WO2019181510A1

WO2019181510A1 - Aerosol product

Info

Publication number: WO2019181510A1
Application number: PCT/JP2019/008878
Authority: WO
Inventors: 拓也山科; 康輝稲田; 敏郎松村
Original assignee: 株式会社マンダム
Priority date: 2018-03-19
Filing date: 2019-03-06
Publication date: 2019-09-26
Also published as: JPWO2019181510A1

Abstract

The present invention pertains to an aerosol product having a liquid concentrate and a propellant filled in a container body, wherein the liquid concentrate contains components A, B, and C indicated below, and the propellant contains a liquefied petroleum gas. Such an aerosol product exhibits high stability of lysozyme chloride, and thus is preferably applicable for use in deodorant agents. Component A: lysozyme chloride. Component B: non-ionic surfactant. Component C: water.

Description

Aerosol products

The present invention relates to an aerosol product.

It is said that body odors such as foul odor, foot odor, scalp odor and sweat odor that cause discomfort to humans are caused by the fact that sweat mixes with sebum and is decomposed by normal skin bacteria. In order to suppress these body odors, a bactericidal composition containing a bactericidal component such as triclosan or isopropylmethylphenol and a lysozyme (salt) such as lysozyme chloride is known (Patent Document 1).

JP 2007-144771 A

Since lysozyme chloride is water-soluble, when preparing a composition containing lysozyme chloride, it is common to select a water-based formulation. In addition, when a water-based composition is used as a stock solution for an aerosol product, dimethyl ether having a relatively high solubility in water is generally used as a propellant.

Therefore, as a result of studying a prescription in which the present inventors combined lysozyme chloride and dimethyl ether, it was found that lysozyme chloride loses its activity over time. This was presumed to be due to inactivation of lysozyme chloride by dimethyl ether.

Therefore, an object of the present invention is to provide an aerosol product having a composition containing lysozyme chloride and water as a stock solution, in which deactivation of lysozyme chloride is suppressed.

The present invention is an aerosol product in which a container body is filled with a stock solution and a propellant,
The stock solution relates to an aerosol product containing the following component A, component B and component C, and the propellant containing liquefied petroleum gas.
Component A: Lysozyme chloride Component B: Nonionic surfactant Component C: Water

Even if the aerosol product of the present invention is an aerosol product using a water-based composition containing lysozyme chloride as a stock solution, the deactivation of lysozyme chloride is suppressed, that is, the stability of lysozyme chloride is high. Play.

As a result of further investigation by the inventors, as a stock solution, lysozyme chloride, a nonionic surfactant, and water were used, and a water-insoluble liquefied petroleum gas was used as a propellant. It was found that the stability of lysozyme chloride can be improved unexpectedly by using an aerosol product emulsified with liquefied petroleum gas, and the present invention has been completed.

In the composition containing lysozyme chloride and water, since water is a good solvent for lysozyme chloride, lysozyme chloride can exist stably without being deactivated. However, in the aerosol product having the above composition as a stock solution, when dimethyl ether having high solubility in water is used as a propellant, dimethyl ether is dissolved in the water in the stock solution, and the solubility of lysozyme chloride in water decreases. Conceivable. As a result, it is presumed that lysozyme chloride is denatured or lysozyme chloride aggregates and is inactivated. However, in the aerosol product of the present invention, water is maintained as a good solvent for lysozyme chloride by deliberately using liquefied petroleum gas having low solubility in water as a propellant, and deactivation of lysozyme chloride is suppressed. That is, it is presumed that the effect of high stability of lysozyme chloride is exerted.

<Undiluted solution>
The stock solution in the aerosol product of the present invention contains component A: lysozyme chloride, component B: nonionic surfactant, and component C: water as essential components. The aerosol product of the present invention preferably further contains component D: ethanol in addition to the essential components. Further, components other than component A to component D (other components) may be further contained. Each of Component A to Component D and other components may be used alone or in combination of two or more.

Component A is lysozyme chloride. Component A is a polysaccharide hydrolase that is a component of the bacterial cell membrane, and has pharmacological actions such as lysis. Component A can be easily obtained as a commercial product.

The content of component A in 100% by mass of the stock solution in the present invention is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, from the viewpoint of achieving a sufficient bactericidal effect. From the viewpoint of cost effectiveness and solubility in the stock solution, it is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less.

Component B is a nonionic surfactant, and the stability as a preparation can be improved by stably emulsifying the liquefied petroleum gas contained in the stock solution and the propellant. Component B may be used alone or in combination of two.

Component B includes alkyl glucoside, glycerin fatty acid ester, polyglycerin fatty acid ester, ethylene oxide condensate of glycerin fatty acid ester, polyethylene glycol fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, ethylene oxide condensate of sorbitan fatty acid ester, poly Examples thereof include oxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, and polyoxyethylene lanolin.

Specific examples of glycerin fatty acid esters include glyceryl monocaprylate, glyceryl monocaprate, glyceryl monolaurate, glyceryl monomyristate, glyceryl monopalmitate, glyceryl monostearate, glyceryl monoisostearate, glyceryl monobehenate, monooleic acid Examples include glyceryl, glyceryl monoerucate, glyceryl sesquioleate, glyceryl distearate, glyceryl diisostearate, and glyceryl diarachiate.

Specific examples of the polyglyceryl fatty acid ester include diglyceryl monocaprylate, decaglyceryl monocaprylate, hexaglyceryl monocaprate, tetraglyceryl monolaurate, hexaglyceryl monolaurate, decaglyceryl monolaurate, poly (4 to 10 polylaurate) ) Glyceryl, decaglyceryl monomyristate, decaglyceryl monostearate, decaglyceryl monoisostearate, poly (2-10) glyceryl monostearate, diglyceryl monooleate, hexaglyceryl monooleate, diglyceryl sesquioleate, Poly (2-10) glyceryl diisostearate, poly (6-10) glyceryl distearate, diglyceryl triisostearate, poly (10) glyceryl tristearate Like it is exemplified.

Specific examples of the ethylene oxide condensate of glycerin fatty acid ester include polyoxyethylene glyceryl monostearate and polyoxyethylene glyceryl monooleate.

Specific examples of the polyethylene glycol fatty acid ester include polyethylene glycol monooleate, polyethylene glycol monostearate, polyethylene glycol monolaurate, and the like. As a commercial item of polyethylene glycol monolaurate, for example, trade name “Emanon 1112” (manufactured by Kao Corporation, average added mole number of oxyethylene group: 12) and the like can be mentioned.

Specific examples of the propylene glycol fatty acid ester include propylene glycol monostearate, propylene glycol monolaurate, propylene glycol monooleate and the like.

Specific examples of sorbitan fatty acid esters include sorbitan monooleate, sorbitan monostearate, sorbitan monoisostearate, sorbitan monopalmitate, sorbitan monolaurate, sorbitan trioleate, sorbitan tristearate, sorbitan sesquistearate, sesquiolein Examples include acid sorbitan, sorbitan sesquiisostearate, coconut oil fatty acid sorbitan, and the like.

Specific examples of the ethylene oxide condensate of sorbitan fatty acid ester include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene monoisostearate Examples include ethylene sorbitan, mono coconut oil fatty acid polyoxyethylene sorbitan, polystearic acid polyoxyethylene sorbitan, and trioleic acid polyoxyethylene sorbitan. Examples of the polyoxyethylene sorbitan monostearate include trade name “Rheidol TW-S120V” (manufactured by Kao Corporation, average added mole number of oxyethylene groups: 20).

Examples of commercially available polyoxyethylene hydrogenated castor oil include trade name “EMALEX HC-20” (manufactured by Nippon Emulsion Co., Ltd.), trade name “EMALEX HC-50” (manufactured by Japan Emulsion Co., Ltd.), and the like.

Preferred oxyalkylene groups in the polyoxyalkylene alkyl ether include oxyethylene groups and oxypropylene groups. The average added mole number of the oxyalkylene group in the polyoxyalkylene alkyl ether is preferably 8 to 42, more preferably 10 to 40. The oxyalkylene group in the polyoxyalkylene alkyl ether may be only one type, or two or more types, for example, a polyoxyethylene polyoxypropylene (POEPOP) group in which an oxyethylene group and an oxypropylene group are combined. In addition, the average added mole number when the oxyalkylene group in the polyoxyalkylene alkyl ether contains two or more oxyalkylene groups is the total of the average added mole numbers of the two or more oxyalkylene groups.

The alkyl group in the polyoxyalkylene alkyl ether is preferably a saturated or unsaturated group having 12 to 28 carbon atoms. Specific examples include a lauryl group, a cetyl group, a stearyl group, an oleyl group, an isocetyl group, a decyltetradecyl group, and the like.

Specific examples of the polyoxyalkylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxypropylene cetyl ether, Examples include polyoxypropylene isocetyl ether, polyoxypropylene stearyl ether, polyoxypropylene oleyl ether, polyoxyethylene polyoxypropylene decyl tetradecyl ether, polyoxyethylene polyoxypropylene cetyl ether and the like. Among these, polyoxyethylene polyoxypropylene decyl tetradecyl ether is preferable from the viewpoint of easily obtaining a cracking spray that emits a cracking sound.

As a commercially available product of polyoxyalkylene alkyl ether, for example, as a polyoxyethylene polyoxypropylene decyl tetradecyl ether, a trade name “Nikkol PEN-4612” (manufactured by Nikko Chemicals, average added mole number of oxyethylene group: 12, Average addition mole number of oxypropylene group: 6), trade name “Nikkol PEN-4630” (manufactured by Nikko Chemicals, average addition mole number of oxyethylene group: 30, average addition mole number of oxypropylene group: 6); poly Examples of the oxyethylene polyoxypropylene cetyl ether include trade name “PBC-44” (manufactured by Nippon Surfactant Kogyo Co., Ltd., average added mole number of oxyethylene group: 20, average added mole number of oxypropylene group: 8) and the like. .

The content of component B in 100% by mass of the stock solution in the present invention is preferably 0.05% by mass or more, more preferably 0.1% by mass from the viewpoint of stably emulsifying the stock solution and liquefied petroleum gas. On the other hand, from the viewpoint of suppressing stickiness and odor derived from component B, it is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less. The content of component B is the total amount of all components B contained in the stock solution.

Component C is water. Component C serves as a medium in the stock solution.

The content of Component C in 100% by mass of the stock solution in the present invention is preferably 55.0% by mass or more, more preferably 60.0% by mass or more, from the viewpoint of improving the stability of Component A, and more preferably Preferably, it is 65.0% by mass or more. On the other hand, from the viewpoint of exerting the effect of components other than Component C, it is preferably 99.0% by mass or less, more preferably 90.0% by mass or less, and further Preferably it is 85.0 mass% or less.

The stock solution in the aerosol product of the present invention preferably further contains component D ethanol.

The content of the component D in 100% by mass of the stock solution in the present invention is that the quick drying property is imparted to the discharged product, the user is given a feeling of cooling, or the components other than the components A and C are added to the stock solution. From the viewpoint of improving the solubility, it is preferably 1.0% by mass or more, more preferably 10.0% by mass or more, while from the viewpoint of the stability of Component A, preferably 30.0% by mass or less. More preferably, it is 25.0 mass% or less, More preferably, it is 22.0 mass% or less.

The stock solution in the aerosol product of the present invention can optionally contain components other than component A to component D (other components). Other components include, for example, bactericides other than Component A such as benzalkonium chloride, benzethonium chloride, halocarban, trichlorocarbanilide, chlorhexidine hydrochloride, isopropylmethylphenol, triclosan, and chlorhexidine gluconate; aluminum chloride, aluminum sulfate Antiperspirant components such as potassium, aluminum sulfate, aluminum acetate, chlorohydroxyaluminum, allantoin chlorohydroxyaluminum and zinc paraphenol sulfonate; metal oxides (such as zinc oxide), alkyldiethanolamide, hydroxyapatite, tea extract, fragrance Deodorant ingredients such as antioxidants, surfactants other than Component B, coloring agents, chelating agents, refreshing agents, vitamins, neutralizing agents, amino acids, pH adjusting agents, whitening agents, anti-inflammatory agents, animal and plant extracts Film forming agents; silicones; higher alcohols; humectants; powders and the like. Only 1 type may be used for the said other component, and 2 or more types may be used for it.

The stock solution can be prepared by a conventional method. For example, the above-described constituent components are mixed and a known method, specifically, a method of stirring with a homomixer or the like can be mentioned.

<Propellant>
The propellant in the aerosol product of the present invention contains liquefied petroleum gas. It does not specifically limit as liquefied petroleum gas, The liquefied petroleum gas used for aerosol products can be employ | adopted, for example, 1 type of liquefied gas chosen from the group which consists of propane, normal butane, isobutane, and isopentane, or 2 It can be a mixed gas of liquefied gas of more than seeds.

The content of liquefied petroleum gas in 100% by mass of the propellant is preferably 95.0% by mass or more, more preferably 100% by mass, from the viewpoint of injection stability.

Examples of the propellant that can be used in combination with liquefied petroleum gas include compressed gas such as nitrogen gas and carbon dioxide gas. From the viewpoint of the stability of component A, the propellant is liquefied petroleum gas and compressed gas alone or liquefied petroleum. Preferably only gas. On the other hand, from the viewpoint of the stability of Component A, the propellant in the aerosol product of the present invention preferably does not contain a liquefied gas having high solubility in water such as dimethyl ether.

<Aerosol products>
In the aerosol product of the present invention, the mass ratio of the stock solution to the propellant (stock solution / propellant) is preferably 20/80 or more, more preferably from the viewpoint of facilitating emulsification of the liquefied petroleum gas and the stock solution. 30/70 or more. On the other hand, 95/5 or less is preferable from the viewpoint of securing the momentum of injection, the viewpoint of giving a refreshing feeling during use, the viewpoint of improving the cooling feeling by liquefied petroleum gas, or the viewpoint of injecting the stock solution to the end, and 92/8 or less More preferred.

The aerosol product of the present invention can be produced by filling an aerosol container with a stock solution and a propellant by a conventional method.

吐出 Spray form, foam form, etc. are mentioned as the discharge form of aerosol products. As the spray form, it is also possible to provide a cracking spray that emits a cracking sound and cracking sound immediately after discharge, and can give an appropriate stimulation to the discharge surface.

The parts to which the aerosol product of the present invention is applied include the scalp, face (for example, forehead, eyes, eyes, cheeks, mouth, etc.), arms, elbows, back of hands, fingertips, feet, knees, heels, neck, heel, back, etc. Is mentioned. In addition, since the aerosol product of the present invention can be uniformly injected in a state in which the stock solution and liquefied petroleum gas are emulsified, the user feels a refreshing feeling due to the momentum of injection and a cooling feeling due to volatilization of the liquefied petroleum gas. Can do. Therefore, the use to an antiperspirant, a deodorant, an antiperspirant deodorant, and a deodorant agent is preferable. Especially, when a discharge form is a cracking spray, it is more preferable to set it as a deodorant agent.

The aerosol product of the present invention may be, for example, any of cosmetics, quasi drugs, medicines, and miscellaneous goods.

Hereinafter, the present invention will be described in more detail based on examples and the like, but the present invention is not limited only to these examples and the like. In addition, the compounding quantity and content of each component in a table | surface are the quantity converted into the pure part, and unless otherwise indicated, "mass%" is represented.

Examples 1 to 10, Comparative Examples 1 to 7 (Manufacture of aerosol products)
The stock solution having the composition described in Table 1 and Table 2 was filled into an aerosol container (φ35 mm × 105 mm, aluminum can, full container amount: 91 mL), and an aerosol valve was clinched into the container. Next, a propellant (liquefied petroleum gas or dimethyl ether) was filled from the stem so as to be a mass part of Table 1 and Table 2 with respect to the stock solution, and a suitable spout was attached to produce an aerosol product. The total amount of the stock solution and the propellant filled in the aerosol container was 40 g in any of the examples and comparative examples.

Details of main components in Examples, Comparative Examples and Formulation Examples are as follows. In addition, the amount described in Table 1 and Table 2 is not the amount of merchandise but the amount of each component (amount of active ingredient).
Lysozyme chloride: Made by QP Corporation, trade name “Lysozyme Chloride”
POEPOP decyl tetradecyl ether: manufactured by Nikko Chemicals, trade name “Nikkoru PEN-4630”, average addition mole number of oxyethylene group: 30, average addition mole number of oxypropylene group: 6
Polyoxyethylene cetyl ether: manufactured by Nikko Chemicals Co., Ltd., trade name “Nikkol BC-40”, average added mole number of oxyethylene group: 40
Polyoxyethylene hydrogenated castor oil: manufactured by Nippon Emulsion Co., Ltd., trade name “EMALEX HC-50”, average added mole number of oxyethylene group: 50
Polystearic acid polyoxyethylene sorbitan: manufactured by Kao Corporation, trade name “Leodol TW-S120V”, average number of added oxyethylene groups: 20
Polyethylene glycol monolaurate: manufactured by Kao Corporation, trade name “Emanon 1112”, average added mole number of oxyethylene group: 12
IPMP: Osaka Kasei Co., Ltd., trade name “Isopropylmethylphenol”
Liquefied petroleum gas: vapor pressure 0.29 MPa at 20 ° C

(Evaluation Test 1: Evaluation of Stability of Lysozyme Chloride)
Test aerosol products after storage at 40 ° C. for the period shown in Tables 1 and 2 with initial titers of lysozyme chloride (mg (titer) / mg) in the discharge product of test aerosol products immediately after production The titer (mg (titer) / mg) of lysozyme chloride in the discharged product was measured as a test value. The residual rate (%) was calculated from the measured initial value and test value. In Tables 1 and 2, the case where the residual rate was 90% or more was designated as “A”, and the case where it was less than 90% was designated as “B”.

The titer of lysozyme chloride in each discharge was determined by the method described in the 17th revision Japanese Pharmacopoeia “Lysozyme Hydrochloride”.
In other words, the ejected material was ejected from the stem of each test aerosol product, and the obtained propellant was subjected to ultrasonic treatment to volatilize the remaining propellant as a sample sample. A sample solution was appropriately diluted with a pH 6.2 phosphate buffer. 3 mL of the sample solution heated in a 35 ° C. water bath was added to 3 mL of pH 6.2 phosphate buffer and 3 mL of a substrate solution for lysozyme chloride (Micrococcus lysodeikticus at pH 6.2). In a phosphate buffer solution, and added to a mixture solution with a transmittance of 10% at a wavelength of 640 nm), followed by reaction at 35 ° C. for exactly 10 minutes to reduce the decrease in absorbance. The amount was quantified by comparing with a decrease by a lysozyme standard solution (a solution obtained by diluting a quantified lysozyme chloride standard product with a pH 3.0 hydrochloric acid solution).

From Table 1 and Table 2, it can be seen that the stability of lysozyme in the comparative example using the propellant not containing liquefied petroleum gas is inferior compared to the example using the propellant containing liquefied petroleum gas. It was. This tendency was the same even when various nonionic surfactants were used as Component B.

Furthermore, the following is a formulation example of the aerosol product of the present invention.

Formulation Example 1 (Deodorant Spray)
(Stock solution)
Lysozyme chloride 0.40
Isopropylmethylphenol 0.20
Zinc paraphenol sulfonate 0.20
POEPOP decyl tetradecyl ether 0.60
Ethanol 20.00
Fragrance 0.30
Purified water 78.30
Total 100.00 (mass%)
(Propellant)
Liquefied petroleum gas 100.00
Total 100.00 (mass%)
Stock solution: propellant = 70: 30 (mass ratio)

Formulation example 2 (deodorant spray)
(Stock solution)
Lysozyme chloride 0.15
Isopropylmethylphenol 0.15
Zinc paraphenol sulfonate 0.40
POEPOP decyl tetradecyl ether 0.80
Ethanol 22.00
Menthol 0.20
Purified water 76.30
Total 100.00 (mass%)
(Propellant)
Liquefied petroleum gas 100.00
Total 100.00 (mass%)
Stock solution: propellant = 50: 50 (mass ratio)

The aerosol product manufactured in the above preferable range can uniformly inject the stock solution and the liquefied petroleum gas, so that the user can feel the refreshing feeling due to the momentum of the injection and the cooling feeling due to the volatilization of the liquefied petroleum gas. . Therefore, the use to a deodorant agent and a refreshing agent, such as a bad smell inhibitor, is preferable.

Claims

An aerosol product in which a container body is filled with a stock solution and a propellant,
An aerosol product in which the stock solution contains the following components A, B and C, and the propellant contains liquefied petroleum gas.
Component A: Lysozyme chloride Component B: Nonionic surfactant Component C: Water
The aerosol product according to claim 1, wherein the stock solution further contains the following component D, and the content of component D is 30.0% by mass or less in 100% by mass of the stock solution.
Component D: Ethanol
The aerosol product according to claim 1 or 2, wherein the content of component A is 0.1% by mass or more and 1.5% by mass or less in 100% by mass of the stock solution.
The aerosol product according to any one of claims 1 to 3, wherein the content of component B is from 0.05% by mass to 1.5% by mass in 100% by mass of the stock solution.