An aerosol hair growth agent that stays localized without dripping and has a high anti-itch effect.

Abstract

To provide "non-drip" aerosol hair growth agent that contains a sufficient amount of an antipruritic ingredient (menthol) and a cooling ingredient (dimethyl ether).SOLUTION: Provided is an aerosol hair growth agent consisting of a drug stock solution containing the following ingredients (A) to (D): (A) 10 to 35 mass% of ethanol; (B) 0.6 to 1 mass% of menthol; (C) 0.05 to 1 mass% of water-soluble polymer; and (D) water, and (E) liquefied gas as a propellant, the mass ratio of the drug stock solution to the propellant being 70:30 to 40:60, the water-soluble polymer having a blending amount of ethanol as component (A) of 30 mass% and being one or more types selected from alkyl-modified carboxyvinyl polymer, hydroxypropyl methylcellulose, and hydrophobized hydroxypropyl methylcellulose, which do not cause deposition and precipitation even if 0.1 mass% or more is added to the aerosol hair growth agent, when the mass ratio of the drug stock solution to the propellant is 50:50.SELECTED DRAWING: None

Description

[Technical Field] 【0001】 This invention relates to an aerosol hair growth agent. [Background technology] 【0002】 In developing aerosol hair growth products, it is crucial to include sufficient amounts of antipruritic and cooling ingredients to effectively relieve itching. Furthermore, since itching often occurs locally and persistently on the scalp, a formulation that remains localized and acts without dripping is desirable. 【0003】 In aerosol formulations, due to their manufacturing characteristics, the formulation design must ensure stability and uniformity in both the undiluted formulation (without propellant) and the filled formulation (undiluted formulation + propellant). 【0004】 Conventionally, aerosol hair growth agents containing a high concentration (0.6% or more) of menthol, an antipruritic ingredient, typically required a manufacturing process that involved increasing the ethanol concentration of the formulation concentrate to 40% or more in order to ensure a stable solubilized product. Furthermore, when using liquefied gas as a propellant, if the ratio of liquefied gas to the formulation concentrate in the filled formulation exceeds a certain level, the ratio of organic solvent (ethanol + liquefied gas) increases. This prevents the stable dissolution of thickening agents such as water-soluble polymers, making it impossible to create a "non-dripping" formulation. [Overview of the project] [Problems that the invention aims to solve] 【0005】 The present invention aims to provide an aerosol hair growth agent that does not drip while containing sufficient amounts of an antipruritic ingredient (menthol) and a cooling ingredient (liquefied gas). [Means for solving the problem] 【0006】 The gist of this invention is as follows: (1) The following components (A) to (D): (A) Ethanol 10-35% by mass, (B) Menthol 0.6-1% by mass, (C) 0.05 to 1% by mass of water-soluble polymer, and (D)Water An aerosol hair growth agent comprising a formulation concentrate containing (E) and a liquefied gas as a propellant, wherein the mass ratio of the formulation concentrate to the propellant is 70:30 to 40:60, An aerosol hair growth agent in which the water-soluble polymer is one or more selected from alkyl-modified carboxyvinyl polymer, hydroxypropyl methylcellulose, and hydrophobized hydroxypropyl methylcellulose, and does not cause precipitation or sedimentation even when added to the aerosol hair growth agent at a concentration of 0.1% by mass or more when the amount of ethanol in component (A) is 30% by mass and the mass ratio of the formulation stock solution to the propellant is 50:50. (2) The aerosol hair growth agent according to (1), wherein the formulation stock is an emulsion of water-soluble polymers and has a viscosity of 500 to 10,000 mPa·s at 20°C. (3) The aerosol hair growth agent according to (1) or (2) above, wherein the water-soluble polymer is one or more selected from alkyl-modified carboxyvinyl polymer having a viscosity of 500 to 5,000 mPa·s of a 0.2% by mass triethanolamine neutralized product (aqueous solution), hydroxypropyl methylcellulose having a viscosity of 9,000 to 12,000 mPa·s of a 2% by mass aqueous solution at 20°C, and hydrophobized hydroxypropyl methylcellulose having a substitution rate of 0.3 to 0.6% of stearyloxyhydroxypropoxy groups and a substitution rate of 7.0 to 11.0% of hydroxypropoxy groups. [Effects of the Invention] 【0007】 According to the present invention, by using a specific water-soluble polymer, it is possible to provide an aerosol hair growth agent that does not drip while incorporating sufficient amounts of an antipruritic component (menthol) and a cooling component (liquefied gas). [Modes for carrying out the invention] 【0008】 The aerosol hair growth agent of the present invention consists of a formulation concentrate and a propellant. The stock solution of the preparation used in the present invention is an aqueous stock solution, and in addition to water, it contains (A) ethanol, (B) menthol, and (C) a specific water-soluble polymer. 【0009】 In the present invention, water in the stock solution of the preparation is a component as a solvent for forming the stock solution of the preparation. (A) Ethanol in the present invention is a component as an organic solvent for forming the stock solution of the preparation. The compounding amount of ethanol in the stock solution of the preparation is 10 to 35% by mass, preferably 20 to 30% by mass. When it is less than 10%, it is difficult to stably compound menthol in the stock solution of the preparation. On the other hand, when it exceeds 35% by mass, precipitation and sedimentation of the water-soluble polymer may occur when the aerosol is filled. 【0010】 (B) Menthol in the present invention is a component exhibiting an antipruritic effect and a hair growth effect. For menthol, especially l-menthol, either a purified product from nature or a synthetic product can be used, and essential oils containing a large amount of menthol such as peppermint oil and peppermint oil may also be used. The compounding amount of menthol in the stock solution of the preparation is 0.6 to 1% by mass, preferably 0.8 to 1.0% by mass, from the viewpoint of giving a high antipruritic effect and hair growth effect. 【0011】 (C) The water-soluble polymer in the present invention has a thickening effect, is a component for making the stock solution of the preparation into an emulsion, and is a component for preventing dripping. 【0012】 In the present invention, from the viewpoints of imparting viscosity to the stock solution of the preparation to prevent dripping during aerosol spraying and stably emulsifying menthol in the stock solution of the preparation, as the water-soluble polymer, when the compounding amount of ethanol of component (A) is 30% by mass and the mass ratio of the stock solution of the preparation to the aerosol is 50:50, one or more selected from an alkyl-modified carboxyvinyl polymer, hydroxypropyl methylcellulose, and hydrophobized hydroxypropyl methylcellulose are used, and precipitation and sedimentation do not occur even when 0.1% by mass or more is compounded in the aerosol hair growth agent. 【0013】 The type of the water-soluble polymer is preferably selected from components having a thickening effect and an emulsifying power and having good compatibility with the liquefied gas of the propellant (E). For example, a component selected from an alkyl-modified carboxyvinyl polymer, hydroxypropyl methylcellulose, and hydrophobized hydroxypropyl methylcellulose can be used alone or in combination of two or more. 【0014】 In the present invention, the alkyl-modified carboxyvinyl polymer refers to a copolymer of acrylic acid and / or methacrylic acid and an alkyl acrylate and / or an alkyl methacrylate thereof. As the alkyl-modified carboxyvinyl polymer, an acrylic acid / alkyl methacrylate copolymer is preferable. The acrylic acid / alkyl methacrylate mainly refers to a copolymer of acrylic acid and an alkyl methacrylate (C 10 ~C 30 ). 【0015】 The hydrophobized hydroxypropyl methylcellulose refers to a cellulose ether in which a stearyl group is introduced into hydroxypropyl methylcellulose. 【0016】 When an alkyl-modified carboxyvinyl polymer is used as the water-soluble polymer of the component (C), it is preferable to adjust the pH of the stock solution of the preparation to near neutrality using a neutralizing agent. The preferable range of pH is pH 5 to 9, and the particularly preferable range is pH 6 to 8. If the pH is on the acidic side or the alkaline side outside this range, sufficient thickening and emulsifying effects may not be exhibited. [[ID= {17}]] [[ID= {18}]] 【0017】 [[ID= {19}]] The type of neutralizing agent used is not particularly limited, and any component can be selected from those commonly used as neutralizing agents, such as sodium hydroxide, potassium hydroxide, ammonia, L-arginine, tromethamine, triethanolamine, aminomethylpropanol, tetrahydroxypropylethylenediamine, diisopropanolamine, triisopropanolamine, PEG-15 cocamine, etc., and used in combination of one or more types. On the other hand, when the propellant (E) liquefied gas is filled, the proportion of organic solvents in the formulation system increases, which may cause precipitation or deposition depending on the type of neutralizing agent, leading to poor spraying. Therefore, it is preferable to select a component with high compatibility with organic solvents. Tromethamine, triethanolamine, aminomethylpropanol, tetrahydroxypropylethylenediamine, diisopropanolamine, triisopropanolamine, and PEG-15 cocamine are preferred, and tetrahydroxypropylethylenediamine, diisopropanolamine, triisopropanolamine, and PEG-15 cocamine are particularly preferred. 【0018】 Furthermore, the total amount of the water-soluble polymer in the formulation stock solution is 0.05 to 1% by mass, preferably 0.1 to 0.6% by mass, and particularly preferably 0.1 to 0.4% by mass. If the amount is too low, it is difficult to stably incorporate menthol into the formulation stock solution. On the other hand, if the amount is too high, it will cause stickiness when sprayed. 【0019】 Unless otherwise specified, the method for measuring the viscosity of the water-soluble polymer used in the present invention is as follows. 【0020】 (Viscosity measurement method) • Measuring device: Type B viscometer TV-20 (manufactured by Toki Sangyo Co., Ltd.) ·Measurement conditions: 20℃, M4, 30rpm / sec(60sec) While water-soluble polymers require stirring to dissolve in solution, prolonged and strong stirring can reduce their viscosity. To evaluate viscosity under stable conditions, the water-soluble polymer was added to the solvent and stirred at 3,000 rpm for 60 minutes using a disperser. After confirming complete dispersion and dissolution, the sample was subjected to viscosity measurement. 【0021】 Preferably, the water-soluble polymers used in the present invention include alkyl-modified carboxyvinyl polymers having a viscosity of 500 to 5,000 mPa·s for a 0.2% by mass triethanolamine neutralized solution (aqueous solution), hydroxypropyl methylcellulose having a viscosity of 9,000 to 12,000 mPa·s for a 2% by mass aqueous solution at 20°C, and hydrophobized hydroxypropyl methylcellulose having a substitution rate of 0.3 to 0.6% for stearyloxyhydroxypropoxy groups and a substitution rate of 7.0 to 11.0% for hydroxypropoxy groups. 【0022】 As the water-soluble polymer used in the present invention, for example, the following commercially available products can be used. (Alkyl-modified carboxyvinyl polymer) PEMULEN TM TR-2 (manufactured by Lubrizol, viscosity of 0.2% by mass triethanolamine neutralized solution (aqueous solution): 500-5,000 mPa·s) (Hydroxypropylmethylcellulose) Metros TM 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity of a 2% by mass aqueous solution at 20°C: 10,000 mPa·s) (Hydrophobic hydroxypropyl methylcellulose) Saint-Gerald TM 60L (manufactured by Daido Chemical Industries, Ltd., substitution rate of stearyloxyhydroxypropoxy groups: 0.3-0.6%, substitution rate of hydroxypropoxy groups: 7.0-11.0%) 【0023】 The aerosol hair growth agent of the present invention contains, in addition to the above essential components and hair growth active ingredients, surfactants, oily components, etc., in the undiluted formulation, as long as they do not impair the effects of the present invention. For example, the following can be incorporated: soybean oil, jojoba oil, water-soluble silicone compounds, higher alcohols, lower alcohols other than ethanol, polyhydric alcohols (e.g., glycerin, 1,3-butylene glycol), powders, plant extracts (e.g., seaweed extract, mulberry extract), preservatives (e.g., phenoxyethanol, methylparaben, propylparaben), chelating agents (e.g., disodium edetate), antioxidants (e.g., ascorbic acid, vitamin E), UV absorbers, cooling agents (e.g., l-menthyl glyceryl ether), warming agents (e.g., vanillyl butyl ether), deodorants (e.g., tea extract, persimmon extract), fragrances, pH adjusters (e.g., diisopropanolamine), etc. 【0024】 The aerosol hair growth agent of the present invention preferably has a viscosity of 500 to 10,000 mPa·s at 20°C, more preferably 800 to 8,000 mPa·s, and particularly preferably 1,000 to 5,000 mPa·s, in terms of not dripping when sprayed and having a good, non-sticky feel. 【0025】 The propellant used in this invention is a liquefied gas, which is used to stably solubilize the emulsion-like formulation stock solution during filling. LPG and dimethyl ether can be used as the liquefied gas, but dimethyl ether is preferred in terms of compatibility with the formulation stock solution, good spray characteristics, and cooling effect. 【0026】 The mass ratio of the formulation stock solution to the propellant is 70:30 to 40:60, preferably 60:40 to 40:60. If the mass ratio of the propellant to the formulation stock solution is less than 70:30, the oil-soluble component menthol cannot be completely solubilized. In addition, the internal pressure of the filled formulation is low, resulting in weak spraying and insufficient cooling effect due to the heat of vaporization of the propellant. On the other hand, if the mass ratio of the propellant to the formulation stock solution exceeds 40:60, precipitation of water-soluble polymers may occur, which can cause spraying problems. From the viewpoint of providing good spraying characteristics and sufficient cooling effect due to the heat of vaporization of the propellant, the particularly preferred range is 55:45 to 45:55. 【0027】 The aerosol hair growth agent of the present invention can be manufactured, for example, by filling a metal container such as an aluminum or tin can with a volume of 1 L or less with the formulation concentrate, sealing it with a valve, and then filling it with liquefied gas under high pressure. In this case, the pressure inside the product container at 35°C inside the aerosol can is 0.8 MPa or less from the viewpoint of safe storage. 【0028】 The aerosol hair growth agent of the present invention is characterized by having an ethanol concentration of 10 to 35% by mass in the formulation concentrate, adding a specific water-soluble polymer to make the formulation concentrate an emulsion, and then filling it with liquefied gas, thereby stably solubilizing the specific water-soluble polymer by lowering the ratio of organic solvent (ethanol + liquefied gas) in the filled formulation while increasing the ratio of water. [Examples] 【0029】 The present invention will be described in more detail below with reference to examples and comparative examples, but the scope of the present invention is not limited to the following examples. The numerical values ​​of the formulation amounts in Tables 1 to 4 are in mass percent. 【0030】 [Examples 1-19 and Comparative Examples 1-25] 1. Preparation of the formulation Aerosol hair growth agents were prepared by conventional methods using raw materials with the compositions of Examples 1-19 and Comparative Examples 1-25 shown in Tables 1-5. 【0031】 As the water-soluble polymer, the following commercially available products were used. (Alkyl-modified carboxyvinyl polymer) PEMULEN TM TR-2 (manufactured by Lubrizol, viscosity of 0.2 mass% triethanolamine neutralized product (aqueous solution): 2,020 mPa·s) PEMULEN TM TR-1 (manufactured by Lubrizol, viscosity of 0.2 mass% triethanolamine neutralized product (aqueous solution): 7,310 mPa·s) PEMULEN TM EZ-4U (manufactured by Lubrizol, viscosity of 0.2 mass% triethanolamine neutralized product (aqueous solution): 8,820 mPa·s) NTC CARBOMER TM FD10 (manufactured by Nikko Chemicals Co., Ltd., viscosity of 0.2 mass% triethanolamine neutralized product (aqueous solution): 8,220 mPa·s) NTC CARBOMER TM FD21 (manufactured by Nikko Chemicals Co., Ltd., viscosity of 0.2 mass% triethanolamine neutralized product (aqueous solution): 17,350 mPa·s) Carbopol TM 1382 (manufactured by Lubrizol, viscosity of 0.2 mass% triethanolamine neutralized product (aqueous solution): 14,570 mPa·s) Carbopol TM ETD 2020 (manufactured by Lubrizol, viscosity of 0.2 mass% triethanolamine neutralized product (aqueous solution): 9,800 mPa·s) Carbopol TM Ultrez 20 (manufactured by Lubrizol, viscosity of 0.2 mass% triethanolamine neutralized product (aqueous solution): 10,350 mPa·s) Carbopol TM Ultrez 21 (manufactured by Lubrizol, viscosity of 0.2 mass% triethanolamine neutralized product (aqueous solution): 9,630 mPa·s) 【0032】 (Carboxyvinyl polymer) Hibiscus Wako 104 (manufactured by Fujifilm Wako Pure Chemical Corporation) NTC CARBOMER TM 380 (Manufactured by Nikko Chemicals Co., Ltd.) Carbopol TM 940 (manufactured by Lubrizol) Carbopol TM (Lubrizol 980) Carbopol TM (Manufactured by Lubrizol, Inc.) Carbopol TM (2984 Lubrizol) Carbopol TM Ultrez 10 (manufactured by Lubrizol) 【0033】 (Hydroxypropylmethylcellulose) Metros TM 60SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity of a 2% by mass aqueous solution at 20°C: 4,000 mPa·s) Metros TM 65SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity of a 2% by mass aqueous solution at 20°C: 4,000 mPa·s) Metros TM 90SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity of a 2% by mass aqueous solution at 20°C: 4,000 mPa·s) Metros TM 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity of a 2% by mass aqueous solution at 20°C: 10,000 mPa·s) Metros TM 65SH-15000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity of a 2% by mass aqueous solution at 20°C: 15,000 mPa·s) Metros TM 90SH-15000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity of a 2% by mass aqueous solution at 20°C: 15,000 mPa·s) 【0034】 (Hydrophobic hydroxypropyl methylcellulose) Saint-Gerald TM60M (manufactured by Daido Chemical Industries, Ltd., substitution rate of stearyloxyhydroxypropoxy groups: 1.0-2.0%, substitution rate of hydroxypropoxy groups: 7.0-11.0%) Saint-Gerald TM 60L (manufactured by Daido Chemical Industries, Ltd., substitution rate of stearyloxyhydroxypropoxy groups: 0.3-0.6%, substitution rate of hydroxypropoxy groups: 7.0-11.0%) Saint-Gerald TM 90M (manufactured by Daido Chemical Industries, Ltd., substitution rate of stearyloxyhydroxypropoxy groups: 1.0-2.0%, substitution rate of hydroxypropoxy groups: 7.0-11.0%) 【0035】 2. Evaluation Method The following evaluation was conducted. 【0036】 (1) Properties of the preparation • Properties of the undiluted formulation: The undiluted formulation was evaluated by visual inspection of its appearance to determine if precipitation or separation occurred at 40°C, room temperature, and low temperature (5°C). (Judgment criteria) ◎...Under all conditions, no precipitation or separation occurred for more than 30 days. ○...Under all conditions, no precipitation or separation occurred for more than 7 days but less than 30 days. ×...Precipitation or separation occurred in less than 7 days under any of the following conditions. 【0037】 • Properties of the filled formulation: The undiluted formulation was evaluated by visual inspection of its appearance to determine if precipitation or separation occurred at 40°C, room temperature, and low temperature (5°C). (Judgment criteria) ◎...Under all conditions, no precipitation or separation occurred for more than 30 days. ○...Under all conditions, no precipitation or separation occurred for more than 7 days but less than 30 days. ×...Precipitation or separation occurred in less than 7 days under any of the following conditions. 【0038】 (2) Feeling of use Regarding the usability of the aerosol hair growth agent, which showed favorable results in "(1) Properties of the Formulation" above, 10 monitors sprayed an appropriate amount onto their scalps and evaluated it according to the following criteria. The evaluation was conducted by recording an integer value on a 4-point scale from 0 to 3. The evaluation was determined based on the average score of all monitors. The results of each evaluation are summarized below. ◎ (2.5 to 3 points): Very good 〇(more than 2 points but less than 2.5 points): Good △ (More than 1 point but 2 points or less): Not considered a problem. × (0 to less than 1 point): There is a problem. 【0039】 • Spray state We evaluated whether the spraying process was smooth, without foaming or clogging. 3 points: It was excellent, with absolutely no foaming or clogging. 2 points: There was almost no foaming or clogging, which was somewhat good. One point: I noticed some foaming and clogging, but it wasn't a problem. 0 points: There are issues with foaming and clogging. 【0040】 • Non-sticky After spraying, the feeling of stickiness on the scalp and hair was evaluated. 3 points: It wasn't sticky at all, which was great. 2 points: It wasn't sticky at all, which was a plus. 1 point: I felt some stickiness, but it wasn't a problem. 0 points: It feels very sticky, which is a problem. 【0041】 • Non-drip performance The performance of the product, including whether it dripped after being sprayed onto the scalp, was evaluated. 3 points: It didn't drip at all, which was great. 2 points: It hardly dripped at all, which was a plus. 1 point: There was some dripping, but it wasn't a problem. 0 points: There is a lot of dripping, which is problematic. 【0042】 • Antipruritic effect 3 points: I felt a high level of effectiveness, and it was very good. 2 points: I felt an effect, and it was somewhat good. 1 point: The effect felt somewhat weak, but it was not problematic. 0 points: No effect was felt; there was a problem. 【0043】 3.Results (1) Properties of the preparation The following three water-soluble polymers yielded favorable results in both the stock solution and the filled formulation. • Example 1 Acrylic acid / alkyl methacrylate copolymer, PEMULEN TM TR-2 (manufactured by Lubrizol, viscosity of 0.2% by mass triethanolamine neutralized solution (aqueous solution): 2,020 mPa·s) 【0044】 • Example 2 Hydroxypropyl methylcellulose, methyl cellulose TM 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity of a 2% by mass aqueous solution at 20°C: 10,000 mPa·s) 【0045】 • Example 3 Hydrophobized hydroxypropyl methylcellulose, Sanjelose TM 60L (manufactured by Daido Chemical Industries, Ltd., substitution rate of stearyloxyhydroxypropoxy groups: 0.3-0.6%, substitution rate of hydroxypropoxy groups: 7.0-11.0%) 【0046】 (2) Feeling of use All three formulations listed in the examples were good (○) or very good (◎). 【0047】 [Table 1] 【0048】 [Table 2] 【0049】 Table 3 【0050】 Table 4 【0051】 Table 5

Claims

[Claim 1] The following components (A) to (D): (A) Ethanol 10-35% by mass, (B) Menthol 0.6 to 1% by mass, (C) 0.05 to 1% by mass of water-soluble polymer, and (D) Water An aerosol hair growth agent comprising a formulation concentrate containing (E) and a liquefied gas as a propellant, wherein the mass ratio of the formulation concentrate to the propellant is 70:30 to 40:60, The water-soluble polymer is one or more selected from alkyl-modified carboxyvinyl polymer, hydroxypropyl methylcellulose, and hydrophobized hydroxypropyl methylcellulose, which do not cause precipitation or sedimentation even when added to the aerosol hair growth agent at a concentration of 0.1% by mass or more, when the amount of ethanol in component (A) is 30% by mass and the mass ratio of the formulation stock solution to the propellant is 50:

50. Aerosol hair growth agent comprising one or more water-soluble polymers selected from: an alkyl-modified carboxyvinyl polymer having a viscosity of 500 to 5,000 mPa·s for a 0.2% by mass triethanolamine neutralized solution (aqueous solution) at 20°C; hydroxypropyl methylcellulose having a viscosity of 9,000 to 12,000 mPa·s for a 2% by mass aqueous solution at 20°C; and hydrophobized hydroxypropyl methylcellulose having a stearyloxyhydroxypropoxy group substitution rate of 0.3 to 0.6% and a hydroxypropoxy group substitution rate of 7.0 to 11.0%. [Claim 2] The aerosol hair growth agent according to claim 1, wherein the formulation stock is an emulsion of a water-soluble polymer and has a viscosity of 500 to 10,000 mPa·s at 20°C. [Claim 3] The aerosol hair growth agent according to claim 1 or 2, wherein the total amount of water-soluble polymer in the formulation stock solution is 0.1 to 0.4% by mass.

Images