JP2007112746A - Foamy aerosol makeup detergent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a foamy aerosol makeup detergent that exhibits good foamability, maintains high deterging performances, causes no external cloudiness even when water is added while being used and gives good safety and causes less irritation to eyes. <P>SOLUTION: The detergent comprises a stock solution comprising (A) 27-40 mass%, relative to the stock solution, of a nonionic surfactant having an HLB of 6-14, particularly polyoxyethylene (POE) glyceryl isostearate, (B) 5-25 mass%, relative to the stock solution, of an oily component and (C) 20-50 mass%, relative to the stock solution, of water, and a propellant, where the stock solution forms a bicontinuous microemulsion phase. The stock solution further comprises (D) ethanol. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a foam aerosol makeup detergent, and more particularly to a foam aerosol makeup detergent that has good foaming properties and can maintain transparency even when water is added during use.

The foam form of the cleaning agent can be applied to a large surface area at the time of administration, and since the spreading on the skin is light, the cleaning agent has to be administered to fine parts It is also effective when it is necessary to administer with low physical stimulation control. In recent years, foams having the above-mentioned characteristics have been mainly used since the type of makeup has prevented the secondary adhesion such as foundation and lipstick and the type including high molecular weight silicone such as mascara. The value in the market for scouring detergents is very high.
Usually, such foam dosage forms are formed by jetting an oil-in-water emulsion emulsified with soap or a nonionic surfactant with a gas or the like. (For example, see Patent Documents 1 to 3).
However, conventional foam aerosol makeup cleansers are generally white and cloudy, and becoming cloudy when applied to the skin is not desirable because it impairs cleansing performance to consumers. In addition, since it is often used on wet faces after washing in a bathroom, it can be used with wet hands, so even in such cases, a foam aerosol makeup cleanser that can maintain transparency during use. Was desired.

Japanese translation of PCT publication No. 2002-522372 Special table 2003-500197 gazette JP 2005-68034 A

  Therefore, the problem to be solved by the present invention is that it has good foaming property, maintains high cleaning performance, and does not appear cloudy even when water is added during use, and has good safety with little eye irritation. It is an object to provide a foam aerosol makeup cleanser having

  The present invention comprises (A) a nonionic surfactant having an HLB of 6 to 14 in a stock solution of 27 to 40% by mass, (B) an oily component in a stock solution of 5 to 25% by mass, and (C) water in a stock solution. A foamy aerosol makeup detergent comprising a stock solution containing 20 to 50% by mass of a medium and a propellant, wherein the stock solution is a micellar aqueous solution phase or a bicontinuous microemulsion phase.

  According to the present invention, a foamy aerosol having good foaming property, maintaining high cleaning performance, having no appearance white turbidity even when water is added during use, and having good safety with little eye irritation. It can be used as a makeup cleanser.

Hereinafter, embodiments of the present invention will be described in detail.
The (A) nonionic surfactant used in the present invention is a surfactant that is ionized in an aqueous solution and has no charge. As the hydrophobic group, a type using a long-chain alkyl and a type using dimethyl silicone are known. Specifically, as the former, for example, glycerin fatty acid ester, ethylene oxide derivative of glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, ethylene oxide derivative of propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, polyethylene glycol alkyl ether, Examples include polyethylene glycol alkyl phenyl ether, polyethylene glycol castor oil derivatives, polyethylene glycol hydrogenated castor oil derivatives, and the like. Examples of the latter include polyether-modified silicone and polyglycerin-modified silicone. The type using alkyl as the hydrophobic group is preferred.

  The nonionic surfactant of the present invention preferably has an HLB between 6 and 14. In general, when HLB is 7, it is known that the solubility in water and the solubility in oil are balanced. That is, the surfactant suitable in the present invention has an oil / water solubility from a middle level to a slightly hydrophilic level. If the HLB is less than 6, good washability cannot be obtained at the time of washing away the detergent, and if it exceeds 14, the solubility in oil is remarkably lowered, so that an oily cleansing composition cannot be formed. The nonionic surfactant of the present invention is preferably in a liquid state at normal temperature.

In the case of the alkyl type, the nonionic surfactant used in the present invention desirably has an alkyl chain length of 16 or more. When the alkyl chain length is shortened, the eye irritation tends to increase.
The lipophilic group of the component (A) surfactant is preferably a branched or unsaturated alkyl group, more preferably an isosteal group or an oleyl group, and most preferably an isostear group. In the present invention, the most preferred component (A) surfactant is POE glyceryl isostearate.

  The compounding quantity of a component (A) is 27-40 mass% in a stock solution, Preferably it is 29-36 mass%. If it is less than 27% by mass, the effect of preventing white turbidity is not sufficient, and if it is more than 40% by mass, it is difficult to discharge in the form of bubbles.

  (B) As the oil, one or more of those generally used in cosmetics can be selected as long as the stability is not impaired. Desirable are hydrocarbon oils, silicone oils and polar oils. When silicone oil is mixed, cleaning performance is improved.

Hydrocarbon oils include liquid paraffin, squalane, squalene, paraffin, isoparaffin, ceresin and the like.
Examples of the silicone oil include chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
It is desirable to add a small amount of polar oil as long as stability is not impaired. Polar oils include liquid oils and ester oils. Liquid oils include linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, large There are bean oil, peanut oil, triglycerin, glycerin trioctanoate, glycerin triisopalmitate and the like. Ester oils include cetyl octanoate, hexyl laurate, isopropyl myristate, octyl palmitate, isocetyl stearate, isopropyl isostearate, octyl isopalmitate, isodecyl oleate, glyceryl tri-2-ethylhexanoate, tetra-2-ethyl Examples include pentaerythritol hexanoate, 2-ethylhexyl succinate, and diethyl sebacate.
In the present invention, the most preferable oil component is to use decamethylcyclopentasiloxane and cetylisooctanoate in combination.

  (B) The compounding quantity of oil is 5-25 mass% normally, and 10-20 mass% is especially preferable. If it is less than 5% by mass, the make-up removal effect is insufficient, and if it exceeds 25% by mass, it becomes difficult to obtain a transparent phase.

  Moreover, it is desirable to mix | blend so that mass ratio of a component (A) and a component (B) may become (A) :( B) = 1: 4-2: 1. When the component (A) is added beyond this, a sticky feel may be given, and the massage properties expected when water is mixed cannot be exhibited, which is not preferable. In the case of a blending amount below this, there is a problem such as white turbidity when water is mixed.

  The compounding quantity of (C) water in this invention is 20-50 mass% in a stock solution, Preferably it is 30-45 mass%. When the amount exceeds 50% by mass, make-up drop decreases, and when the amount is less than 20% by mass, the persistence of the foam decreases.

  The stock solution in the present invention preferably contains 3 to 6% by mass of (D) ethanol with respect to the stock solution. A more preferable blending amount of ethanol is 4 to 5% by mass in the stock solution. If the amount is less than 3% by mass, the liquid tends to thicken. If the amount exceeds 6% by mass, defoaming is fast.

  In the stock solution in the foam aerosol makeup detergent of the present invention, in addition to the above-mentioned essential components within the range not impairing the effects of the present invention, preservatives, chemicals, powders, fragrances, ultraviolet absorbers, humectants, solid oils, half A solid oil, a higher alcohol, a higher fatty acid, an antioxidant, a salt and the like can be blended.

  Next, in the present invention, the stock solution containing the components (A) to (C) needs to be a bicontinuous microemulsion phase.

Next, a method for investigating a change in state when water is mixed will be described below.
It is widely known to use a triangle diagram to understand a three-component system consisting of an oil component, water, and a surfactant. Three types of components are arranged at each vertex of the triangle, and each component has a composition of 100% by mass. The region of the phase obtained by mixing the components is shown on a triangular diagram as a three-component phase diagram. All the arbitrary mixing ratios of the respective components are included on the three-component phase diagram. Moreover, what arrange | positioned the mixture at each vertex by the property of a component is a pseudo | simulation ternary system phase diagram. For example, when a mixture of water and ethanol having a constant concentration is arranged at the apex as an aqueous component, a pseudo three-component phase diagram can be created with four components of water, ethanol, surfactant, and oil.

  The stock solution of the foam aerosol makeup cleanser of the present invention comprises a nonionic surfactant and an oil (one or more), and a three-component phase diagram is formed by adding water thereto. Here, when a lower alcohol or a polyhydric alcohol is included, the surfactant and the alcohol are regarded as one component, and when two or more kinds of oil are used, the pseudo three-component system phase is assumed. A diagram can be created.

  The bicontinuous microemulsion phase which is the condition of the present invention has the following characteristics and can be distinguished. Both the micellar aqueous phase and the bicontinuous microemulsion phase are optically isotropic transparent low viscosity solutions. The only other isotropic transparent low-viscosity solution obtained with a surfactant system is a reverse micelle oil solution. A method for discriminating these will be described below.

  The bicontinuous microemulsion phase is infinitely associated with an increased number of surfactants, resulting in dramatically improved water and oil solubilization and continuous water and oil channels. It is a thing. This phase is determined by appearance determination, creation of a phase equilibrium diagram, measurement of electrical conductivity, measurement of self-diffusion coefficient by NMR, observation of a replica prepared using a freeze fracture method, and the like.

  In appearance, the bicontinuous microemulsion is a transparent low-viscosity one-phase region and is optically isotropic. The optically anisotropic liquid crystal phase can be distinguished by holding the sample while combining two polarizing plates with a phase difference of 90 degrees and confirming that there is no light transmission. The following method is further effective for distinguishing between the isotropic surfactant continuous phase and the other micelle aqueous solution and reverse micelle oil solution which are other isotropic one-phase regions.

  In the three-component phase equilibrium diagram composed of water / oil / surfactant (including cosurfactant), it is an isotropic transparent low-viscosity one-phase region, and it is not a continuous region from either water or oil apex. However, this feature varies depending on the system to be constructed. It is known that the electric conductivity of a bicontinuous microemulsion obtained by measuring electric conductivity takes about 2/3 of the aqueous micelle phase obtained in the same system. The self-diffusion coefficient measurement by NMR is a method described in detail by Lindman et al. In J. Colloid Interface Sci. 1981, 83, 569 and the like. According to electron microscopic observation of a bicontinuous microemulsion prepared using the freeze fracture method, it is possible to obtain an image in which both water and oil are continuous. According to this image, water or oil can be easily distinguished from a spherical aggregate image obtained in a continuous micelle aqueous solution phase. This method is described in detail in the colloid polym. Sci. 1994, 272, 604 by Imae et al. In the phase diagram, the ratio of water to oil is often about 7: 3 to 3: 7 with a ratio of about 1: 1 as the center. Further, it is often obtained as a continuous region from the aqueous micelle solution, and in this case, it is obtained as a continuous region from the top of the water.

  From these, the mass ratio of the nonionic surfactant of the component (A) and the oil component of the component (B) is 1: 4 to 2: 1, and when the water is further mixed, optically etc. Isotropic transparent, low viscosity solutions can be micellar aqueous solutions or bicontinuous microemulsions.

  Since the surfactant used in the present invention has an HLB of 6 to 14 and is hydrophilic, on the phase diagram, in the present invention, a continuous region as a bicontinuous microemulsion phase passes from the top of the water to the aqueous micelle region. It is often obtained as.

  In the region where the surfactant concentration is lower than this, it becomes an O / W emulsified region which is completely clouded as judged from the HLB. In the O / W emulsified region, the surfactant forms micelles in water, and the oil is dispersed with a size of about several μm. Therefore, the light is scattered in all wavelengths and exhibits a white color. Further, since the continuous outer phase is water, the desired cleaning effect cannot be satisfied.

  In addition, liquid crystals are often formed in regions where the surfactant concentration is higher than this. In the region containing the liquid crystal, it becomes cloudy and the viscosity becomes high, and the massage properties desired in the present invention cannot be satisfied.

  The propellant used for this invention can use the propellant normally used for aerosol products. Specific examples include chlorofluorocarbons such as trichloromonofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, and dichlorotetrafluoroethane, propane, isobutane, normal butane, and liquefied petroleum gas (hereinafter abbreviated as LPG). ) Liquefied gas, dimethyl ether, isopentene, carbon dioxide gas, nitrogen gas and the like. When LPG is used, a highly viscous product is obtained. Further, when dimethyl ether is used, there is a feature that bubbles are quickly blown out. These gases can be used alone or in admixture of two or more.

  It is preferable that the compounding quantity of a propellant is 5-30 mass% with respect to the whole quantity which match | combined the undiluted | stock solution and the propellant, More preferably, it is 10-15 mass%. If the amount is too small, good foam at low temperatures cannot be obtained.

Next, the present invention will be described in more detail with reference to examples. Note that the present invention is not limited to this. A compounding quantity represents the mass%.
Prior to this example, the evaluation method performed in this example will be described.

(1) Judgment standard of stock solution transparency The transparency of the stock solution at room temperature was evaluated according to the following criteria.
○: A transparent single phase. (Bicontinuous microemulsion phase is one phase.)
Δ: Translucent. (Of these, * indicates that separated when left standing.)
X: Opaque or two-phase state.

(2) Compatibility The stock solution and the LPG gas were mixed in a stock solution at a stock solution: LPG = 92: 8 (mass ratio), and after shaking, the transparency when allowed to stand overnight was evaluated according to the following criteria.
○: A transparent single phase. (Bicontinuous microemulsion phase is one phase.)
* 1: Separates into two layers and becomes milky white.
* 2: Separates into two layers and becomes translucent.

(3) Viscosity during compatibilization The stock solution and the LPG gas were mixed in a glass bottle at a stock solution: LPG = 92: 8 (mass ratio), and the ease of mixing when shaken was -2 to +5 Evaluated in 8 grades. 0 was moderately easy to mix, and the more negative, the easier it was to mix. Four or more are gel-like and practically difficult to mix.

(4) Foam quality The stock solution and LPG gas were mixed in a stock bottle at a stock solution: LPG = 92: 8 (mass ratio), and the foam quality when shaken was evaluated according to the following criteria.
A: Bubbles are stably maintained for 30 seconds or more.
○: Bubbles are kept stable for 10 to 30 seconds.
Δ: Bubbles collapse in less than 10 seconds.

Test Examples 1 to 78 Foam aerosol makeup cleanser (stock solution formulation)
Part A
(1) 23.3 parts by mass of propylene glycol
(2) POE (8) glyceryl isostearate 67.6
(Emalex GWIS-108, manufactured by Nippon Emulsion Co., Ltd.)
(3) Ethanol 9.1
Part B
(1) 62.3 parts by mass of dodecamethylcyclohexasiloxane
(2) Octyl palmitate 37.7
Part C
(1) 99.0 parts by mass of water
(2) Sodium citrate 1.0
(Filling prescription)
Stock solution 92.0% by mass
LPG 8.0 mass%

[Production method]
A part to C part were mixed in the blending amounts described in Tables 1 to 8 below, respectively, heated and stirred, dispersed with a homomixer, filled into an aerosol can, crimped with a valve, and then filled with LPG.
Thereafter, for each sample, the stock solution transparency, compatibility, viscosity at the time of compatibility, and foam quality were evaluated according to the evaluation criteria described above. The results are also shown in Tables 1-8.

  Pseudo three-component phase diagram (A (surfactant) -B (oil content) -C (water)) at the main points when a foam aerosol makeup detergent is prepared with the formulations shown in Tables 1 to 8 above is a diagram. It becomes like 1. In the figure, the ● point is a compatible clearing point, the ○ point is a compatible translucent point, and the Δ point is a compatible opaque point.

FIG. 2 shows a pseudo three-component phase diagram (A (surfactant) -B (oil content) at another main point when a foam aerosol makeup detergent is prepared according to the formulations shown in Tables 1 to 8 above. -C (water)). In the figure, the solid line and the solid line are the boundary lines of the undiluted solution transparent area, and the solid line and the dotted line are the boundary lines of the transparent area during propellant compatibility. It can be seen from FIG. 2 that the undiluted solution transparent region and the transparent region at the time of compatibility substantially overlap.
Further, FIG. 3 is a diagram in which the foamable dischargeable area is indicated by oblique lines together with the undiluted solution transparent area boundary line and the propellant compatible transparent area boundary line in FIG.

  1 to 3, GWIS-108 is glyceryl isostearate, PG is propylene glycol, and PO is octyl palmitate.

Test examples 79-82
Using the same stock solution formulation as in Test Example 78 above, changing the stock solution: propellant ratio as shown in Table 9 below, and evaluating the effect on the product internal pressure and foam quality due to the difference in filling rate and propellant pressure did. The container used AL40φ-118 (Toago B2 Kai), the valve used 04-1220 stem φ0.46HG4 slot (Precision), and the internal capacity was 80 g.
Table 9 shows the internal pressure (MPa) at 25 ° C. and 5 ° C. of each sample of Test Example 78 and Test Examples 79 to 82, and the use test results when stored at room temperature (22 ° C.) and refrigerated (5 ° C.). Shown in The evaluation criteria for the usage test results are as follows.

(Evaluation criteria for usage test results)
○: No problem in use (good compatibility and moderate ejection properties)
△: Some problem in use ×: Unusable

* 1: Although the discharge amount is large, it is within the allowable range.
* 2: Compatibility is good, but foam disappears quickly.

It is a figure which shows the pseudo | simulation ternary system phase diagram (A (surfactant) -B (oil content) -C (water)) in the main point of the foam aerosol makeup cleaning material in the Example of this invention. At the time of compatibility with the stock solution transparent region of the pseudo three-component phase diagram (A (surfactant) -B (oil content) -C (water)) at another main point of the foam aerosol makeup detergent in the embodiment of the present invention It is a figure which shows the transparent area | region. In the foamed aerosol makeup cleansing agent in another embodiment of the present invention, in a foamy state with the undiluted solution transparent region of the pseudo three-component phase diagram (A (surfactant) -B (oil) -C (water)) at another main point. It is a figure which shows the area | region which can be discharged.

Claims (5)

(A) A nonionic surfactant having an HLB of 6 to 14 is 27 to 40% by mass in the stock solution, (B) an oily component is 5 to 25% by mass in the stock solution, and (C) water is 20 to 50% in the stock solution. Consisting of a stock solution containing mass% and a propellant,
A foamy aerosol makeup cleanser characterized in that the stock solution is a bicontinuous microemulsion phase.   The foam aerosol makeup cleansing agent according to claim 1, wherein the amount of the propellant is 5 to 30% by mass based on the total amount of the stock solution and the propellant.   Furthermore, (D) 3-6 mass% of ethanol is mix | blended in undiluted | stock solution, The foam aerosol makeup cleaning material of Claim 1 characterized by the above-mentioned.   The foam aerosol makeup cleanser according to claim 1, wherein the mass ratio of the component (A) to the component (B) is (A) :( B) = 1: 4 to 2: 1. (A) The non-ionic surfactant is polyoxyethylene (POE) glyceryl isostearate, The foam aerosol makeup cleanser according to claim 1.

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