WO2015122044A1

WO2015122044A1 - Foamable aerosol product

Info

Publication number: WO2015122044A1
Application number: PCT/JP2014/075831
Authority: WO
Inventors: 絋川越
Original assignee: 株式会社ミルボン
Priority date: 2014-02-12
Filing date: 2014-09-29
Publication date: 2015-08-20
Also published as: JP6505365B2; JP2015151342A

Abstract

Provided is a foamable aerosol product, in which the concentration of carbon dioxide in a container can be kept at a certain level or higher when the upper limit of a gauge pressure is set and a liquefied gas and carbon dioxide are used in combination as charged gases. A foamable aerosol product which comprises [A] an undiluted solution containing an anionic surfactant, [B] a liquefied gas or both a liquefied gas and isopentane and [C] carbon dioxide, wherein the components [A], [B] and [C] are filled in a container, the gauge pressure in the container is 0.80 MPa or less at 25ºC, the ratio of the content of the component [B] to the content of the component [A], i.e., [B]/[A], is 3.0/97.0 or more by mass, and the concentration of the component [C] filled in the container is 1.20% by mass or more.

Description

Effervescent aerosol products

The present invention relates to a foamable aerosol product.

For cosmetics such as hair sprays, facial cleansing foams, and hair styling products, foamable aerosol products that fill the container with the stock solution together with the propellant and apply foam formed after spraying from the container have become popular. Yes.

In recent years, the effect of carbon dioxide (carbon dioxide gas) on promoting blood circulation in the skin has attracted attention, and carbon dioxide is filled in a container as a propellant in the foamable aerosol product as described above, and foaming is achieved by jetting from this container. Techniques for causing the formed foam to act on the skin are known (see JP 2013-213062 A, JP 2009-269914 A, and JP 2010-248098 A).

By the way, the gauge pressure (pressure difference between the internal pressure of the container and the atmospheric pressure) of the foamable aerosol product is generally set to an upper limit from the viewpoint of safety. When the pressure upper limit is made constant, when the action on the skin based on carbon dioxide is desired to be increased, it is desired to increase the amount of carbon dioxide filled in the container. This increase is easily achieved if only carbon dioxide is used as the filling gas. However, if only carbon dioxide is used, the foaming property becomes insufficient, so it is necessary to use a liquefied gas in combination as the gas to be filled. On the other hand, a decrease in the filling amount of carbon dioxide is expected.

In view of the above circumstances, the present invention sets the upper limit of the gauge pressure from the viewpoint of safety and the like, and when using liquefied gas and carbon dioxide as a filling gas, the carbon dioxide concentration in the container is set to a certain level or more. The purpose is to provide foamable aerosol products.

As a result of intensive studies by the inventor on the combined use of carbon dioxide and liquefied gas and a gauge pressure of 0.80 MPa or less, the concentration of carbon dioxide tends to increase if the mass ratio of liquefied gas and isopentane to the stock solution is increased. The inventors have found that the concentration of carbon dioxide charged in the container can be 1.20% by mass or more, and have completed the present invention.

That is, the foamable aerosol product according to the present invention is a foamable aerosol product in which the following [A], [B] and [C] are filled in a container, and the gauge pressure of the container at 25 ° C. is 0.80 MPa. Hereinafter, the mass ratio [B] / [A] of the [B] to the [A] is 3.0 / 97.0 or more, and the concentration of the [C] filled in the container is 1.20% by mass. It is the above.
[A] Stock solution containing an anionic surfactant [B] Liquefied gas, or liquefied gas and isopentane [C] Carbon dioxide

The foamable aerosol product according to the present invention is used, for example, as a shampoo. The persistence on the hair of the foam comprising the [A] stock solution in which water is the medium decreases as the hydrophilicity of the hair increases due to damage caused by oxidative hair dyeing treatment, etc. In the foamable aerosol product according to the invention, since the mass ratio [B] / [A] is 3.0 / 97.0 or more as described above, a decrease in the sustainability is suppressed.

The gauge pressure at 25 ° C. of the foamable aerosol product according to the present invention is, for example, 0.45 MPa or more.

The mass ratio [B] / [A] of the foamable aerosol product according to the present invention is, for example, 30.0 / 70.0 or less.

The pressure of the liquefied gas in [B] at 20 ° C. of the foamable aerosol product according to the present invention is preferably 0.10 MPa or more and 0.45 MPa or less. When it is 0.10 MPa or more, it is preferable for foaming properties, and when it is 0.45 MPa or less, it is preferable for sustainability of the formed bubbles.

The concentration of [C] in the container of the foamable aerosol product according to the present invention is, for example, 0.45 mass% or more and 3.00 mass% or less.

According to the present invention, since the concentration of carbon dioxide in the container can be increased by increasing the mass ratio of the liquefied gas and isopentane to the stock solution, the combined use of carbon dioxide and liquefied gas and the gauge pressure of 0.80 MPa or less are also required. The carbon dioxide concentration can be made 1.20% by mass or more.

The present invention will be described below based on the foamable aerosol product of the present embodiment. The foamable aerosol product of this embodiment is suitable for shampoo use for washing hair, and [A] undiluted solution, [B] liquefied gas, or liquefied gas and isopentane, and [C] carbon dioxide The container is filled and the gauge pressure is set to a predetermined value or less.

([A] undiluted solution)
[A] The stock solution is a mixture of an anionic surfactant and water (the amount of water in the [A] stock solution is, for example, 70% by mass or more). Moreover, you may mix | blend what is well-known as a shampoo raw material with [A] stock solution in the range which does not impair the effect of this invention.

Anionic surfactant is a component that removes dirt such as the scalp and contributes to foaming properties. One or more types of anionic surfactants are blended in the [A] stock solution.

Examples of the anionic surfactants include carboxylic acid anionic surfactants such as N-acyl amino acid salts and alkyl ether carboxylates; sulfonic acid anionic surfactants such as N-acylmethyl taurate; alkyl sulfates. , Sulfate anionic surfactants such as polyoxyethylene alkyl ether sulfates; sulfosuccinate anionic surfactants such as polyoxyethylene sulfosuccinic acid alkyls, etc. Salt, potassium salt, triethanol salt, monoethanol salt, etc.). N-acyl amino acid salts are said to be anionic surfactants with low irritation to the scalp. Examples of the N-acyl amino acid salt include N-acyl glutamate, N-acyl alanine, N-acyl sarcosine, N-acyl glycine, and N-acyl aspartate.

[A] The amount of the anionic surfactant in the stock solution is preferably 3% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 25% by mass or less from the viewpoint of effective soil removal and foaming properties. 10 mass% or more and 20 mass% or less are more preferable.

[A] As described above, a known shampoo raw material is arbitrarily mixed in the [A] stock solution. Examples of the optional raw material include amphoteric surfactants, nonionic surfactants, cationic polymers, lower alcohols, polyhydric alcohols, saccharides, amino acids, animal and plant extracts, inorganic compounds, fragrances, and preservatives.

Blending of nonionic surfactants such as polyglycerin fatty acid esters is suitable for foaming properties and foam persistence. [A] The blending amount of the nonionic surfactant in the stock solution is, for example, 0.1% by mass or more. The upper limit of the blending amount is preferably 5% by mass, preferably 4% by mass, more preferably 3% by mass, and still more preferably 1% by mass in order to lower the viscosity of the stock solution [A] that affects foamability.

The blending of amphoteric surfactants such as betaine acetate type amphoteric surfactants is suitable for foaming and foam sustainability. [A] The compounding amount in the stock solution is 0.1% by mass or more for the amphoteric surfactant, for example. The upper limit of the blending amount is preferably 8% by mass, preferably 6% by mass, more preferably 4% by mass, and still more preferably 2% by mass in order to lower the viscosity of the stock solution [A] that affects foamability.

Also, the addition of the cationic polymer [A] improves the fingering property when washing the stock solution from the hair. Examples of the cationic polymer include cationized cellulose, cationized guar gum, vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, N, N-dimethylaminoethyl diethyl methacrylate sulfate / N, N-dimethylacrylamide / polyethylene glycol dimethacrylate copolymer and the like. [A] The blending amount of the cationic polymer in the stock solution is, for example, 0.1% by mass or more and 1% by mass or less.

[A] The dosage form of the stock solution should be liquid. When the viscosity of the liquid [A] stock solution is measured using a B-type viscometer (temperature: 25 ° C., rotor: appropriately set according to the viscosity, rotor rotational speed: appropriately set according to the viscosity) The value 60 seconds after the start of viscosity measurement is preferably 10 mPa · s or more and 1,000 mPa · s or less, more preferably 20 mPa · s or more and 500 mPa · s or less, and further preferably 30 mPa · s or more and 400 mPa · s or less.

[A] The pH of the stock solution should be neutral or weakly acidic. By keeping the pH weakly acidic, the effect of promoting blood circulation can be enhanced by suppressing carbon dioxide from becoming carbonate, and [A] deterioration of foamability and dischargeability due to an increase in viscosity of the stock solution accompanying a decrease in pH. Is suppressed. [A] The pH of the stock solution is preferably from 4.0 to 7.5, preferably from 5.0 to 7.0, more preferably from 5.0 to 6.8, and from 5.0 to 6.5. The following is more preferable.

In the foamable aerosol product of the present embodiment, the filling amount of the [A] stock solution in the container is set as appropriate. The filling amount is, for example, preferably 40 g or more and 65 g or less, and preferably 45 g or more and 60 g or less per 100 ml volume of the container. By making it 40 g or more, the use period of the product becomes longer, and by making it 65 g or less, it is preferable for increasing the amount of [C] carbon dioxide filled in the container.

([B] Liquefied gas or liquefied gas and isopentane)
The container in the foamable aerosol product of this embodiment is filled with [B] liquefied gas, or liquefied gas and isopentane. Both the filled liquefied gas and isopentane are in a vapor-liquid equilibrium state by filling with [C] carbon dioxide. The liquefied gas and isopentane both foam the [A] stock solution ejected from the container, and filling with isopentane is suitable for the sustainability of the foam.

The pressure of the liquefied gas should be set as appropriate, but it is preferably 0.10 MPa or more and 0.45 MPa or less at 20 ° C., preferably 0.15 MPa or more and 0.35 MPa or less, and more preferably 0.15 MPa or more and 0.30 MPa or less. Preferably, it is 0.15 MPa or more and 0.25 MPa or less. By setting the pressure to 0.15 MPa or more, the foamability is improved, and by setting the pressure to 0.45 MPa or less, the sustainability of the formed foam is improved and the amount of carbon dioxide that can be filled in the container can be increased.

The liquefied gas in this embodiment is liquefied petroleum gas (LPG), and may be propane and n-butane, propane and i-butane, or propane, n-butane and i-butane. In the case of filling the container with liquefied gas and isopentane, propane and n-butane and isopentane, propane and i-butane and isopentane, or propane, n-butane, i-butane and isopentane are preferable.

The mass ratio [B] / [A] of [B] ([B] liquefied gas or liquefied gas and isopentane) to [A] ([A] stock solution) when filling the container is 3.0 / 97. 0.0 or more, preferably 5.0 / 95.0 or more, preferably 10.0 / 90.0 or more, and more preferably 15.0 / 85.0 or more. Further, the mass ratio [B] / [A] is preferably 30.0 / 70.0 or less, and preferably 25.0 / 75.0 or less. When the mass ratio [B] / [A] is 3.0 / 97.0 or more, the amount of [C] carbon dioxide charged in the container can be increased, and the mass ratio [B] / [A] is 30.0 / If it is 70.0 or less, the amount of anionic surfactant in the formed foam can be increased. In the above mass ratio [B] / [A], when [B] is a liquefied gas, the mass ratio is calculated by the amount of liquefied gas, and when [B] is a liquefied gas and isopentane. , Mass ratio calculated by the total amount of liquefied gas and isopentane.

Moreover, when isopentane is filled together with the liquefied gas, the amount of the liquefied gas is preferably larger than that of isopentane. Thereby, foamability becomes favorable.

([C] carbon dioxide)
In the foamable aerosol product of the present embodiment, the concentration of [C] carbon dioxide filled in the container is 1.20% by mass or more, preferably 1.30% by mass or more, and 1.40% by mass or more. Preferably, 1.50 mass% or more is more preferable, 1.60 mass% or more is further preferable, and 1.70 mass% or more is further more preferable. On the other hand, the upper limit of the concentration of [C] carbon dioxide filled in the container is, for example, 3.00% by mass, and is set by increasing both the mass ratio [B] / [A] and the gauge pressure of the container. This is a possible concentration. Here, the concentration of [C] carbon dioxide charged in the container is “([C] carbon dioxide charged in the container) / ([A] stock solution, [B] liquefied gas, isopentane charged in the container). , And [C] carbon dioxide) × 100 ”.

A part of [C] carbon dioxide filled in the container is contained in the liquid phase part composed of the filled [A] stock solution, [B] liquefied gas, and isopentane. At this time, the concentration of [C] carbon dioxide contained in the liquid phase part is preferably 0.45% by mass or more, preferably 0.60% by mass or more, more preferably 0.75% by mass or more, and 0.90. % By mass or more is more preferable, and 1.00% by mass or more is more preferable. On the other hand, the upper limit of the concentration of [C] carbon dioxide contained in the liquid phase part is a concentration that can be set by increasing the gauge pressure of the container, for example, 2.50% by mass.

As the concentration of [C] carbon dioxide contained in the liquid phase part, a value calculated from a gas state equation or the like is adopted as follows.
PV = w / M · RT
Concentration of [C] contained in the liquid phase portion = ([C] filling amount−w) / ([A] and [B] filling amount + [C] filling amount−w) × 100
w (g): Carbon dioxide gas amount in the gas phase in the container P (atm): Gauge pressure (MPa) of the container at 25 ° C. × 9.87 + 1 atm
V (L): Calculated volume of the gas phase in the container (capacity of the container−filling mass / specific gravity)
M: 44 (molecular weight of carbon dioxide)
R (atm · L / K · mol): 0.082
T (K): 273 + 25 ° C
[A] (g): Stock solution [B] (g): Liquefied gas and isopentane [C] (g): Carbon dioxide

[C] The case where a part of carbon dioxide is contained in the liquid phase part is as described above, and [C] all the carbon dioxide contained in the liquid phase part is assumed to be contained in the [A] stock solution. The concentration of [C] carbon dioxide contained in the stock solution [A] is “([C] filling amount−w) / ([A] filling amount + [C] filling amount−w) × 100”. Is calculated by [A] The concentration of [C] carbon dioxide contained in the stock solution is preferably 0.50% by mass or more, preferably 0.70% by mass or more, more preferably 0.85% by mass or more, and 1.00% by mass. The above is more preferable, and 1.10% by mass or more is even more preferable. On the other hand, the upper limit of the concentration of [C] carbon dioxide contained in the [A] stock solution is, for example, 2.80% by mass.

(container)
The container in the foamable aerosol product of the present embodiment may be a known pressure-resistant container, and the material thereof is made of metal such as aluminum, aluminum alloy, tinplate, and steel. This container may have a resin layer laminated on the inner surface or an inner bag inside.

(Gauge pressure)
The gauge pressure of the container in the foamable aerosol product of the present embodiment is 0.80 MPa or less and preferably 0.65 MPa or less at a temperature condition of 25 ° C. from the viewpoint of safety. On the other hand, the lower limit of the gauge pressure at 25 ° C. is preferably 0.45 MPa, preferably 0.50 MPa, more preferably 0.55 MPa in order to increase the filling amount of [C] carbon dioxide into the container. 0.60 MPa is more preferable.

(Use)
The foamable aerosol product of this embodiment can be used as a shampoo for washing hair and the like because [A] an anionic surfactant is blended in the stock solution. Even if the hair to be cleaned has increased hydrophilicity due to damage, by maintaining the mass ratio [B] / [A] to 3.0 / 97.0 or more, the persistence of the foam Will improve. This is thought to be because, in the foam with an increased mass ratio [B] / [A], the concentration of the hydrophilic [A] stock solution is low, so that the absorbability of the foam into the hair is suppressed. .

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

The foamable aerosol products of Examples, Comparative Examples and Reference Examples were produced. The details are as follows.
([A] Stock solution)
A mixture of water and other raw materials, and adjusted to pH 5.60 with citric acid was used as [A] stock solution used in Examples, Comparative Examples and Reference Examples. The raw materials and blending concentrations were as follows. Sodium polyoxyethylene lauryl ether acetate (designated name: laureth-4 carboxylic acid Na) 9% by mass, disodium polyoxyethylene sulfosuccinate 7% by mass, polyglyceryl monolaurate (designated name: polyglyceryl-10 laurate) 0.5 % By mass, polyoxypropylene (1) coconut oil fatty acid monoisopropanolamide (designated name: PPG-2 cocamide) 3% by mass, N, N-dimethylaminoethyl diethyl methacrylate sulfate, N, N-dimethylacrylamide, dimethacryl Acid polyethylene glycol copolymer (display name: polyquaternium-52) 0.2 mass%, polyethylene glycol 1540 (display name: PEG-32) 0.4 mass%, cationized cellulose (display name: polyquaternium-10) 2 The amount% l-menthol 0.6% by weight, PCA menthyl 0.1 wt%, ethanol 0.1 weight%, 1,3-butylene glycol 0.2 wt%, perfume 0.5%

(Foaming aerosol products)
The container is filled with [A] stock solution, [B] liquefied gas LPG and isopentane, and finally [C] carbon dioxide is filled to produce foamable aerosol products of Examples, Comparative Examples and Reference Examples. did. Table 1 below shows details of products such as the filling amounts of [A], [B], and [C] filled in the container.

In Table 1, “[A] Stock solution volume (ml)” is a value calculated by “[A] Stock solution (g)” / “[A] Stock solution specific gravity”, and “[B] LPG And “total volume (ml) of isopentane” is a value calculated by “total amount of [B] LPG and isopentane (g)” / “mixed specific gravity of [B] LPG and isopentane”, and “volume of liquid phase part” “(Ml)” is a value calculated by “[A] volume of stock solution (ml)” + “total volume of [B] LPG and isopentane (ml)”, and “volume of gas phase part (ml)”. Is a value calculated by “volume of container (ml)” − “volume of liquid phase part (ml)”.

Tables 2 to 5 below show mass ratios [B] / [A] of Examples, Comparative Examples, and Reference Examples. In these tables, “[C] carbon dioxide concentration (%) charged in the container” is a value calculated from the values in Table 1, and “[C] carbon dioxide (g)” / “[[ A] Stock solution, [B] LPG, isopentane and [C] total amount of carbon dioxide (g) ”× 100. The “[C] carbon dioxide mass (g) in the gas phase portion in the container” is “w” calculated based on the above equation of state. The “[C] carbon dioxide mass (g) contained in the liquid phase part in the container” is calculated by “[C] carbon dioxide” − “w” in Table 1. “[A] Concentration of carbon dioxide contained in [A] stock solution (%)” means that all of [C] carbon dioxide contained in the liquid phase part is contained in [A] stock solution. [C] Carbon dioxide mass (g) contained in the inner liquid phase portion] / “[A] Stock solution (g)” + “[C] Carbon dioxide mass (g) contained in the liquid phase portion in the container” ”× 100. “[C] carbon dioxide concentration (%) contained in the liquid phase part in the container” is “[C] carbon dioxide mass (g) contained in the liquid phase part in the container” ”/“ “[A] Stock solution, [B] Total amount of LPG and isopentane (g) ”+“ [C] carbon dioxide mass (g) contained in liquid phase part in container ”” × 100

In Table 2 below, as the value of “mass ratio [B] / [A]” is larger, “[C] carbon dioxide concentration (%) filled in the container”, “[A] contained in the stock solution [ It can be confirmed that the values of “C] carbon dioxide concentration (%)” and “[C] carbon dioxide concentration (%) contained in the liquid phase portion in the container” are increased. In addition, when applied to hair having a history of oxidative hair dyeing treatment, the greater the value of “mass ratio [B] / [A]”, the higher the foam persistence.

In Table 3 below, even if the mass ratio [B] / [A] is relatively low, if the gauge pressure is increased, “[C] carbon dioxide concentration (%) filled in the container”, “[A] It can be confirmed that “[C] carbon dioxide concentration (%) contained in the stock solution” and “[C] carbon dioxide concentration (%) contained in the liquid phase portion in the container” increased.

In Table 4 below, the same tendency as in Table 2 can be confirmed. Moreover, the tendency of persistence of bubbles was the same.

JP 2013-213062 A JP 2009-269914 A JP 2010-248098 A

Claims

The following [A], [B] and [C] are foamable aerosol products filled in a container,
The gauge pressure at 25 ° C. of the container is 0.80 MPa or less,
The mass ratio [B] / [A] of [B] to [A] is 3.0 / 97.0 or more,
A foamable aerosol product, wherein the concentration of the [C] filled in the container is 1.20% by mass or more.
[A] Stock solution containing an anionic surfactant [B] Liquefied gas, or liquefied gas and isopentane [C] Carbon dioxide
The foamable aerosol product according to claim 1 used as a shampoo.
The foamable aerosol product according to claim 1 or 2, wherein the gauge pressure at 25 ° C is 0.45 MPa or more.
The foamable aerosol product according to any one of claims 1 to 3, wherein the mass ratio [B] / [A] is 30.0 / 70.0 or less.
The foamable aerosol product according to any one of claims 1 to 4, wherein the pressure of the liquefied gas in [B] at 20 ° C is 0.10 MPa or more.
The foamable aerosol product according to any one of claims 1 to 5, wherein the pressure of the liquefied gas in [B] at 20 ° C is 0.45 MPa or less.
The foamable aerosol product according to any one of claims 1 to 6, wherein the concentration of [C] contained in the liquid phase part in the container is 0.45 mass% or more.
The foamable aerosol product according to any one of claims 1 to 7, wherein the concentration of [C] in the container is 3.00% by mass or less.