WO2021075549A1

WO2021075549A1 - Multilayer cleansing composition

Info

Publication number: WO2021075549A1
Application number: PCT/JP2020/039094
Authority: WO
Inventors: 奈津美平山; 裕人白神
Original assignee: 株式会社資生堂
Priority date: 2019-10-17
Filing date: 2020-10-16
Publication date: 2021-04-22
Also published as: JPWO2021075549A1; CN114555041A

Abstract

The present invention aims to provide a multilayer cleansing composition that maintains a sufficient makeup-removal effect similar to oil, is easy to wash off and has a soft texture similar to gel, and has an aesthetically pleasing appearance. The present invention pertains to a multilayer cleansing composition that contains (a) a non-ionic surfactant having an HLB of 8-12, (b) oil, (c) a moisturizing agent, and (d) water. The ratio [(a)/(b)] between the blended amount of non-ionic surfactant (a) and the blended amount of oil (b) is within the range of 0.4–0.8. When left to stand, the multilayer cleansing composition separates into a plurality of layers including (A) at least one bi-continuous micro-emulsion phase and (B) at least one oil phase. The composition reversibly becomes a single layer of gel by being shaken.

Description

Multi-layer cleansing composition

The present invention relates to a multi-layer cleansing composition. More specifically, the present invention relates to a multi-layer cleansing composition having a gel-like ease of washing and a soft texture while maintaining an excellent makeup removing effect, and having an aesthetically pleasing appearance.

Due to the improved function of makeup cosmetics, many products with excellent water resistance and sweat resistance (waterproof) are on the market, and they are very difficult to remove from the viewpoint of face washing. Among the wash pigments used for makeup remover, these products include cleansing oils containing oil as the main component and a small amount of surfactant and ethanol, and emulsions containing a large amount of oil as water-soluble polymers. Cleansing gel that has been thickened with is widely used.

However, cleansing oil tends to leave an oily component on the skin even after rinsing with water, and a refreshing feel cannot be obtained. On the other hand, although the cleansing gel gives a refreshing feeling after rinsing, the makeup removing effect may not be sufficient in some cases. Further, in recent years, cosmetics are required to have not only excellent functions as cosmetics (for example, cleansing performance) but also aesthetics such as a beautiful appearance.

Patent Document 1 states that a two-layer cleansing cosmetic composed of a liquid water layer and a liquid oil layer achieves both a feeling of use of an aqueous cleansing cosmetic and a stain removing effect of an oil-based cleansing cosmetic. In Patent Document 1, a two-layer cleansing cosmetic consisting of a liquid aqueous layer containing benzalkonium chloride or N-palm oil fatty acid acyl-L-arginine ethyl DL-pyrrolidone carboxylate and a liquid oil layer. The aqueous layer contains an amphoteric surfactant, a polyhydric alcohol, hydroxyethyl cellulose and / or xanthan gum, an acylamino acid salt-type anionic surfactant and / or a nonionic surfactant having an HLB value of 8 to 12. It is described that by forming a two-layer cleansing cosmetic containing a liquid oil agent in the oil layer, the appearance of a transparent two-layer system is maintained at the time of storage, and the mixture is uniformly mixed at the time of mixing. .. However, even if they are mixed uniformly, there is a problem that the appearance becomes opaque and cloudy, the beauty is lost, and the viscosity is low, so that it easily drips from the hand.

On the other hand, Patent Document 2 describes an oil-based cleansing composition containing (A) a nonionic surfactant having an HLB of 6 to 14 and (B) an oil-based component, and the amount of water blended is less than 5% by mass. Is disclosed, and when the composition and water are mixed in a ratio of 4: 6, they become an aqueous micellar phase or a bicontinuous microemulsion phase, so that even if water is mixed, transparency, cleaning performance, and massage It is said that the basic performance does not deteriorate. The oil-based cleansing composition of Patent Document 2 forms an aqueous micellar phase or a bicontinuous microemulsion phase having a certain viscosity when mixed with water. These phases are more viscous than conventional cleansing oils and double-layer cleansing cosmetics, but have not reached such a viscosity that they do not drip at all. Moreover, the effect of removing waterproof mascara and lipstick was not sufficient. Further, since the appearance of the composition is composed of one layer (oil phase) and does not change, it may not be sufficiently satisfactory from an aesthetic point of view.

Japanese Patent No. 5419506 Japanese Patent No. 4757446

In view of the current state of technology as described above, the present invention has a cleansing gel-like ease of washing and a soft texture while maintaining a sufficient makeup-removing effect like a cleansing oil, and is aesthetically superior. It is an object of the present invention to provide a multi-layer cleansing composition having an appearance.

The inventors have found that (A) at least one bicontinuous microemulsion phase and (B) at least one oil phase are separated from each other to form a multilayer composition when allowed to stand, and when mixed during use, a transparent one layer is formed. As a result of diligent studies to obtain a multi-layer cleansing composition to be a gel, the present invention has been achieved.

That is, the present invention
(A) Nonionic surfactant with HLB of 8-12,
(B) Oil content,
Contains (c) moisturizer and (d) water,
The ratio [(a) / (b)] of the amount of the nonionic surfactant (a) to the amount of the oil (b) is in the range of 0.4 to 0.8.
Provided is a multi-layer cleansing composition that separates into a plurality of layers including (A) at least one bicontinuous microemulsion phase and (B) at least one oil phase upon standing.

The multi-layer cleansing composition of the present invention has a multi-layer structure that is beautifully separated into at least two layers, (A) bicontinuous microemulsion phase and (B) oil phase, when it is allowed to stand (when stored), and is light when used. It has an attractive appearance that becomes a transparent one-layer gel just by shaking. Further, the multi-layer cleansing composition of the present invention can obtain a gel that is easy to wash off and a soft texture while maintaining an excellent makeup removing effect.

It is a figure which shows the phase diagram (water-surfactant-oil content) of the three-component system for demonstrating the state of the composition of this invention. In the composition of the present invention, the total volume of the composition when the ratio [(a) / (b)] of (a) the blending amount of the nonionic surfactant and (b) the blending amount of the oil content is changed. It is a graph which shows the change of the volume ratio of the (A) bicontinuous microemulsion phase in the (A).

The multilayer cleansing composition of the present invention will be described in detail below.
The multilayer cleansing composition according to the present invention (hereinafter, also simply referred to as “composition” or “multilayer composition”) includes (a) a nonionic surfactant having an HLB of 8 to 12, (b) an oil content, and (c). ) Moisturizer and (d) water.

(A) Nonionic Surfactant with HLB of 8 to 12 The (a) Nonionic Surfactant (hereinafter, also referred to as "Component (a)") in the composition of the present invention has an HLB value of 8 to 12. It is not particularly limited as long as it is within the range of. Among them, nonionic surfactants having an HLB in the range of 9 to 12 are preferably used.
The component (a) in the present invention may consist of one type of nonionic surfactant having an HLB of 8 to 12, or may consist of a combination of two or more types. Additivity is observed in the HLB value, and when two or more nonionic surfactants are used in combination, the HLB value of the combination as a whole is shown by the weighted average of the HLB values of each surfactant alone. Will be done.

The component (a) of the present invention requires that the HLB contains at least one nonionic surfactant having an HLB of 8 to 12, but optionally, the HLB is outside the above range, that is, less than 8 or 12. It may contain more nonionic surfactants. However, it is preferable that the HLB value of the entire component (a) is within the range of 8 to 12. (A) If the HLB of the entire component is less than 8 or more than 12, it becomes difficult to obtain a multilayer composition containing the intended bicontinuous microemulsion phase.

In addition, "HLB (Hydrophilic Lipophilic Balance)" in this specification is the following formula (I) :.

(However, MW represents the molecular weight of the hydrophilic base and MO represents the molecular weight of the lipophilic base) (defined by the "Kawakami formula").

The (a) nonionic surfactant used in the present invention is not particularly limited as long as it can be used in cosmetics and the like. For example, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, polyoxyethylene castor oil, polyoxyethylene hydrogenated Examples thereof include castor oil, polyoxyethylene sterol / hydrogenated sterol, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyethylene glycol fatty acid ester.

In the compositions of the present invention, polyoxyethylene hydrogenated castor oil, such as PEG-40 hydrogenated castor oil (HLB = 12), PEG-20 hydrogenated castor oil (HLB = 10.5), and PEG-30 water. At least one nonionic surfactant selected from bean paste oil (HLB = 11) and the like, and polyoxyethylene glyceryl isostearate, for example, PEG-8 glyceryl isostearate (HLB = 10), PEG-isostearate- At least one nonionic surfactant selected from 10 glyceryl (HLB = 10), PEG-15 glyceryl isostearate (HLB = 12), etc. is used in combination in terms of make-up removing effect and emulsion stability. Is preferable. Of these, a combination of PEG-8 glyceryl isostearate and PEG-40 hydrogenated castor oil is preferably used.

(A) The blending amount of the nonionic surfactant is preferably 10% by mass to 33% by mass, more preferably 15% by mass to 30% by mass, based on the total amount of the composition. (A) When the blending amount of the nonionic surfactant is less than 10% by mass or more than 33% by mass, it becomes difficult to obtain the intended multilayer composition.

(B) Oil content (b) As the oil content, one or more selected from the liquid oily components usually used in cosmetics and the like can be used. In particular, it is preferable to contain polar oil from the viewpoint of improving the makeup removing effect.

Examples of polar oils include liquid oils and fats and ester oils. Liquid fats and oils include flaxseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, southern ka oil, sunflower oil, saflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, and large Examples thereof include soybean oil, peanut oil, triglycerin, glycerin trioctanoate, and glycerin triisopalmitate.

Ester oils include cetyl ethylhexanate, triethylhexanoin, cetyl octanoate, hexyl laurate, isopropyl myristate, octyl palmitate, isocetyl stearate, isopropyl isostearate, octyl isopalmitate, isodecyl oleate, tri 2 Examples thereof include glyceryl ethylhexanate, pentaerythlit tetra2-ethylhexanoate, 2-ethylhexyl succinate, and diethyl sebacate. Among these, cetyl ethylhexanoate and triethylhexanoin are particularly preferably used in the present invention.

(B) The oil component may contain other oil components in addition to the polar oil, and examples of the other oil components include hydrocarbon oils and silicone oils.
Examples of the hydrocarbon oil include liquid paraffin, squalane, squalene, paraffin, isoparaffin, and selecin. Examples of the silicone oil include chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

As the oil content in the present invention, it is preferable to select an oil content having a refractive index difference of 0.5 or less from (d) water. If the difference in refractive index between (b) oil and (d) water exceeds 0.5, the composition after shaking may become opaque.

(B) The blending amount of the oil content is usually 20% by mass to 55% by mass, preferably 30% by mass to 50% by mass, based on the total amount of the composition. (B) If the blending amount of the oil content is less than 20% by mass, the makeup removing effect is lowered, and if the blending amount exceeds 55% by mass, it becomes difficult to obtain the intended multilayer composition.

(C) Moisturizer By blending (c) a moisturizer with the composition of the present invention, it is possible to give the skin a fresh and moisturizing feeling when used as a cleansing agent.

The moisturizer (c) used in the present invention is not particularly limited as long as it is used in cosmetics and the like. (C) Specific examples of the moisturizer include 1,3-butylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, glycerin, diglycerin, xylitol, maltitol, maltitol, D-mannitol and the like. These can be mentioned, and one kind or a combination of two or more kinds can be blended.

The amount of the moisturizer (c) blended in the composition of the present invention is usually in the range of 10% by mass to 30% by mass, preferably 15% by mass to 25% by mass, based on the total amount of the composition. (C) If the blending amount of the moisturizer is less than 10% by mass, the intended effect cannot be obtained, and if it exceeds 30% by mass, a sticky feel may be given.

(D) Water The blending amount of (d) water in the present invention is usually 5% by mass to 20% by mass, preferably 6% by mass to 15% by mass, and more preferably 7% by mass to the total amount of the composition. It is in the range of 10% by mass. (D) If the blending amount of water is less than 5% by mass or more than 20% by mass, it becomes difficult to obtain the intended multilayer composition.

(A) Mixing amount ratio of nonionic surfactant and (b) oil [(a) / (b)]
In the composition of the present invention, the ratio [(a) / (b)] of the compounding amount of the (a) nonionic surfactant to the compounding amount of the oil (b) is 0.4 to 0.8. It is indispensable to set it in the range of. By setting this ratio (mass ratio) within the above-mentioned predetermined range, the mixture is separated into a plurality of layers including (A) at least one bicontinuous microemulsion phase and (B) at least one oil phase at rest. A beautiful multi-layered form is achieved. The ratio [(a) / (b)] is more preferably in the range of 0.5 to 0.7.

If the ratio [(a) / (b)] is less than 0.4, the ratio of the oil phase (B) becomes too large even if the layers are separated into multiple layers, and the usability is lowered. When the ratio [(a) / (b)] exceeds 0.8, almost all of the composition is occupied by the (A) bicontinuous microemulsion phase, which is shaken to form a gel. When the viscosity is low, it may drip from the hand.

When the ratio [(a) / (b)] is about 0.4, the ratio of the (A) bicontinuous microemulsion phase to the total volume of the multilayer composition at rest is about 0.5. When the ratio [(a) / (b)] is about 0.8, it is about 0.95. Therefore, it is necessary to set the ratio [(a) / (b)] to 0.4 to 0.8 from the viewpoint of aesthetics when separated into multiple layers.

(A) Bi-Continuous Microemulsion Phase In the bi-continuous microemulsion phase, the number of associations of surfactants increases and the associations indefinitely, resulting in a dramatic improvement in the solubilization amount of water and oil. Both water and oil are said to form continuous channels. The bicontinuous microemulsion phase can be determined by appearance, creating a phase equilibrium diagram, measuring electrical conductivity, measuring the self-diffusion coefficient by NMR, and observing a replica prepared using the freeze fracture method with an electron microscope. It is determined.

The bicontinuous microemulsion phase is a low-viscosity one-phase region that is transparent in appearance and is optically isotropic. The distinction from the optically anisotropic liquid crystal phase is possible by holding the sample while combining the 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 an isotropic surfactant continuous phase from another isotropic one-phase region such as a micellar aqueous solution or a reverse micelle oil solution.

It is known that the conductivity of the bicontinuous microemulsion obtained by measuring the electrical conductivity takes about two-thirds of the value of the aqueous micellar 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. Electron microscopy of bicontinuous microemulsions prepared using the freeze fracture method makes it possible to obtain continuous images of both water and oil. According to this image, it is easy to distinguish from a spherical aggregate image obtained by water or oil in a continuous aqueous micellar phase. This method is described in detail in the literature Colloid polymer. Sci. 1994, 272, 604 by Imaei et al.

The bicontinuous microemulsion phase is an isotropic transparent low-viscosity one-phase region on the phase equilibrium diagram of a three-component system composed of water / oil / surfactant, and is continuous from both the water and oil peaks. It can be identified by having a feature such as not being a region to be formed, but this feature differs depending on the system to be constructed. FIG. 1 shows a general phase diagram having a bicontinuous microemulsion phase.

In FIG. 1, Lα means a liquid crystal phase, and “I _bicon ” means a one-phase bicontinuous microemulsion phase. The multilayer composition of the present invention at rest is considered to be a two-layer separated phase represented by "II" in FIG.

(B) Oil phase The (B) oil phase in the composition of the present invention is a phase composed of the same oil as the oil constituting the (A) bicontinuous microemulsion phase. That is, the multilayer composition of the present invention has a fixed amount of water (surfactant: oil content ratio) in the one-phase bicontinuous microemulsion phase represented by _{"I bicon" in the phase diagram of FIG.} It is considered that when the oil is changed in the oil-rich direction, it enters the region represented by "II" and is separated into two layers. In other words, it is understood that the oil component that cannot be completely incorporated into the (A) bicontinuous microemulsion phase appears in the upper layer of the (A) bicontinuous microemulsion phase to form the (B) oil phase.

The composition of the present invention separated into a plurality of layers (two layers) as described above becomes a one-layer gel-like composition by gently shaking. This change is reversible, and the single-layer gel-like composition is allowed to stand to return to the phase-separated state again. Therefore, it is possible to give the user an impact based on a large change in appearance.

In addition to the above essential ingredients, the composition of the present invention contains other optional ingredients usually used for cosmetics, quasi-drugs, etc., particularly cleansing cosmetics, etc., as long as the effects of the present invention are not impaired. can do. Other optional ingredients include, but are not limited to, dyes, various agents, buffers, chelating agents, preservatives, fragrances and the like.

As the dye as another optional component, a water-soluble dye and / or an oil-soluble dye is used. If a water-soluble dye is used, only the (A) bicontinuous microemulsion phase is colored in a multi-layered state, and if it is shaken into a gel, the entire composition is colored. You can enjoy the change of.

The composition (cosmetics) of the present invention can be produced, for example, by the following steps.
(1) Dissolve water-soluble components to prepare water-soluble parts.
(2) Oil-soluble components are uniformly mixed to prepare oil-soluble parts.
(3) The above (1) water-soluble parts and (2) oil-soluble parts are well stirred to obtain a composition.
(4) The obtained composition is allowed to stand and separated into (A) bicontinuous microemulsion phase and (B) oil phase.

The composition of the present invention is a multi-layer composition that is beautifully separated into at least two layers when left to stand, and when shaken lightly, it becomes a gel having an appropriate viscosity so that it does not drip from the hand. It is a cleaning agent with excellent washability and feel. Therefore, the compositions of the present invention are particularly suitable for provision as cleansing cosmetics.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these descriptions. The blending amount means mass% unless otherwise specified.

The compositions of each example were prepared according to the above method according to the formulations shown in Tables 1 to 3 below.
The composition of each example was allowed to stand and the appearance was visually observed, and the presence or absence of two-layer separation into (A) bicontinuous microemulsion phase and (B) oil phase, the ratio of the oil phase, and the state of each layer were evaluated. did.
Next, the composition of each example was vigorously shaken 10 times to evaluate the presence or absence of a change to a one-layer gel, and then allowed to stand again to return to the original two-layer separation state (speed of separation). ..

The results of evaluation of (1) "ratio of oil phase" and (2) "speed of separation" based on the following criteria are described.
(1) Percentage of oil phase ++: 50% or more +: 40% to 49%
±: 30% -39%
-: 20% -29%
-: Less than 20% (however, it is separated into two layers)
XX: 1 layer without separation (2) Speed of separation (time until separation)
++: Less than 1 minute +: 1 minute or more and less than 10 minutes ±: 10 minutes or more and less than 6 hours-: 6 hours or more

Examples 1 to 12, which are the compositions of the present invention, are separated into (A) bicontinuous microemulsion phase and (B) oil phase when left to stand, and shaken to form a single layer gel-like composition. It became a thing. When the gel-like compositions were allowed to stand, they returned to the separated state again. Moreover, when the compositions of Examples 1 to 12 were used as a cleansing agent in the state of a gel-like composition, they were excellent in a make-up removing effect, and were also excellent in washability and soft feel.

In Comparative Example 1 in which the ratio of (a) nonionic surfactant to (b) oil content [(a) / (b)] is less than 0.4, although phase separation occurs, the oil phase is 60% of the composition. It occupies the above, and the appearance is not beautiful. Also, when used as a cleansing agent, oiliness remained after rinsing. On the contrary, Comparative Example 2 in which the ratio [(a) / (b)] exceeds 0.8 did not separate into two layers and had a common appearance.

(A) In Comparative Examples 3 to 6 in which a nonionic surfactant having an overall HLB value of more than 12 was used as the nonionic surfactant, the two layers were separated, but the lower layer was a bicontinuous micro. The emulsion phase was not formed, and when shaken, a non-uniform opaque composition was obtained.

Next, the compositions of the formulations listed in Table 4 below were prepared, and the ratio of the volume of the bicontinuous microemulsion phase to the total volume of the composition in a separated state after standing was measured. The results are shown in Table 4 and FIG.

As shown in Table 4 and FIG. 2, if (a) the ratio of the nonionic surfactant to (b) the oil content [(a) / (b)] is within the range of 0.4 to 0.8, The ratio of the volume of the bicontinuous microemulsion phase (bicon phase) to the total volume of the composition is about 50% or more. Therefore, for example, if a water-soluble dye is blended and the bicon phase is colored, about half or more of the composition has an appearance that can give a colored impact. However, when the ratio [(a) / (b)] exceeds 0.8, all the oil content is incorporated into the bicon phase to form a one-layer composition.

The composition of Example 1 of the present invention, a conventional one-phase bicontinuous microemulsion type cleansing agent (Comparative Example A: hereinafter, also referred to as "one-phase type cleansing agent"), and a conventional cleansing oil (Comparative Example). B) was prepared and each make-up remover effect was evaluated. The formulations of the one-phase cleansing agent of Comparative Example A and the cleansing oil of Comparative Example B are as shown in Table 5 below.

(Evaluation method)
A predetermined amount of various make-up products were uniformly applied to the surface of white (L value: 93.37 (L0)) artificial leather using a doctor blade. Twelve hours after the application, the L value (L1) of the portion to which the cosmetic was applied was measured with a color difference meter. Next, the artificial leather make-up product-applied portion was rubbed 20 times with a tissue coated with 0.2 g of each make-up remover base of Example 1, Comparative Example A, or Comparative Example B, and the L value of the rubbed portion (L value of the rubbed portion). L2) was measured with a color difference meter.
The above measured value is expressed by the following formula:
Cleaning rate (%) = (L2-L1) / (L0-L1) x 100
The cleaning rate was calculated by substituting into.

Table 6 below shows the results (cleaning rate) of the above measurements using commercially available (1) liquid foundation and (2) waterproof mascara as make-up cosmetics.

As shown in Table 6, the multi-layer cleansing composition of the present invention (Example 1) is based on the conventional one-phase cleansing agent (Comparative Example A) and cleansing oil (Comparative Example B) for an emulsifying liquid foundation. Has excellent cleansing properties. It was confirmed that the waterproof mascara is inferior to the cleansing oil (Comparative Example B), but exhibits remarkably excellent detergency as compared with the conventional one-phase cleansing agent (Comparative Example A).

Claims

(A) Nonionic surfactant with HLB of 8-12,
(B) Oil content,
Contains (c) moisturizer and (d) water,
The ratio [(a) / (b)] of the amount of the nonionic surfactant (a) to the amount of the oil (b) is in the range of 0.4 to 0.8.
A multi-layer cleansing composition that separates into multiple layers when allowed to stand, including (A) at least one bicontinuous microemulsion phase and (B) at least one oil phase.
The composition according to claim 1, wherein the nonionic surfactant (a) comprises PEG-8 glyceryl isostearate and PEG-40 hydrogenated castor oil.
The composition according to claim 1 or 2, wherein the amount of the nonionic surfactant (a) blended is in the range of 10% by mass to 33% by mass with respect to the total amount of the multilayer cleansing composition.
The composition according to any one of claims 1 to 3, wherein the oil (b) contains a polar oil.
The composition according to any one of claims 1 to 4, wherein the difference between the refractive index of the oil component (b) and the refractive index of the water (d) is 0.5 or less.
The composition according to any one of claims 1 to 5, which reversibly becomes a one-layer gel by shaking.