JP2021115532A - Foamable composition and discharge product - Google Patents

Abstract

To provide a foamable composition that keeps a container body interior at low pressure, is likely to be discharged at constant pressure and has excellent foamability when being discharged, and to provide a discharge product.SOLUTION: A foamable composition includes aqueous stock solution and a liquefied gas, where the aqueous stock solution includes water, a foaming agent and a hydrofluoroolefin of which boiling point is 5-40°C. The foamable composition has a pressure of 0.05-0.3 MPa at 25°C.SELECTED DRAWING: Figure 1

Description

The present invention relates to effervescent compositions and discharge products. More specifically, the present invention relates to a foamable composition and a discharge product in which the inside of the container body is maintained at a low pressure, is easily discharged at a constant pressure, and has excellent foamability when discharged.

Conventionally, a discharge product filled with an effervescent composition has been developed. A general foaming composition is composed of an aqueous stock solution and a liquefied gas, and is discharged to the outside in a state where the liquefied gas is emulsified in the aqueous stock solution, and the volume expands due to the vaporization of the liquefied gas. Forming bubbles. There is also a discharge product that discharges a foamable composition with a compressed gas (Patent Document 1).

JP-A-2002-37362

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

The present invention has been made in view of such conventional problems, and has an effervescent composition in which the inside of the container body is maintained at a low pressure, is easily discharged at a constant pressure, and has excellent foamability when discharged. The purpose is to provide goods and discharge products.

The present invention that solves the above problems mainly includes the following configurations.

(1) An effervescent composition containing an aqueous stock solution and a liquefied gas. The aqueous stock solution contains water, a foaming agent, and a hydrofluoroolefin having a boiling point of 5 to 40 ° C., and the effervescent composition. A foaming composition in which the pressure of the object at 25 ° C. is 0.05 to 0.3 MPa.

According to such a configuration, in the effervescent composition, a large amount of vaporized gas of liquefied gas is dissolved in the aqueous stock solution. As a result, the effervescent composition promotes the volatilization of the hydrofluoroolefin at the time of discharge, and easily efferves. Further, when such an effervescent composition is filled in a container body and used, the inside of the container body is likely to be maintained at a low pressure.

(2) The effervescent 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, when the content of the hydrofluoroolefin is within the above range, the amount of the vaporized gas of the liquefied gas dissolved in the effervescent composition is large, and it is easy to maintain the low pressure. Further, in the effervescent composition, the volatilization of the hydrofluoroolefin is more easily promoted by the vaporized gas dissolved at the time of discharge, and the effervescent composition is easily foamed.

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

According to such a configuration, the effervescent composition is easily dissolved in the hydrofluoroolefin and easily foamed when the content of the liquefied gas is within the above range.

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

According to such a configuration, the foamable composition tends to foam at the time of discharge because the saturated vapor pressure of the liquefied gas is within the above range.

(5) From the container body filled with the effervescent composition according to any one of (1) to (4) and filled with the aqueous stock solution, the gas container filled with the liquefied gas, and the gas container. The container body is provided with an injection device for releasing the vaporized gas of the liquefied gas, and the injection device includes a holder for accommodating the gas container and an adjusting valve for adjusting the release amount of the vaporized gas. Discharge products with and.

According to such a configuration, in the discharge product, the vaporized gas of the liquefied gas is discharged into the container body by the injection device until the inside of the container body reaches a predetermined pressure. As a result, the pressure inside the container body is kept constant. Therefore, the discharge product tends to maintain a constant pressure until the final stage without adjusting the initial pressure to a high pressure. In addition, the amount of the vaporized gas dissolved in the aqueous stock solution is likely to be kept constant, and the discharged product 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 discharge product has a low pressure and is highly safe. Further, since it is not necessary for the discharge product to adopt a container body having a high pressure resistance that can withstand a higher internal pressure, the weight of the container body can be reduced and the amount of material used can be reduced.

According to the present invention, it is possible to provide a foamable composition and a discharge product in which the inside of the container body is maintained at a low pressure, the container body is easily discharged at a constant pressure, and the foamability is excellent when discharged.

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

<Effervescent composition>
The effervescent composition of one embodiment of the present invention contains an aqueous stock solution and a liquefied gas. The aqueous stock solution contains water, a foaming agent, and a hydrofluoroolefin having a boiling point of 5 to 40 ° C. The pressure of the effervescent composition at 25 ° C. is 0.05 to 0.3 MPa. In the effervescent composition of the present embodiment, a large amount of vaporized gas as a liquefied gas is dissolved in an aqueous stock solution. As a result, the effervescent composition promotes the volatilization of the hydrofluoroolefin at the time of discharge, and easily efferves. Further, when the effervescent composition of the present embodiment is used by being filled in the container body, the inside of the container body is easily maintained at a low pressure. Each will be described below.

(Aqueous undiluted solution)
The aqueous stock solution contains water, a foaming agent, and a hydrofluoroolefin having a boiling point of 5 to 40 ° C.

-Water Water is used as a solvent. The inclusion of water allows the effervescent composition to form foam when discharged.

Water is not particularly limited. For example, the water is purified water, ion-exchanged water, physiological saline, deep sea water and the like.

The water content is not particularly limited. As an example, the amount of water in the aqueous stock solution is preferably 20% by mass or more, and more preferably 30% by mass or more. Further, the amount 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 effervescent composition exhibits excellent effervescence, and it is easy to blend hydrofluoroolefin, which will be described later, in an appropriate amount.

-Effervescent agent The foaming agent is blended to emulsify water and a hydrofluoroolefin having a boiling point of 5 to 40 ° C. and foam it when it is discharged to the outside.

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

The polymer compound is not particularly limited. For example, the polymer compound is a synthetic water-soluble polymer such as polyether urethane, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, polyethyleneimine, sodium polyacrylate, agar, casein, dextrin, gelatin. , Pectin, starch, sodium alginate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, nittle cellulose, crystalline cellulose and other natural water-soluble polymers. The polymer compound may be used in combination. Among these, the polymer compound preferably contains a polyether urethane from the viewpoint of 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, and polyoxy. Nonionic surfactants such as ethylene alkyl ether fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester; alkyl phosphoric acid and its salt such as fatty acid soap and lauryl phosphoric acid, polyoxyethylene alkyl ether acetic acid and its salt. , Polyoxyethylene alkyl ether sulfuric acid and salts thereof, anionic surfactants such as alkyl ether carboxylate; N-acylglutamate, N-acylglycine salt, N-acylalanine salt; amino acid type anionic surfactant; Silicone-based surfactants; carboxybetaine types such as cocamidopropyl betaine; alkylimidazole types; amino acid types; amphoteric surfactants such as amine oxide types. Surfactants may be used in combination.

The content of the foaming agent is not particularly limited. As an example, the content of the foaming agent is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more in the aqueous stock solution. The content of the foaming agent is preferably 30% by mass or less, and more preferably 25% by mass or less. When the content of the foaming agent is within the above range, the foamable composition has a viscosity that facilitates foam formation and filling, is less sticky, and has an excellent usability.

Hydrofluoroolefins having a boiling point of 5 to 40 ° C. Hydrofluoroolefins having a boiling point of 5 to 40 ° C. are blended to dissolve a large amount of vaporized gas of liquefied gas to foam an effervescent composition.

The hydrofluoroolefin having a boiling point of 5 to 40 ° C. is not particularly limited. As an example, hydrofluoroolefins having a boiling point of 5 to 40 ° C. are trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd (E), boiling point 19 ° C.), cis-1-chloro. -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 the hydrofluoroolefin having a boiling point of 5 to 40 ° C. is not particularly limited. As an example, the content of the hydrofluoroolefin having a boiling point of 5 to 40 ° C. is preferably 1% by mass or more, and more preferably 5% by mass or more in the aqueous stock solution. The content of the hydrofluoroolefin having a boiling point of 5 to 40 ° C. is preferably 50% by mass or less, more preferably 30% by mass or less in the aqueous stock solution. When the content of the hydrofluoroolefin having a boiling point of 5 to 40 ° C. is within the above range, the effervescent composition easily foams even at a low pressure.

-Optional ingredients In addition to the above water, foaming agent and hydrofluoroolefin having a boiling point of 5 to 40 ° C, the aqueous stock solution contains optional ingredients such as monosaccharides, alcohols, oils, powders and active ingredients depending on the intended use. May include.

The monosaccharide is preferably blended for the purpose of adjusting the foamability of the effervescent composition.

The monosaccharide is not particularly limited. For example, monosaccharides include sugar alcohols such as sorbitol, erythritol, arabitol, galactitol, glucitol, martitol, mannitol, xylulose; tetroses such as erythritol, D-erythulose, D-treose; D-arabinose, L. -Pentoses such as arabinose, D-xylulose, D-lyxose, L-lyxose, D-ribose, D-xylulose, L-xylulose, D-libulose, L-libulose; D-altrose, L-altrose, D -Lyxose such as galactose, L-galactose, D-glucose, D-talose, D-mannose, L-sorbitol, D-tagatose, D-psicose, D-fructose, D-mannose and the like. Monosaccharides may be used in combination.

When a monosaccharide is blended, the content of the monosaccharide is not particularly limited. As an example, the content of the monosaccharide is preferably 0.5% by mass or more, and more preferably 1% by mass or more in the aqueous stock solution. The content of the monosaccharide is preferably 20% by mass or less, more preferably 15% by mass or less in the aqueous stock solution. When the content of the monosaccharide is within the above range, the effect of blending the monosaccharide can be easily obtained. In addition, the effervescent composition tends to form stable effervescent properties.

Alcohols may be blended as a solvent for an active ingredient that is difficult to dissolve in water. Further, alcohols may be blended for the purpose of adjusting the foamability of the foaming 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 pentaerythritol, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol and mannitol, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, diglycerin and polyethylene. It is a polymer of a polyhydric alcohol such as glycol or triglycerin. Alcohols may be used in combination.

When alcohols are blended, the content of alcohols is not particularly limited. As an example, the content of alcohols is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the aqueous stock solution. The content of alcohols is preferably 25% by mass or less, more preferably 20% by mass or less. When the content of alcohols is within the above range, the effect of blending alcohols can be easily obtained. In addition, the effervescent composition can easily obtain the desired effervescent property.

The oil agent is suitably blended for the purpose of improving the feel of the obtained foam, improving finger passage, and the like.

The oil agent is not particularly limited. As an example, the oil agent is dimethicone, methylpolysiloxane, cyclopentasiloxane, cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, methylcyclopolysiloxane, tetrahydrotetramethylcyclotetra. Silicone oils such as siloxane, octamethyltrisiloxane, decamethyltetrasiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane; hydrocarbon oils such as liquid paraffin and isoparaffin; methylpentanediol dineopenate, diethylpentanediol dineopentanoate, di -2-Ethylene neopentyl glycol hexaneate, neopentyl glycol dicaprate, propylene glycol dilaurate, ethylene glycol distearate, diethylene glycol dilaurate, diethylene glycol distearate, diethylene glycol diisostearate, diethylene glycol dioleate, triethylene glycol dilaurate, distearate Triethylene glycol acid, triethylene glycol diisostearate, triethylene glycol dioleate, propylene glycol monostearate, propylene glycol monooleate, ethylene glycol monostearate, glyceryl tri2-ethylhexanoate, tri (capryl capric acid) ) Ester oils such as glycerin, isononyl isononanoate, isotridecyl isononanoate, diethoxyethyl succinate, diisostearyl malate, isopropyl myristate, isopropyl palmitate, cetyl isooctanoate, octyl hydroxystearate, ethylhexyl hydrosixistearate, etc. Fats and oils such as olive oil, camellia oil, corn oil, castor oil, saflower 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. As an example, the content of the oil agent is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more in the aqueous stock solution. The content of the oil agent is preferably 20% by mass or less, more preferably 15% by mass or less in the aqueous stock solution. When the content of the oil agent is within the above range, the effect of blending the oil agent can be easily obtained. In addition, the effervescent composition is less likely to have lower foamability, less dryness, and less stickiness.

The powder is suitably blended in order to improve the usability, such as imparting a smooth 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. The powder may be used in combination.

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

The active ingredient may be formulated according to the purpose of the product. The active ingredient is not particularly limited. For example, the active ingredient is an ultraviolet absorber such as hexyl diethylaminohydroxybenzoyl benzoate, 2-ethylhexyl paramethoxysilicate, ethylhexyltriazone, oxybenzene, hydroxybenzophenone sulfonic acid, sodium dihydroxybenzophenone sulfonate, dihydroxybenzophenone. , Ultraviolet scattering agents such as zinc oxide and titanium oxide, blood circulation promoters such as carpronium chloride and capacitinki, retinol, retinol acetate, retinol palmitate, calcium pantothenate, ascorbic acid, sodium ascorbate, dl-α-tocopherol, acetic acid Vitamins such as tocopherol, tocopherol, tocopherol nicotinate, dibenzoylthiamine, riboflavin and mixtures thereof, keratolytic agents such as salicylic acid and resorcin, various extracts such as assembly extract and rosemary extract, mint and menthol, etc. Cooling agents, bactericidal disinfectants such as cetylpyridinium chloride and isopropylmethylphenol, anti-inflammatory agents such as dipotassium glycyrrhizinate and tranexamic acid, floral, green, citrus green, green floral, citrus, rose, rosewood, herbal wood, lemon, Fragrances such as peppermint, pH adjusters such as citric acid and lactic acid, chelating agents such as disodium edetate, and preservatives such as paraben and phenoxyethanol.

When the active ingredient is blended, the content of the active ingredient is not particularly limited. As an example, the content of the active ingredient is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more in the aqueous stock solution. The content of the active ingredient is preferably 20% by mass or less, more preferably 15% by mass or less in the aqueous stock solution. When the content of the active ingredient is within the above range, the effervescent composition can easily obtain the effect 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 foaming agent, a hydrofluoroolefin having a boiling point of 5 to 40 ° C., and an optional component to be appropriately blended in an appropriate container.

(Liquefied gas)
The liquefied gas is used as a propellant for injecting an aqueous stock solution by pressurizing the inside of the container with the vaporized gas. Further, the vaporized gas of the liquefied gas is dissolved in the aqueous stock solution, particularly in the hydrofluoroolefin, so that the vaporization of the hydrofluoroolefin is promoted when it is discharged to the outside, and the foamability of the effervescent composition is improved.

The liquefied gas is not particularly limited. For example, the liquefied gas is normal butane, isobutane, propane and a mixture thereof, such as liquefied petroleum gas, dimethyl ether, and a hydrofluoroolefin 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. because it is easily dissolved in a hydrofluoroolefin having a boiling point of 5 to 40 ° C.

The hydrofluoroolefin having a boiling point of less than 5 ° C. is not particularly limited. As an example, hydrofluoroolefins having a boiling point of less than 5 ° C. are trans-1,3,3,3-tetrafluoropropa-1-ene (HFO-1234ze (E), boiling point -19 ° C.), 2,3. , 3,3-Tetrafluoro-1-propen (HFO-1234yf, boiling point −29.4 ° C.) and the like.

In order to pressurize the inside of the container, a compressed gas may be used in combination with the vaporized gas of the liquefied gas. The compressed gas is not particularly limited. As an example, the compressed gas is nitrogen, air, oxygen, hydrogen, carbon dioxide, nitrous oxide and the like. Among these, the compressed gas is preferably nitrogen, air, or hydrogen, which has low solubility in water, because it is easily dissolved in an aqueous stock solution to form fine bubbles. The pressure inside the container body is preferably adjusted to 0.2 to 0.5 MPa by the compressed gas.

The content of the liquefied gas is preferably 1% by mass or more, and more preferably 2% by mass or more in the effervescent composition. The content of the liquefied gas is preferably 25% by mass or less, and more preferably 20% by mass or less in the effervescent composition. 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 effervescent composition, and the effervescent composition discharged is further discharged. It is suitably easy to foam.

Returning to the description of the entire effervescent composition, the effervescent composition of the present embodiment may have a pressure of 0.05 MPa or more at 25 ° C., preferably 0.1 MPa or more. Further, the effervescent composition may have a pressure of 0.3 MPa or less at 25 ° C., preferably 0.2 MPa or less. Since the pressure of the effervescent composition at 25 ° C. is within the above range, the effervescent composition of the present embodiment does not adjust the initial pressure to a high pressure, for example, when it is prepared as a discharge product described later. However, constant pressure is likely to be maintained until the end. Therefore, the obtained discharge product has a low pressure and is highly safe. Further, since it is not necessary for the discharge product to adopt a container body having a high pressure resistance that can withstand a higher internal pressure, the weight of the container body can be reduced and the amount of material used can be reduced.

Further, the saturated vapor pressure of the liquefied gas is not particularly limited. As an example, the saturated vapor pressure of the liquefied gas is preferably 0.35 MPa or more, more preferably 0.4 MPa or more at 25 ° C. The saturated vapor pressure of the liquefied gas is preferably 0.6 MPa or less, more preferably 0.5 MPa or less at 25 ° C. When the saturated vapor pressure of the liquefied gas is within the above range, the effervescent composition is dissolved in a hydrofluoroolefin having a boiling point of 5 to 40 ° C. in a container, for example, when it is prepared as a discharge product described later. While maintaining a low pressure, it tends to foam when discharged to the outside.

The method for preparing the effervescent composition of the present embodiment is not particularly limited. As an example, the effervescent composition can be prepared by pressure-filling a container filled with the above-mentioned aqueous stock solution with a vaporized gas of a liquefied gas and dissolving the vaporized gas in the aqueous stock solution. Preferably, the effervescent composition of the present embodiment is prepared by filling the container body of the discharge product shown in the discharge product embodiment (see FIG. 1) described later with an aqueous stock solution and filling the gas container with the liquefied gas. It can be prepared by releasing the vaporized gas into the main body of the container and dissolving it in the aqueous stock solution.

As described above, in the effervescent composition of the present embodiment, the vaporized gas of the liquefied gas is dissolved in the aqueous stock solution. As a result, the effervescent composition is easily foamed because the volatilization of the hydrofluoroolefin is promoted at the time of discharge. Further, such an effervescent composition has a low pressure inside the container and is highly safe. Further, since such an effervescent composition may be filled at a low pressure, the container body does not need to adopt a container body having a high pressure resistance that can withstand a higher internal pressure, and the weight can be reduced. .. In addition, the container body filled with the effervescent composition can reduce the amount of material used.

<Discharge product>
The discharge product of one embodiment of the present invention is a discharge product filled with the above-mentioned foamable composition. FIG. 1 is a schematic cross-sectional view of the discharge product 1 of the present embodiment. FIG. 2 is a schematic cross-sectional view for explaining a state in which the discharge product 1 of the present embodiment is being discharged. The discharge product 1 is 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 liquefied gas from the gas container 3 into the container body 2. 4 and. The injection device 4 includes a holder 5 for accommodating the gas container 3 and a regulating valve 6 for adjusting the amount of vaporized gas released. Each will be described below. The discharge product 1 of the present embodiment includes the container body 2, the gas container 3, and the injection device 4 described above. Therefore, the other configurations shown below are examples, and the design can be changed as appropriate.

(Container body 2)
The container body 2 is a pressure-resistant container filled with an effervescent composition. The container body 2 has a substantially bottomed tubular shape, a body portion 21 having a reduced diameter only at the upper portion, and a tubular neck portion 22 having a diameter smaller than that of the body portion 21 and integrally provided on the upper portion of the body portion 21. Consists of. An opening is formed in the upper part of the neck portion 22. The opening is a filling port for filling the aqueous stock solution C, and is closed by a valve assembly 23 described later. A screw portion is spirally formed on the outer circumference of the neck portion 22. The cover cap 7 can be detachably attached by screwing the screw portion formed on the inner peripheral surface of the large diameter portion 71 of the cover cap 7, which will be described later, into the screw portion. As a result, the gas container 3 is housed in a predetermined position in the container body 2, and the cover cap 7 is positioned on the container body 2. Therefore, the user can appropriately remove the cover cap 7 from the container body 2 to replace the gas container 3 and refill the aqueous stock solution C.

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

・ Valve assembly 23
The valve assembly 23 is a member for closing and sealing the opening of the container body 2. Further, the valve assembly 23 is attached to the housing 23a, the stem 23b in which the stem hole 23d communicating the inside and outside of the container body 2 is formed, and the stem rubber 23c for closing the stem hole 23d. Mainly equipped with.

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 so as 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 connected to the upper end of the large-diameter portion 71 and having a smaller diameter than the large-diameter portion 71. At the lower part of the inner circumference of the large diameter portion 71, a screw portion to be screwed into the screw portion of the container body 2 is formed. The flat portion 73 formed at the upper end of the large diameter portion 71 is in contact with the flange portion 23e of the 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. As a result, the stem 23b can move up and down. The flat portion formed at the upper end of the small diameter portion 72 is in contact with the upper end of the stem rubber 23c and the housing 23a.

・ Housing 23a
The housing 23a houses the stem 23b and the 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. The outer cylindrical portion 23f is formed with a circumferential flange portion 23e extending in the outward direction. 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 23 g is a flat surface, and the bottom surface of the gas container 3 housed in the holder 5 in a state where the cover cap 7 is attached to the container body 2 (the discharge product 1 of the present embodiment is shown in FIG. 1). Since the gas container 3 is housed in the holder 5 in an inverted state as shown in the above, the bottom surface of the gas container 3 is located on the upper side of the paper surface), and the gas container 3 is held 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 for taking in the effervescent composition taken in through the tube 8 described later into the housing 23a. The foamable composition taken into the housing 23a passes through the stem hole 23d and the stem inner passage 23i and is discharged to the outside.

・ Stem 23b
The stem 23b is a substantially cylindrical portion, and an in-stem passage 23i through which the foamable composition taken into the housing 23a at the time of discharge passes is formed. A stem hole 23d is formed in the vicinity of the lower end of the in-stem passage 23i to communicate the space in the housing 23a with the in-stem passage 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. The spring 23j urges the stem 23b upward. As a result, when the downward push-down 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 attached around the stem hole 23d and is a member for appropriately blocking the internal space and the outside of the housing 23a. The stem rubber 23c is a disk-shaped member, and when not ejected, the inner peripheral surface of the stem 23b is brought into close contact with the outer peripheral surface of the stem 23b on which the stem hole 23d is formed, and the stem hole 23d is closed. On the other hand, in the stem rubber 23c, the central portion of the stem rubber 23c bends downward as the stem 23b moves downward, and the stem hole 23d is opened. As a result, the outside and the inside of the container body 2 communicate with each other, and the foamable composition is discharged. As shown in FIG. 2, in the discharge product 1, when the stem 23b is moved downward by pushing down a discharge member (not shown), the central portion of the stem rubber 23c is bent downward and the stem hole 23d is opened. As a result, the outside and the inside of the container body 2 communicate with each other, and the foamable composition is discharged.

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

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

The size of the gas container 3 may be any size as long as it is accommodated in the holder 5. The size (outer diameter) of the gas container 3 is preferably somewhat smaller than the inner diameter of the holder 5 because it is easy to accommodate and replace with respect to the holder 5.

As shown in FIG. 1, in the present embodiment, the gas container 3 is housed in the holder 5 in an inverted state. In the state of being housed in the holder 5, the upper end of the stem 23b of the gas container 3 is inserted into the fitting recess 61 formed at the upper end of the adjusting valve 6 and comes into contact with the step portion 62 in 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 in a state where the cover cap 7 is attached to the container body 2. As a result, the gas container 3 is held and positioned in the holder 5.

The saturated vapor pressure of the liquefied gas filled in the gas container 3 is not particularly limited. As an example, the saturated vapor pressure of the liquefied gas is preferably in the range of 0.35 to 0.6 MPa at 25 ° C., more preferably in the range of 0.4 to 0.5 MPa. Since the saturated vapor pressure of the liquefied gas is within the above range, the pressure inside the container is maintained at a low pressure, and even if it is discharged to the outside, it easily foams.

(Injection device 4)
The injection device 4 is a mechanism for discharging the vaporized gas of the liquefied gas from the gas container 3 into the container main body 2. The injection device 4 includes a holder 5 for accommodating the gas container 3 and a regulating valve 6 for adjusting the amount of vaporized gas released.

・ Holder 5
The holder 5 is a member housed in the container body 2, and houses the gas container 3 and the adjusting valve 6 inside. Further, a tube 8 for taking in the effervescent composition is inserted into the holder 5.

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

The upper cylindrical portion 51 is formed with a communication hole 53 on the side surface that communicates 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 similar 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 hole 56 is a hole through which the incorporated effervescent composition passes. The tube 8 has one end extending along the outer circumference of the upper cylindrical portion 51 of the holder 5 and being inserted into the tube insertion hole 55, and the other end opening into the foamable composition C.

The upper cylindrical portion 51 and the lower cylindrical portion 52 are connected by a flat portion 57. The flat portion 57 is formed with a contacted portion 58 extending inward. When the gas container is not accommodated in the contacted portion 58, the contact portion 63 of the adjusting valve 6, which will be described later, comes into contact with the contacted portion 58 to prevent the adjusting valve 6 from coming off.

The adjusting valve 6 is mainly housed in the lower cylindrical portion 52. The adjusting 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 in which a substantially cylindrical internal space is formed, and a lower regulating valve 65 having a diameter larger than that of the upper regulating valve 64 and formed below the upper regulating valve 64. ..

A fitting recess 61 communicating with the internal space is formed at the upper end of the upper adjusting valve 64. The fitting recess 61 is a recess into which the stem 32a of the gas container 3 is inserted, and a step portion 62 with which the stem 32a abuts is formed on the inner peripheral surface of the fitting recess 61. The step portion 62 is in contact with only a part of the stem 32a. Therefore, the step 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 lower space of the lower cylindrical portion 52, which will be described later, is filled and the adjusting valve 6 is urged upward by the compressed air, the stem 32a in contact with the step portion 62 is pushed down by the required operating distance. .. As a result, the vaporized gas of the liquefied gas is appropriately released from the gas container 3. The vaporized gas of the released liquefied gas proceeds to fill the internal space, then fills the upper cylindrical portion 51 of the holder 5, and is discharged into the container body 2 through the communication hole 53 of the upper cylindrical portion 51.

An abutting portion 63 that abuts the abutted portion 58 is provided on the outer peripheral surface of the upper adjusting valve 64. When the contact portion 63 comes into contact with the contacted portion 58, the adjusting valve 6 is prevented from coming off.

The outer peripheral surface of the lower adjusting 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 vertically partitions the internal space of the lower cylindrical portion 52 (upper space S1 and lower space S2). Vaporized gas (for example, air) is compressed in the lower space S2. As a result, the regulating valve 6 moves up and down so that the stress for expanding 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 opening and closing of the valve assembly 23 to discharge the foamable composition, and is attached to the upper end of the stem 23b. The discharge member mainly includes a nozzle portion and an operation portion operated by the 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. The effervescent 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 a substantially circular shape, a substantially angular shape, or the like.

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

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

Next, as shown in FIG. 4, the cover cap 7 and the valve assembly 23 are attached to the container body 2. As a result, the discharge 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 bottom surface of the gas container 3 housed in the holder 5 is formed by the lower surface of the inner cylindrical portion 23g of the housing 23a. It is pressed and positioned in 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 enclosed in the lower space S2 is compressed. As a result, the regulating valve 6 is subjected to an upward urging force by the compressed air.

The upward urging force applied to the regulating valve 6 pushes down the stem 23b of the gas container 3. As a result, the 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 in the container body 2 and dissolves in the aqueous stock solution C to form an effervescent composition.

When the vaporized gas of the liquefied gas continues to be released, the vaporized gas fills the gas phase portion in the container body 2 while being dissolved in the aqueous stock solution, and the inside of the container body 2 is in a pressurized state. After that, when the internal pressure of the container body 2 pressurized by the released vaporized gas increases and exceeds the upward urging force of the compressed air, the adjusting valve 6 is pushed down. As a result, the regulating valve 6 moves somewhat downward, compresses the air in the lower space S2 somewhat, stops pushing down the stem 32a of the gas container 3, and releases the vaporized gas of the liquefied gas from the gas container 3. Stop. As a result, the stress for expanding 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 in an equilibrium state.

Here, when the effervescent composition is ejected using the ejection product 1 of the present embodiment, 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 effervescent composition is consumed by using the discharge product 1 of the present embodiment. As shown in FIG. 5, when the volume of the gas phase portion in the container body 2 increases, the gas phase portion is filled with the vaporized gas of the liquefied gas, so that the internal pressure of the container body 2 is higher than that before use. descend. As a result, the stress for expanding the air compressed in the lower space S2 becomes larger than the internal pressure of the container body 2, and the regulating valve 6 is again urged upward and moves from the gas container 3. The vaporized gas of the liquefied gas is released. The arrow A1 indicates the flow of the vaporized gas of the liquefied gas released from the gas container 3.

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

As described above, in the discharge product 1 of the present embodiment, when the effervescent composition is consumed by use, the vaporized gas of the liquefied gas is replenished from the gas container 3, and the inside of the container body 2 is appropriately pressurized again. NS. As a result, the pressure inside the container body 2 is maintained constant. Therefore, the discharge product 1 can be discharged until the final stage without adjusting the initial pressure to a high pressure. Further, the dissolved amount of the vaporized gas dissolved in the aqueous stock solution C is likely to be kept constant, and the discharged product is likely to form stable bubbles.

More specifically, the internal pressure of the container body 2 of the discharge product 1 of the present embodiment is preferably adjusted to be 0.05 MPa or more, and is adjusted to 0.1 MPa or more at 25 ° C. It is more preferable to have. 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., 0. It is more preferable that the pressure is adjusted to 2 MPa or less. In the discharge product 1 of the present embodiment, as described above, the pressure (equilibrium pressure) of the discharge product is adjusted to be lower than the saturated vapor pressure of the liquefied gas, so that the vaporized gas of the liquefied gas introduced into the container body is used. A part of the gas is dissolved in the undiluted solution, and the rest is present in the gas phase part, so that the pressure change due to the temperature change is small and a stable foam can be obtained. Therefore, the discharge product 1 has a low pressure and is highly safe. Further, since it is not necessary for the discharge product 1 to adopt the container body 2 having a high pressure resistance that can withstand a higher internal pressure, the weight of the container body 2 can be reduced and the amount of material used can be reduced. ..

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

(Example 1)
An aqueous stock solution 1 was prepared according to the formulation (unit: mass%) shown in Table 1 below, and 40 g of the synthetic resin container body shown in FIG. 1 was filled. Next, an injection device equipped with a holder and a regulating valve was attached to the container body, and made of aluminum filled with 10 g of transformer-1,3,3,3-tetrafluoropropa-1-ene (HFO-1234ze (E)) as a liquefied gas. The gas container was housed and the valve assembly was installed. The vaporized gas of the liquefied gas was released from the gas container into the container body, and the vaporized gas was dissolved in the stock solution to bring it into an equilibrium state, thereby producing a discharged product. Air is sealed in the space under the holder. The pressure inside the container body (25 ° C.) was 0.2 MPa when the pressure inside the container body and the pressure at which the air in the lower space expanded were in equilibrium. The amount of vaporized gas released from the gas container was 1.4 g (3.5% by mass in the effervescent composition).

(Examples 2 to 14)
An effervescent composition was prepared and a discharged product was produced by the same method as in Example 1 except that the types of the aqueous stock solution and the vaporized gas were changed to the formulations shown in Tables 1 and 2.

(Comparative Example 1)
An aqueous stock solution 1 was prepared according to the formulation (unit: mass%) shown in Table 1 above, and 40 g of the synthetic resin container body shown in FIG. 1 was filled. Next, the valve assembly was attached to the container body. A discharge product was manufactured by filling carbon dioxide gas from the stem of the valve assembly. The pressure inside the container body was 0.5 MPa (25 ° C.).

(Comparative Example 2)
An effervescent composition was prepared by the same method except that nitrogen was filled in place of carbon dioxide gas of Comparative Example 1, and a discharged product was produced.

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

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

As shown in Table 2, the effervescent compositions ejected by the ejected products of Examples 3 to 8 and 13 to 14 all had no difference in effervescence between the initial stage and the final stage, and formed very fine bubbles. .. Further, the effervescent 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 stage and the final stage, and fine bubbles were formed. In addition, the foamable composition discharged by the discharge products of Examples 1 and 2 was easy to spread. The foamable compositions discharged by the discharge products of Examples 9 and 10 had no difference in foamability between the initial stage and the final stage, and although very fine bubbles were formed, it was difficult to spread the coating. The foamable compositions discharged by the discharge products of Examples 11 and 12 had no difference in foamability between the initial stage and the final stage, but had weak foamability and formed slightly coarse foam. Therefore, the effervescent composition discharged by the discharge products of Examples 1 to 14 was maintained at a low pressure in the container and was easily discharged at a constant pressure. On the other hand, the foamable compositions discharged by the discharge products of Comparative Examples 1 and 2 were slightly foamed at the initial stage but coarse bubbles, and could not form bubbles at the final stage.

1 Discharge product 2 Container body 21 Body 22 Neck 23 Valve assembly 23a Housing 23b Stem 23c Stem rubber 23d Stem hole 23e Flange part 23f Outer cylindrical part 23g Inner cylindrical part 23h Through hole 23i Stem inner passage 23j Spring 3 Gas container 31 Gas container Main body 32 Valve assembly 32a Stem 4 Injection device 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 Contacted part 6 Adjusting valve 61 Fitting recess 62 steps Part 63 Contact part 64 Upper adjustment valve 65 Lower adjustment 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 (6)

An effervescent composition containing an aqueous stock solution and a liquefied gas.
The aqueous stock solution contains water, a foaming agent, and a hydrofluoroolefin having a boiling point of 5 to 40 ° C.
The pressure of the effervescent composition at 25 ° C. is 0.05 to 0.3 MPa.
Effervescent composition. The effervescent composition according to claim 1, wherein the content of the hydrofluoroolefin is 1 to 50% by mass in the aqueous stock solution. The effervescent composition according to claim 1 or 2, wherein the content of the liquefied gas is 1 to 25% by mass in the effervescent composition. The effervescent composition according to any one of claims 1 to 3, wherein the saturated vapor pressure of the liquefied gas at 25 ° C. is 0.35 to 0.6 MPa. The effervescent composition according to any one of claims 1 to 4 is filled with the foaming composition.
The container body filled with the aqueous stock solution and
A gas container filled with the liquefied gas and
An injection device for discharging the vaporized gas of the liquefied gas from the gas container into the container body is provided.
The injection device is a discharge product including a holder for accommodating the gas container and a regulating valve for adjusting the amount of the vaporized gas released. The discharge product according to claim 5, wherein the pressure in the container body at 25 ° C. is 0.05 to 0.3 MPa.

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