside, and uses the property that the volume expands as the liquefied gas evaporates to create a fine texture. forming bubbles. There is also a discharge product that discharges a foamable composition using compressed gas (Patent Document 1).

Japanese Patent Application Publication No. 2002-37362

In conventional discharge products consisting of an aqueous stock solution and a liquefied gas, the liquefied gas such as liquefied petroleum gas is lipophilic and therefore hardly dissolves in the aqueous stock solution, so it separates from the aqueous stock solution and exists in a liquid state within the container. . Therefore, the pressure inside the container is close to the saturated vapor pressure of the liquefied gas, and is as high as 0.4 to 0.5 MPa (25° C.). Further, in the discharge product of Patent Document 1 which is pressurized with compressed gas and discharged, the pressure inside the container tends to change from the initial stage to the final stage as the product is continuously used. Therefore, the discharge product cannot form a stable discharge. Further, in such a discharged product, in order to discharge the contents to the end, it is necessary to increase the initial pressure to about 0.8 MPa (25° C.). Therefore, conventional discharge products require a container body with high pressure resistance, and there is room for improvement in terms of weight reduction and material usage.

The present invention was made in view of such conventional problems, and provides a foamable composition that maintains a low pressure inside the container body, is easily discharged at a constant pressure, and has excellent foaming properties when discharged. The purpose is to provide products and discharge products.

The present invention for solving the above problems mainly includes the following configurations.

(1) A foaming composition comprising an aqueous stock solution and a liquefied gas, wherein the aqueous stock solution contains water, a blowing agent, and a hydrofluoroolefin having a boiling point of 5 to 40°C; A foamable composition whose pressure at 25° C. is 0.05 to 0.3 MPa.

According to such a configuration, in the foamable composition, a large amount of vaporized gas of the liquefied gas is dissolved in the aqueous stock solution. As a result, the foamable composition promotes volatilization of the hydrofluoroolefin during discharge, and easily foams. Further, when such a foamable composition is used by being filled into a container body, the inside of the container body is easily maintained at a low pressure.

(2) The foamable composition according to (1), wherein the content of the hydrofluoroolefin is 1 to 50% by mass in the aqueous stock solution.

According to such a configuration, in the foamable composition, since the content of hydrofluoroolefin is within the above range, the amount of dissolved gas in the liquefied gas is increased, and the pressure can be easily maintained at low pressure. Further, in the foamable composition, the volatilization of the hydrofluoroolefin is more likely to be promoted by the vaporized gas dissolved at the time of discharge, and the composition is more likely to foam.

(3) The foamable composition according to (1) or (2), wherein the content of the liquefied gas is 1 to 25% by mass in the foamable composition.

According to such a configuration, since the content of the liquefied gas is within the above range, the foamable composition easily dissolves in the hydrofluoroolefin and foams easily.

(4) The foamable composition according to any one of (1) to (3), wherein the liquefied gas has a saturated vapor pressure of 0.35 to 0.6 MPa at 25°C.

According to such a configuration, the foamable composition easily foams when being discharged because the saturated vapor pressure of the liquefied gas is within the above range.

(5) A container body filled with the foamable composition according to any one of (1) to (4) and filled with the aqueous stock solution, a gas container filled with the liquefied gas, and a container body filled with the foamable composition according to any one of (1) to (4); The container body includes an injection device for discharging vaporized gas of the liquefied gas, and the injection device includes a holder for accommodating the gas container and a regulating valve for adjusting the amount of the vaporized gas released. A discharged product comprising:

According to such a configuration, in the discharged product, vaporized gas of the liquefied gas is discharged into the container body by the injection device until a predetermined pressure is reached within the container body. This keeps the pressure within the container body constant. Therefore, the discharge product tends to maintain a constant pressure until the final stage without adjusting the initial pressure to a high pressure. Furthermore, the amount of vaporized gas dissolved in the aqueous stock solution is likely to be maintained constant, and the discharged material is likely to form stable bubbles.

(6) The discharge product according to (5), wherein the internal pressure of the container body is 0.05 to 0.3 MPa (25° C.).

According to such a configuration, the discharged product has a low pressure and is highly safe. Furthermore, since the discharged product does not need to have a highly pressure-resistant container body that can withstand higher internal pressures, the container body can be made lighter and the amount of materials used can be reduced.

According to the present invention, it is possible to provide a foamable composition and a discharged product that are maintained at a low pressure within a container body, are easily discharged at a constant pressure, and have excellent foaming properties when discharged.

FIG. 1 is a schematic cross-sectional view of a discharged product according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view for explaining a state in which a discharged product according to an embodiment of the present invention is being discharged. FIG. 3 is a schematic cross-sectional view for explaining the state in which the gas container is accommodated in the holder. FIG. 4 is a schematic cross-sectional view for explaining how the valve assembly and cover cap are attached to the container body. FIG. 5 is a schematic cross-sectional view illustrating a state in which the foamable composition is consumed using the ejected product according to an embodiment of the present invention.

<Foamable composition>
The foamable composition of one embodiment of the present invention includes an aqueous stock solution and a liquefied gas. The aqueous stock solution contains water, a blowing agent, and a hydrofluoroolefin with a boiling point of 5 to 40°C. The pressure of the foamable composition at 25° C. is 0.05 to 0.3 MPa. In the foamable composition of this embodiment, a large amount of vaporized gas of liquefied gas is dissolved in the aqueous stock solution. As a result, the foamable composition promotes volatilization of the hydrofluoroolefin during discharge, and easily foams. Furthermore, when the foamable composition of the present embodiment is used after being filled into a container main body, the inside of the container main body is easily maintained at a low pressure. Each will be explained below.

(aqueous stock solution)
The aqueous stock solution contains water, a blowing agent, and a hydrofluoroolefin with a boiling point of 5 to 40°C.

・Water Water is used as a solvent. The inclusion of water allows the foamable composition to form a foam when dispensed.

Water is not particularly limited. For example, the water may be purified water, ion exchange water, physiological saline, deep ocean water, or the like.

The content of water is not particularly limited. For example, the content of water in the aqueous stock solution is preferably 20% by mass or more, more preferably 30% by mass or more. Furthermore, the content of water in the aqueous stock solution is preferably 95% by mass or less, more preferably 90% by mass or less. When the water content is within the above range, the foamable composition exhibits excellent foaming properties, and it is easy to blend the hydrofluoroolefin described below in an appropriate amount.

- Foaming agent A foaming agent is blended to emulsify water and hydrofluoroolefin with a boiling point of 5 to 40°C, and to cause foaming when discharged to the outside.

The blowing agent is not particularly limited. For example, the blowing agent is a polymer compound, a surfactant, or the like.

The polymer compound is not particularly limited. For example, polymer compounds include synthetic water-soluble polymers such as polyether urethane, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, polyethyleneimine, sodium polyacrylate, agar, casein, dextrin, gelatin, etc. , pectin, starch, sodium alginate, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, nitrilecellulose, crystalline cellulose, and other natural water-soluble polymers. A polymer compound may be used in combination. Among these, the polymer compound preferably contains polyether urethane because of its excellent foamability.

The surfactant is not particularly limited. For example, surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, fatty acid alkanolamide, polyethylene glycol fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene glycerin fatty acid ester, polyoxyethylene Nonionic surfactants such as ethylene alkyl ether fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester; fatty acid soap, alkyl phosphoric acid and its salts such as lauryl phosphoric acid, polyoxyethylene alkyl ether acetic acid and its salts , anionic surfactants such as polyoxyethylene alkyl ether sulfate and its salts, alkyl ether carboxylates; N-acyl glutamate, N-acyl glycine salt, N-acylalanine salt; amino acid type anionic surfactant; These include silicone surfactants; carboxybetaine type such as cocamidopropyl betaine; amphoteric surfactants such as alkylimidazole type; amino acid type; and amine oxide type. Surfactants may be used in combination.

The content of the blowing agent is not particularly limited. For example, the content of the blowing agent in the aqueous stock solution is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. Further, the content of the blowing agent is preferably 30% by mass or less, more preferably 25% by mass or less. When the content of the foaming agent is within the above range, the foamable composition easily forms foam, has a viscosity that is easy to fill, is less sticky, and has an excellent feel when used.

- Hydrofluoroolefin with a boiling point of 5 to 40°C Hydrofluoroolefin with a boiling point of 5 to 40°C is blended in order to dissolve a large amount of vaporized gas in the liquefied gas and foam the foamable composition.

Hydrofluoroolefins having a boiling point of 5 to 40°C are not particularly limited. For example, hydrofluoroolefins with a boiling point of 5 to 40°C include trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E), boiling point 19°C), cis-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E), boiling point 19°C), -3,3,3-trifluoropropene (HFO-1233zd(Z), boiling point 39°C) and the like. Hydrofluoroolefins having a boiling point of 5 to 40°C may be used in combination.

The content of hydrofluoroolefin having a boiling point of 5 to 40°C is not particularly limited. For example, the content of hydrofluoroolefins having a boiling point of 5 to 40° C. in the aqueous stock solution is preferably 1% by mass or more, more preferably 5% by mass or more. Further, the content of hydrofluoroolefins having a boiling point of 5 to 40° C. in the aqueous stock solution is preferably 50% by mass or less, more preferably 30% by mass or less. Since the content of the hydrofluoroolefin having a boiling point of 5 to 40° C. is within the above range, the foamable composition can be easily foamed even at low pressure.

・Optional ingredients In addition to the water, blowing agent, and hydrofluoroolefins with a boiling point of 5 to 40°C, the aqueous stock solution may contain optional ingredients such as monosaccharides, alcohols, oils, powders, and active ingredients depending on the application. May include.

Monosaccharides are suitably blended for purposes such as adjusting the foamability of the foamable composition.

Monosaccharides are not particularly limited. For example, monosaccharides include sugar alcohols such as sorbitol, erythritol, arabitol, galactitol, glucitol, maltitol, mannitol, and xylitol; tetroses such as erythritol, D-erythrose, and D-threose; D-arabinose, L - Pentoses such as arabinose, D-xylose, D-lyxose, L-lyxose, D-ribose, D-xylulose, L-xylulose, D-ribulose, L-ribulose; D-altrose, L-altrose, D - Hexoses such as galactose, L-galactose, D-glucose, D-talose, D-mannose, L-sorbose, D-tagatose, D-psicose, D-fructose, and D-mannose. Monosaccharides may be used in combination.

When monosaccharides are blended, the content of monosaccharides is not particularly limited. For example, the monosaccharide content in the aqueous stock solution is preferably 0.5% by mass or more, more preferably 1% by mass or more. Further, the content of monosaccharides in the aqueous stock solution is preferably 20% by mass or less, more preferably 15% by mass or less. When the monosaccharide content is within the above range, the effects of incorporating the monosaccharide can be easily obtained. Moreover, the foamable composition tends to form stable foaming properties.

Alcohols may be blended as a solvent for active ingredients that are difficult to dissolve in water. Moreover, alcohols may be blended for the purpose of adjusting the foamability of the foamable composition.

Alcohols are not particularly limited. For example, alcohols include monohydric alcohols such as ethanol, propanol, isopropanol, isobutyl alcohol, and t-butyl alcohol, dihydric alcohols such as ethylene glycol, propylene glycol, and 1,3-butylene glycol, glycerin, and trimethylol. Trihydric alcohols such as propane, tetrahydric alcohols such as pentaerythritrile, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol and mannitol, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, diglycerin, polyethylene These include polymers of polyhydric alcohols such as glycol and triglycerin. Alcohols may be used in combination.

When alcohol is blended, the content of alcohol is not particularly limited. For example, the content of alcohol in the aqueous stock solution is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. Further, the content of alcohol is preferably 25% by mass or less, more preferably 20% by mass or less. When the content of alcohol is within the above range, the effects of blending alcohol can be easily obtained. Further, the foamable composition can easily obtain desired foamability.

The oil agent is suitably blended for the purpose of improving the feel of the obtained foam and making it easier to run through the fingers.

The oil agent is not particularly limited. For example, oils include dimethicone, methylpolysiloxane, cyclopentasiloxane, cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, tetrahydrotetramethylcyclotetrasiloxane, Silicone oils such as siloxane, octamethyltrisiloxane, decamethyltetrasiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane; Hydrocarbon oils such as liquid paraffin and isoparaffin; Methylpentanediol dineopentanoate, diethylpentanediol dineopentanoate, Neopentyl glycol -2-ethylhexanoate, neopentyl glycol dicaprate, propylene glycol dilaurate, ethylene glycol distearate, diethylene glycol dilaurate, diethylene glycol distearate, diethylene glycol diisostearate, diethylene glycol dioleate, triethylene glycol dilaurate, distearin triethylene glycol diisostearate, triethylene glycol dioleate, propylene glycol monostearate, propylene glycol monooleate, ethylene glycol monostearate, glyceryl tri-2-ethylhexanoate, tri(caprylic/capric acid) ) Ester oils such as glycerin, isononyl isononanoate, isotridecyl isononanoate, diethoxyethyl succinate, diisostearyl malate, isopropyl myristate, isopropyl palmitate, cetyl isooctanoate, octyl hydroxystearate, ethylhexyl hydroxystearate ; Oils and fats such as olive oil, camellia oil, corn oil, castor oil, safflower oil, jojoba oil, and coconut oil; Fatty acids such as isostearic acid and oleic acid; Higher alcohols such as oleyl alcohol and isostearyl alcohol. Oil agents may be used in combination.

When an oil agent is blended, the content of the oil agent is not particularly limited. For example, the content of the oil agent in the aqueous stock solution is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. Further, the content of the oil agent in the aqueous stock solution is preferably 20% by mass or less, more preferably 15% by mass or less. When the content of the oil agent is within the above range, the effects of blending the oil agent can be easily obtained. In addition, the foamable composition is less likely to reduce its foaming properties, less likely to reduce its drying properties, and less likely to cause stickiness.

Powder is suitably blended to improve the feeling of use, such as by imparting a dry feeling.

The powder is not particularly limited. For example, the powder is talc, zinc oxide, titanium oxide, silica, zeolite, kaolin, mica, magnesium carbonate, calcium carbonate, zinc silicate, magnesium silicate, aluminum silicate, calcium silicate, and the like. Powder may be used in combination.

When powder is blended, the powder content is not particularly limited. For example, the content of the powder in the aqueous stock solution is preferably 0.1% by mass or more, more preferably 0.3% by mass or more. Further, the content of the powder in the aqueous stock solution is preferably 5% by mass or less, more preferably 3% by mass or less. When the content of the powder is within the above range, the effect of blending the powder can be easily obtained, and the foamable composition is less likely to clog the discharge passage when being discharged.

Active ingredients can be blended depending on the purpose of the product. The active ingredient is not particularly limited. For example, active ingredients include ultraviolet absorbers such as diethylaminohydroxybenzoylhexylbenzoate, 2-ethylhexyl paramethoxycinnamate, ethylhexyltriazone, oxybenzene, hydroxybenzophenone sulfonic acid, sodium dihydroxybenzophenone sulfonate, and dihydroxybenzophenone. , UV scattering agents such as zinc oxide and titanium oxide, blood circulation promoters such as carpronium chloride and capsicum tincture, retinol, retinol acetate, retinol palmitate, calcium pantothenate, ascorbic acid, sodium ascorbate, dl-α-tocopherol, acetic acid. Vitamins such as tocopherol, tocopherol nicotinate, dibenzoylthiamine, riboflavin and mixtures thereof, keratolytic agents such as salicylic acid and resorcinol, various extracts such as Oriental japonica extract and rosemary extract, mint and menthol. Cooling agents, disinfectants such as cetylpyridinium chloride and isopropyl methylphenol, anti-inflammatory agents such as dipotassium glycyrrhizinate and tranexamic acid, floral, green, citrus green, green floral, citrus, rose, rosewood, herbal wood, lemon, These include fragrances such as peppermint, pH adjusters such as citric acid and lactic acid, chelating agents such as edetate disodium, and preservatives such as parabens and phenoxyethanol.

When an active ingredient is blended, the content of the active ingredient is not particularly limited. For example, the content of the active ingredient in the aqueous stock solution is preferably 0.1% by mass or more, more preferably 0.3% by mass or more. Further, the content of the active ingredient in the aqueous stock solution is preferably 20% by mass or less, more preferably 15% by mass or less. When the content of the active ingredient is within the above range, the foamable composition can easily obtain the effects of blending the active ingredient.

The method for preparing the aqueous stock solution is not particularly limited. The aqueous stock solution can be prepared by a conventionally known method. For example, an aqueous stock solution can be prepared by mixing water, a blowing agent, a hydrofluoroolefin having a boiling point of 5 to 40° C., and optional components that are appropriately blended in a suitable container.

(liquefied gas)
The liquefied gas is used as a propellant to pressurize the inside of the container and inject the aqueous stock solution. In addition, the vaporized gas of the liquefied gas is dissolved in the aqueous stock solution, particularly in the hydrofluoroolefin, so that when it is discharged to the outside, it promotes vaporization of the hydrofluoroolefin and improves the foaming properties of the foamable composition.

The liquefied gas is not particularly limited. For example, liquefied gases include normal butane, isobutane, propane, liquefied petroleum gases such as mixtures thereof, dimethyl ether, and hydrofluoroolefins having a boiling point of less than 5°C. Liquefied gas may be used in combination. The liquefied gas is preferably a hydrofluoroolefin having a boiling point of less than 5°C, since it is easily dissolved in the hydrofluoroolefin having a boiling point of 5 to 40°C.

Hydrofluoroolefins having a boiling point of less than 5°C are not particularly limited. For example, hydrofluoroolefins with boiling points below 5°C include trans-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze(E), boiling point -19°C), 2,3 , 3,3-tetrafluoro-1-propene (HFO-1234yf, boiling point -29.4°C).

In order to pressurize the inside of the container, compressed gas may be used in addition to the vaporized gas of the liquefied gas. The compressed gas is not particularly limited. For example, the compressed gas may be nitrogen, air, oxygen, hydrogen, carbon dioxide, nitrous oxide, or the like. Among these, the compressed gas is preferably nitrogen, air, or hydrogen, which have low solubility in water, because they tend to dissolve in the aqueous stock solution and form fine bubbles. Note that the pressure inside the container body is preferably adjusted to 0.2 to 0.5 MPa using compressed gas.

The content of the liquefied gas in the foamable composition is preferably 1% by mass or more, more preferably 2% by mass or more. Further, the content of liquefied gas in the foamable composition is preferably 25% by mass or less, more preferably 20% by mass or less. When the content of the liquefied gas is within the above range, the vaporized gas of the liquefied gas can be dissolved in the hydrofluoroolefin to lower the pressure of the foaming composition, and furthermore, the discharged foaming composition can be Easy to foam.

Returning to the explanation of the foamable composition as a whole, the foamable composition of the present embodiment may have a pressure at 25° C. of 0.05 MPa or more, preferably 0.1 MPa or more. Further, the foamable composition may have a pressure at 25° C. of 0.3 MPa or less, preferably 0.2 MPa or less. Since the pressure of the foamable composition at 25° C. is within the above range, the foamable composition of this embodiment can be prepared without adjusting the initial pressure to a high pressure, for example, when it is prepared as a discharged product as described below. However, a constant pressure is likely to be maintained until the end stage. Therefore, the resulting discharged product has low pressure and is highly safe. Furthermore, since the discharged product does not need to have a highly pressure-resistant container body that can withstand higher internal pressures, the container body can be made lighter and the amount of materials used can be reduced.

Further, the saturated vapor pressure of the liquefied gas is not particularly limited. For example, the saturated vapor pressure of the liquefied gas at 25° C. is preferably 0.35 MPa or more, more preferably 0.4 MPa or more. Further, the saturated vapor pressure of the liquefied gas at 25° C. is preferably 0.6 MPa or less, more preferably 0.5 MPa or less. By having the saturated vapor pressure of the liquefied gas within the above range, the foamable composition can be dissolved in a hydrofluoroolefin having a boiling point of 5 to 40°C and stored in a container, for example, when it is prepared as a discharge product as described below. When the pressure is maintained at a low level and is discharged to the outside, foaming tends to occur.

The method for preparing the foamable composition of this embodiment is not particularly limited. For example, the foamable composition can be prepared by filling a container filled with the aqueous stock solution with a vaporized gas under pressure and dissolving the vaporized gas in the aqueous stock solution. Preferably, the foamable composition of this embodiment is prepared by filling the container body of a discharged product shown in the embodiment of the discharged product (see FIG. 1) described later with an aqueous stock solution, and then using the liquefied gas filled in the gas container. It may be prepared by releasing a vaporized gas into the container body and dissolving it in an aqueous stock solution.

As described above, in the foamable composition of this embodiment, the vaporized gas of the liquefied gas is dissolved in the aqueous stock solution. As a result, the foamable composition promotes volatilization of the hydrofluoroolefin during discharge, and easily foams. Moreover, such foamable compositions have low pressure inside the container and are highly safe. Further, since such a foamable composition may be filled at low pressure, the container body does not need to have a high pressure resistance that can withstand higher internal pressure, and the weight can be reduced. . Moreover, the amount of material used for the container body filled with the foamable composition can be reduced.

<Discharged product>
A discharged product according to an embodiment of the present invention is a discharged product filled with the above-described foamable composition. FIG. 1 is a schematic cross-sectional view of a discharged product 1 of this embodiment. FIG. 2 is a schematic cross-sectional view for explaining the state in which the discharged product 1 of this embodiment is being discharged. The discharged product 1 includes a container body 2 filled with an aqueous stock solution C, a gas container 3 filled with liquefied gas, and an injection device for discharging vaporized gas of the liquefied gas from the gas container 3 into the container body 2. 4. The injection device 4 includes a holder 5 that accommodates the gas container 3, and an adjustment valve 6 that adjusts the amount of vaporized gas released. Each will be explained below. Note that the discharged product 1 of this embodiment includes the container body 2, the gas container 3, and the injection device 4 described above. Therefore, the other configurations shown below are merely examples, and the design can be changed as appropriate.

(Container body 2)
The container body 2 is a pressure-resistant container filled with a foamable composition. The container body 2 has a substantially cylindrical shape with a bottom, and includes a body part 21 whose diameter is reduced only at the upper part, and a cylindrical neck part 22 which has a smaller diameter than the body part 21 and is integrally provided at the upper part of the body part 21. Consisting of An opening is formed in the upper part of the neck 22. The opening is a filling port for filling the aqueous stock solution C, and is closed by a valve assembly 23, which will be described later. A threaded portion is spirally formed on the outer periphery of the neck portion 22 . The cover cap 7 can be detachably attached by threading a threaded portion formed on the inner circumferential surface of a large diameter portion 71 of the cover cap 7, which will be described later, into the threaded portion. As a result, the gas container 3 is housed in a predetermined position within the container body 2, and the cover cap 7 is positioned on the container body 2. Therefore, the user can remove the cover cap 7 from the container body 2 as appropriate and replace the gas container 3 or refill the aqueous stock solution C.

The material of the container body 2 is not particularly limited. For example, the material of the container body 2 is metal such as aluminum or tin, synthetic resin such as polyethylene terephthalate, pressure-resistant glass, or the like.

・Valve assembly 23
The valve assembly 23 is a member for closing and sealing the opening of the container body 2. The valve assembly 23 also includes a housing 23a, a stem 23b formed with a stem hole 23d that communicates between the inside and outside of the container body 2, and a stem rubber 23c that is attached around the stem hole 23d and closes the stem hole 23d. Mainly equipped with.

Note that the valve assembly 23 is covered with a cover cap 7. The cover cap 7 protects the valve assembly 23 and positions the valve assembly 23 to close the opening of the container body 2.

The cover cap 7 includes a substantially cylindrical large-diameter portion 71 and a small-diameter portion 72 that is connected to the upper end of the large-diameter portion 71 and has a smaller diameter than the large-diameter portion 71 . A threaded portion that is screwed into the threaded portion of the container body 2 is formed at the lower part of the inner circumference of the large diameter portion 71 . A flat portion 73 formed at the upper end of the large diameter portion 71 is in contact with a flange portion 23e of a housing 23a, which will be described later.

An opening having a diameter larger than the outer diameter of the stem 23b is formed in the center of the small diameter portion 72. This allows the stem 23b to move up and down. A flat portion formed at the upper end of the small diameter portion 72 is in contact with the stem rubber 23c and the upper end of the housing 23a.

・Housing 23a
Housing 23a accommodates stem 23b and spring 23j. The lower portion of the housing 23a has a substantially double cylindrical shape and includes an outer cylindrical portion 23f and an inner cylindrical portion 23g. A circumferential flange portion 23e extending outward is formed on the outer cylindrical portion 23f. The lower surface of the flange portion 23e is in close contact with the upper end of the holder 5 via a circumferential gasket.

The lower surface of the inner cylindrical portion 23g is a flat surface, and when the cover cap 7 is attached to the container body 2, the bottom surface of the gas container 3 accommodated in the holder 5 (the discharge product 1 of this embodiment is shown in FIG. As shown in , since the gas container 3 is housed in the holder 5 in an inverted state, the bottom surface of the gas container 3 is pressed (located above the page) to hold the gas container 3 in the holder 5.

A through hole 23h is formed in the side wall of the housing 23a. The through hole 23h is a hole through which a foamable composition taken in through a tube 8, which will be described later, is taken into the housing 23a. The foamable composition taken into the housing 23a passes through the stem hole 23d and the intra-stem passage 23i, and is discharged to the outside.

・Stem 23b
The stem 23b is a substantially cylindrical portion, and has an intra-stem passage 23i through which the foamable composition taken into the housing 23a during discharge passes. A stem hole 23d is formed near the lower end of the stem passageway 23i, which communicates the space within the housing 23a with the stem passageway 23i. A discharge member (not shown) for discharging the foamable composition is attached to the upper end of the stem 23b.

A spring 23j, which is an elastic member, is attached to the lower end of the stem 23b. Spring 23j urges stem 23b upward. Thereby, when the downward push is stopped, the stem 23b automatically returns upward, and the stem hole 23d is closed again by the stem rubber 23c.

・Stem rubber 23c
The stem rubber 23c is a member that is attached around the stem hole 23d and serves to appropriately isolate the interior space of the housing 23a from the outside. The stem rubber 23c is a disc-shaped member, and when not ejecting, its inner circumferential surface is brought into close contact with the outer circumferential surface of the stem 23b where the stem hole 23d is formed, thereby closing the stem hole 23d. On the other hand, as the stem 23b moves downward, the center portion of the stem rubber 23c bends downward to open the stem hole 23d. Thereby, the outside and the inside of the container main body 2 are communicated with each other, and the foamable composition is discharged. As shown in FIG. 2, when the stem 23b of the discharged product 1 is moved downward by pushing down a discharge member (not shown), the center of the stem rubber 23c is bent downward, and the stem hole 23d is opened. Thereby, the outside and the inside of the container main body 2 are communicated with each other, and the foamable composition is discharged.

(Gas container 3)
The gas container 3 includes a gas container body 31 filled with liquefied gas, and a valve assembly 32 for releasing vaporized gas of the liquefied gas from inside the gas container body 31. The valve assembly 32 includes an outwardly projecting stem 32a. The upper end of the stem 32a projects outward. When the stem 32a is pressed downward (in the direction of the inner bottom surface of the gas container 3), a stem rubber (not shown) is bent, and a stem hole (not shown) is opened. As a result, vaporized gas of the liquefied gas is released from inside the gas container body 31, and the inside of the container body 2 is pressurized.

The material of the gas container 3 is not particularly limited. For example, the material of the gas container 3 is metal such as aluminum or tin, various synthetic resins, pressure-resistant glass, or the like.

The gas container 3 may have any size as long as it can be accommodated in the holder 5. It is preferable that the dimensions (outer diameter) of the gas container 3 be somewhat smaller than the inner diameter of the holder 5 in order to facilitate accommodation and replacement in the holder 5 .

As shown in FIG. 1, in this embodiment, the gas container 3 is housed in the holder 5 in an inverted state. When housed in the holder 5, the upper end of the stem 23b of the gas container 3 is inserted into a fitting recess 61 formed at the upper end of the regulating valve 6, and comes into contact with a step 62 inside the fitting recess 61. ing.

The bottom surface of the gas container body 31 is in contact with the lower surface of the inner cylindrical portion 23g of the housing 23a described above when the cover cap 7 is attached to the container body 2. Thereby, the gas container 3 is held and positioned within the holder 5.

The saturated vapor pressure of the liquefied gas filled in the gas container 3 is not particularly limited. For example, the saturated vapor pressure of the liquefied gas at 25° C. is preferably in the range of 0.35 to 0.6 MPa, more preferably in the range of 0.4 to 0.5 MPa. When the saturated vapor pressure of the liquefied gas is within the above range, the pressure within the container is maintained at a low pressure and foaming is likely to occur even when the liquefied gas is discharged to the outside.

(Injection device 4)
The injection device 4 is a mechanism for discharging vaporized gas of liquefied gas from the gas container 3 into the container body 2 . The injection device 4 includes a holder 5 that accommodates the gas container 3 and an adjustment valve 6 that adjusts the amount of vaporized gas released.

・Holder 5
The holder 5 is a member accommodated within the container body 2, and accommodates the gas container 3 and the regulating valve 6 therein. Further, a tube 8 for taking in the foamable composition is inserted into the holder 5.

The holder 5 consists of an upper cylindrical part 51 in which the gas container 3 is mainly accommodated, and a lower cylindrical part 52 in which the regulating valve 6 is mainly accommodated. The lower cylindrical portion 52 has a smaller diameter than the upper cylindrical portion 51.

A communication hole 53 is formed in the side surface of the upper cylindrical portion 51 to communicate the inside of the holder 5 and the inside of the container body 2. The communication hole 53 is a hole through which the vaporized gas of the liquefied gas released from the gas container 3 passes. A flange portion 54 extending outward is formed at the upper end of the upper cylindrical portion 51 . The lower surface of the flange portion 54 is in contact with the upper end of the neck portion 22 of the container body 2 via a gasket.

The flange portion 54 is provided with a tube insertion hole 55 into which the tube 8 for taking in the foamable composition is inserted. The tube insertion hole 55 has an inner diameter comparable to the outer diameter of the tube 8. A through hole 56 is provided at the bottom of the tube insertion hole 55. The through holes 56 are holes through which the incorporated foamable composition passes. The tube 8 extends along the outer periphery of the upper cylindrical portion 51 of the holder 5 and has one end inserted into the tube insertion hole 55 and the other end opened into the foamable composition C.

The upper cylindrical part 51 and the lower cylindrical part 52 are connected by a flat part 57. A contact portion 58 extending inward is formed in the flat portion 57 . When the abutted portion 58 does not accommodate a gas container, an abutting portion 63 of the regulating valve 6, which will be described later, comes into contact with the abutting portion 58, thereby preventing the regulating valve 6 from falling off.

The lower cylindrical portion 52 mainly accommodates the regulating valve 6. The adjustment valve 6 is a member that slides in the lower cylindrical portion 52 of the holder 5 in the vertical direction. The regulating valve 6 includes an upper regulating valve 64 having a substantially cylindrical internal space, and a lower regulating valve 65 having a larger diameter than the upper regulating valve 64 and formed below the upper regulating valve 64. .

A fitting recess 61 is formed at the upper end of the upper regulating valve 64 and communicates with the internal space. The fitting recess 61 is a recess into which the stem 32a of the gas container 3 is inserted, and the inner peripheral surface of the fitting recess 61 is formed with a step 62 against which the stem 32a comes into contact. The stepped portion 62 is in contact with only a portion of the stem 32a. Therefore, the stepped portion 62 does not close the discharge hole (not shown) formed at the tip of the stem 32a. Further, the depth of the fitting recess 61 is longer (deeper) than the required operating distance of the stem 32a required to release the vaporized gas of the liquefied gas from the gas container 3. Therefore, when the regulating valve 6 is urged upward by compressed air that fills the space below the lower cylindrical portion 52, which will be described later, the stem 32a in contact with the stepped portion 62 is pushed down by the required operating distance. . As a result, the vaporized gas of the liquefied gas is appropriately discharged from the gas container 3. The vaporized gas of the released liquefied gas advances to fill the internal space, then fills the upper cylindrical part 51 of the holder 5, and is discharged into the container body 2 through the communication hole 53 of the upper cylindrical part 51.

A contact portion 63 that contacts the above-described contact portion 58 is provided on the outer circumferential surface of the upper regulating valve 64 . Since the abutting portion 63 abuts the abutted portion 58, the regulating valve 6 is prevented from slipping off.

The outer peripheral surface of the lower regulating valve 65 is in contact with the inner peripheral surface of the lower cylindrical portion 52 of the holder 5 via a gasket. The gasket divides the internal space of the lower cylindrical portion 52 into upper and lower sections (an upper space S1 and a lower space S2). A vaporized gas (for example, air) is compressed in the lower space S2. Thereby, the regulating valve 6 moves up and down so that the stress caused by the expansion of the air compressed in the lower space S2 and the combined force of the internal pressure of the container body 2 and the stem operating load of the gas container are balanced.

(Discharge member)
The discharge member (not shown) is a member for operating the valve assembly 23 to open and close to discharge the foamable composition, and is attached to the upper end of the stem 23b. The discharge member mainly includes a nozzle section and an operation section operated by a user with a finger or the like. The nozzle portion is formed with a discharge passage through which the foamable composition passes. An opening (discharge hole) is formed at the tip of the discharge passage. A foamable composition is discharged from the discharge hole. The number and shape of the discharge holes are not particularly limited. There may be a plurality of discharge holes. Further, the shape of the discharge hole may be approximately circular, approximately angular, or the like.

<Explanation of how to assemble the discharged product and the mechanism of internal pressure adjustment>
Next, a method for assembling the discharged product of this embodiment will be described. FIG. 3 is a schematic cross-sectional view for explaining the state in which the gas container 3 is accommodated in the holder 5. FIG. 4 is a schematic cross-sectional view for explaining how the valve assembly 23 and cover cap 7 are attached to the container body 2. As shown in FIG.

As shown in FIG. 3, the container body 2 is filled with an aqueous stock solution C, and a holder 5 is housed therein. A regulating valve 6 is accommodated in the holder 5 . A lower space S2 of the lower cylindrical portion 52 of the holder 5 is filled with vaporized gas (for example, air). In this state, the regulating valve 6 is urged upward by the pressure of the air compressed in the lower space S2, and the abutting portion 63 is in contact with the abutted portion 58 of the holder 5. The gas container 3 is housed in the holder 5 in an inverted state.

The cover cap 7 and valve assembly 23 are then attached to the container body 2, as shown in FIG. Thereby, the discharged product 1 shown in FIG. 1 is assembled. As shown in FIGS. 1 and 2, when the cover cap 7 and the valve assembly 23 are attached to the container body 2, the gas container 3 housed in the holder 5 has a bottom surface formed by the lower surface of the inner cylindrical portion 23g of the housing 23a. It is pressed and positioned within the holder 5.

In the state shown in FIG. 1, the regulating valve 6 is pushed down somewhat by the gas container 3 housed in the holder 5. As a result, the volume of the lower space S2 becomes smaller, so that the air sealed in the lower space S2 is compressed. As a result, an upward biasing force is applied to the regulating valve 6 by the compressed air.

The upward biasing force applied to the regulating valve 6 pushes down the stem 23b of the gas container 3. As a result, vaporized gas of the liquefied gas is released from the gas container 3. The vaporized gas of the released liquefied gas is released into the container body 2 through the communication hole 53 of the upper cylindrical portion 51 of the holder 5 . The vaporized gas of the liquefied gas released into the container body 2 constitutes a gas phase portion within the container body 2, and is dissolved in the aqueous stock solution C to form a foamable composition.

When the vaporized gas of the liquefied gas continues to be released, the vaporized gas fills the gas phase portion within the container body 2 while being dissolved in the aqueous stock solution, and the interior of the container body 2 becomes pressurized. Thereafter, when the internal pressure of the container body 2 pressurized by the released vaporized gas increases and exceeds the upward biasing force of the compressed air, the regulating valve 6 is pushed down. As a result, the regulating valve 6 moves downward to some extent and compresses the air in the lower space S2 to some extent, and the stem 32a of the gas container 3 is stopped from being pushed down, so that the vaporized gas of the liquefied gas is not released from the gas container 3. Stop. As a result, the stress caused by the expansion of the compressed air in the lower space S2 and the combined force of the internal pressure of the container body 2 and the stem operating load of the gas container are in equilibrium.

Here, when the ejected product 1 of this embodiment is used to eject the foamable composition, the effervescent composition in the container body 2 is consumed. FIG. 5 is a schematic cross-sectional view for explaining a state in which the foamable composition is consumed using the ejected product 1 of this embodiment. As shown in FIG. 5, when the volume of the gas phase portion inside the container body 2 increases, the internal pressure of the container body 2 becomes lower than before use because the gas phase portion is filled with vaporized liquefied gas. descend. As a result, the stress caused by the expansion of the air compressed in the lower space S2 becomes greater than the internal pressure of the container body 2, and the regulating valve 6 is again biased upward and moved, causing the gas container 3 to be removed from the gas container 3. A vaporized gas of liquefied gas is released. Arrow A1 indicates the flow of vaporized liquefied gas released from the gas container 3.

The vaporized gas of the liquefied gas is replenished into the gas phase portion within the container body 2 and is dissolved into the aqueous stock solution C. As a result, the stress caused by the expansion of the compressed air in the lower space S2, the combined force of the internal pressure of the container body 2 and the stem operating load of the gas container are again in an equilibrium state.

In this manner, when the ejected product 1 of this embodiment is used and the foamable composition is consumed, the vaporized liquefied gas is replenished from the gas container 3, and the inside of the container body 2 is appropriately pressurized again. Ru. Thereby, the pressure within the container body 2 is maintained constant. Therefore, the discharge product 1 can be discharged to the final stage without adjusting the initial pressure to a high pressure. Further, the amount of vaporized gas dissolved in the aqueous stock solution C is easily maintained constant, and the discharged material is likely to form stable bubbles.

More specifically, the internal pressure of the container body 2 of the discharged product 1 of this embodiment is preferably adjusted to be 0.05 MPa or more at 25° C., and preferably adjusted to be 0.1 MPa or more. It is more preferable to be present. Further, the internal pressure of the container body 2 is preferably lower than the saturated vapor pressure of the liquefied gas filled in the gas container, and is preferably adjusted to 0.3 MPa or less at 25°C, for example. More preferably, the pressure is adjusted to 2 MPa or less. As described above, the discharged product 1 of this embodiment can produce vaporized gas of the liquefied gas introduced into the container body by adjusting the pressure (equilibrium pressure) of the discharged product to be lower than the saturated vapor pressure of the liquefied gas. A part of the foam is dissolved in the stock solution, and the rest is present in the gas phase, resulting in small pressure changes due to temperature changes and a stable foamed product. Therefore, the discharged product 1 has a low pressure and is highly safe. In addition, since the discharged product 1 does not require the use of a container body 2 with high pressure resistance that can withstand higher internal pressures, the container body 2 can be made lighter and the amount of materials used can be reduced. .

Hereinafter, the present invention will be explained in more detail with reference to Examples. The present invention is not limited to these Examples in any way.

(Example 1)
Aqueous stock solution 1 was prepared according to the formulation (unit: mass %) shown in Table 1 below, and 40 g of the solution was filled into the synthetic resin container body shown in FIG. 1. Next, an injection device including a holder and a regulating valve was attached to the container body, and an aluminum container filled with 10 g of trans-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze(E)) as a liquefied gas was attached. A gas container was installed and a valve assembly was installed. A vaporized gas of liquefied gas was released from the gas container into the container body, and the vaporized gas was dissolved in the stock solution to reach an equilibrium state to produce a discharged product. Air is sealed in the space below the holder. The pressure inside the container body (25° C.) when the pressure inside the container body and the pressure at which the air in the lower space expands was in equilibrium was 0.2 MPa. The amount of vaporized gas released from the gas container was 1.4 g (3.5% by mass in the foamable composition).

(Examples 2 to 14)
A foamable composition was prepared and a discharged product was produced in the same manner as in Example 1, except that the aqueous stock solution and the type of vaporized gas were changed to the formulations shown in Tables 1 and 2.

(Comparative example 1)
Aqueous stock solution 1 was prepared according to the formulation (unit: mass %) shown in Table 1 above, and 40 g was filled into the synthetic resin container body shown in FIG. 1. A valve assembly was then attached to the container body. Carbon dioxide gas was filled through the stem of the valve assembly to produce a discharged product. Note that the pressure inside the container body was 0.5 MPa (25° C.).

(Comparative example 2)
A foamable composition was prepared and a discharged product was produced in the same manner as in Comparative Example 1 except that nitrogen was filled instead of carbon dioxide gas.

Using the ejected products prepared in Examples 1 to 14 and Comparative Examples 1 and 2, the initial and final ejected states were evaluated by the following evaluation method. The results are shown in Table 2.

<Discharge status>
The discharged product was immersed in a constant temperature water bath adjusted to 25°C for 1 hour, and the foamable composition was adjusted to 25°C. The dispensed product was taken out from the constant temperature water bath and 1 g was dispensed onto the palm of the hand. The state of the foamable composition at the time of discharge at the first time (initial stage: 100% remaining amount of the foamable composition) and the 80th time (final stage: 10% remaining amount of the foamable composition) was evaluated according to the following evaluation criteria.
(Evaluation criteria)
◎: The foamable composition had no difference in foamability between the initial stage and the final stage, and very fine foam was formed. (Foam density: 0.01-0.05g/mL)
○: The foamable composition had no difference in foamability between the initial stage and the final stage, and formed fine bubbles. (Foam density: 0.06-0.09g/mL)
Δ1: There was no difference in foamability between the initial and final stages of the foaming composition, and although very fine bubbles were formed, it was difficult to spread.
Δ2: There was no difference in foamability between the initial stage and the final stage of the foamable composition, but the foamability was weak and a slightly rough foam was formed. (Foam density: 0.1-0.2g/mL)
×: The foamable composition foamed slightly at the initial stage, but formed coarse foam, and did not form foam at the final stage.

As shown in Table 2, the foaming compositions discharged by the discharge products of Examples 3 to 8 and 13 to 14 had no difference in foaming performance between the initial stage and the final stage, and very fine foam was formed. . Further, the foamable compositions discharged by the discharge products of Examples 3 to 8 and 13 to 14 were easy to spread. In Examples 1 and 2, there was no difference in foamability between the initial and final stages, and fine foam was formed. Further, the foamable compositions discharged by the discharge products of Examples 1 and 2 were easy to spread. The foamable compositions discharged by the discharge products of Examples 9 and 10 showed no difference in foaming properties between the initial and final stages, and although very fine bubbles were formed, they were difficult to spread. The foaming compositions discharged by the discharge products of Examples 11 and 12 showed no difference in foaming properties between the initial stage and the final stage, but the foaming properties were weak and formed somewhat coarse foam. Therefore, the foamable compositions discharged by the discharge products of Examples 1 to 14 were easily discharged at a constant pressure because the pressure inside the container was maintained at a low level. On the other hand, the foamable compositions discharged by the discharge products of Comparative Examples 1 and 2 were all slightly foamed at the initial stage, but were coarse foam, and were unable to form foam at the final stage.

1 Discharged product 2 Container body 21 Body 22 Neck 23 Valve assembly 23a Housing 23b Stem 23c Stem rubber 23d Stem hole 23e Flange 23f Outer cylindrical portion 23g Inner cylindrical portion 23h Through hole 23i Stem inner passage 23j Spring 3 Gas container 31 Gas container Main body 32 Valve assembly 32a Stem 4 Injector 5 Holder 51 Upper cylindrical part 52 Lower cylindrical part 53 Communication hole 54 Flange part 55 Tube insertion hole 56 Through hole 57 Flat part 58 Abutted part 6 Regulating valve 61 Fitting recess 62 Step Part 63 Contact part 64 Upper regulating valve 65 Lower regulating valve 7 Cover cap 71 Large diameter part 72 Small diameter part 73 Flat part 8 Tube A1 Flow of vaporized gas of liquefied gas S1 Upper space S2 Lower space

Claims (4)

A foamable composition comprising an aqueous stock solution and a liquefied gas,
The aqueous stock solution contains water, a blowing agent, and a hydrofluoroolefin with a boiling point of 5 to 40°C,
The pressure of the foamable composition at 25°C is 0.05 to 0.3 MPa,
The content of the hydrofluoroolefin is 1 to 50% by mass in the aqueous stock solution,
The content of the liquefied gas is 1 to 25% by mass in the foamable composition,
Foaming composition. The foamable composition according to claim 1 , wherein the liquefied gas has a saturated vapor pressure of 0.35 to 0.6 MPa at 25°C. Filled with a foaming composition containing an aqueous stock solution and a liquefied gas ,
a container body filled with the aqueous stock solution;
a gas container filled with the liquefied gas;
an injection device for emitting vaporized gas of the liquefied gas from the gas container into the container main body,
The aqueous stock solution contains water, a blowing agent, and a hydrofluoroolefin with a boiling point of 5 to 40°C,
The pressure of the foamable composition at 25°C is 0.05 to 0.3 MPa,
The content of the hydrofluoroolefin is 1 to 50% by mass in the aqueous stock solution,
The injection device is a discharge product, including a holder that accommodates the gas container, and an adjustment valve that adjusts the amount of the vaporized gas released. The dispensed product according to claim 3 , wherein the pressure at 25° C. within the container body is 0.05 to 0.3 MPa.

Images