JP7708529B2 - Multi-layered cosmetics - Google Patents

Description

The present invention relates to a multi-layered cosmetic preparation that separates into an oil phase, a water phase, and a powder phase when left to stand, and can be easily and uniformly mixed by shaking.

Multi-layered cosmetics have the appearance feature of separating into multiple layers when left to stand, and are therefore used as cosmetics aimed at aesthetic appearance. In particular, multi-layered cosmetics containing powders that have no or low viscosity are in high demand because of the powder's sebum absorption effect, astringent effect, skin irregularity correction effect, and non-sticky feel, and are used in lotions, antiperspirants, cleansing lotions, fragrances, etc. (for example, Patent Documents 1 and 2).

Also, in makeup and hair care products, multi-layer cosmetics are known that use pearlescent particles in the powder to provide optical effects of color and shine to the skin, hair, etc. (Patent Document 3).

JP 2006-8547 A JP 2007-126394 A Special Publication No. 2016-515559

In recent years, a new category of makeup tops has emerged that specializes in preventing makeup from coming off and improving the staying power of foundation. These products boast a sebum-absorbing function that prevents makeup from coming off, a barrier function that protects the skin from external factors such as pollen, dust, and dirt and prevents makeup from transferring to masks and clothes, and a moisturizing function that protects made-up skin from drying out. In other words, they are applied over makeup to impart a fixer function to the makeup.

Since multi-layer cosmetics separate into layers when left to stand, they have the advantage that the appropriate cosmetic ingredients, especially active ingredients, can be stably blended in each layer, and therefore the desired functions as described above can be allocated to each layer. In addition, excellent aesthetic appearance is preferable because it leads to a sense of elation and increased positivity in the user.

On the other hand, because multi-layered cosmetic compositions contain powder, they are prone to aggregation. Furthermore, when a multi-layered cosmetic composition is left to stand, the separated layers are made uniform by shaking, and when the composition is left to stand, the layers must be changed to return to their original separated state. For this reason, surfactants are used. However, if the action of the surfactant is too strong, it may take a long time to separate the layers, or emulsified droplets may remain in each layer after separation, making it difficult to obtain transparent separated layers, which is undesirable from an aesthetic point of view.

The present invention has been made in consideration of the above problems, and aims to provide a multi-layered cosmetic composition in which the oil phase and the powder phase are quickly separated and which has an aesthetic appearance.

The multi-layered cosmetic composition of the present invention is a multi-layered cosmetic composition which, when left to stand, has, from the top, an oil phase (A), an aqueous phase (B), and a powder phase (C), in that order,
(A) The oil phase contains a hydrocarbon oil and/or silicone oil; (B) the aqueous phase contains water; and (C) the powder phase contains a hydrophilic clay powder and a hydrophilic spherical powder.

The hydrocarbon oil and/or silicone oil is preferably a combination of a volatile oil and a non-volatile oil.

The volatile oil is preferably a hydrocarbon oil containing a tertiary carbon atom or a hydrocarbon oil having a main chain of 9 to 13 carbon atoms.

The hydrocarbon oil containing a tertiary carbon atom or the hydrocarbon oil having 9 to 13 carbon atoms in the main chain is preferably at least two selected from undecane, tridecane, and isohexadecane.

The hydrophilic clay powder is preferably bentonite and/or kaolin.

The hydrophilic spherical powder is preferably at least one selected from cellulose, (hexamethylene diisocyanate/trimethylol hexyllactone) crosspolymer, silica, polymethyl methacrylate, and (methyl methacrylate/PEG methacrylate/PEG-4/3) crosspolymer.

(B) It is preferred that the aqueous phase further contains sodium chloride.

(A) The oil phase is preferably 15 to 25% by mass of the total cosmetic, and (C) the powder phase is preferably 0.3 to 15% by mass of the total cosmetic.

The multi-layered cosmetic composition of the present invention can be a cosmetic composition filled in a dispenser-type container.
The cosmetic may be a topcoat cosmetic.

It is preferable that the dispenser container is transparent.

The multi-layered cosmetic composition of the present invention is a multi-layered cosmetic composition which, when left to stand, has, from the top, an oil phase (A), an aqueous phase (B), and a powder phase (C), in that order,
(A) The oil phase contains a hydrocarbon oil and/or silicone oil, (B) the aqueous phase contains water, and (C) the powder phase contains a hydrophilic clay powder and a hydrophilic spherical powder. This allows the oil phase and the powder phase to separate quickly, and the composition has an aesthetic appearance.

FIG. 1 is a set of photographs showing the state of phase separation over time in three types of multi-layered cosmetic compositions of the present invention.

The multi-layer cosmetic composition of the present invention will be described in detail below.
The multi-layered cosmetic composition of the present invention is a multi-layered cosmetic composition which, when left to stand, has, from the top, an oil phase (A), an aqueous phase (B), and a powder phase (C), in that order,
(A) The oil phase contains a hydrocarbon oil and/or silicone oil; (B) the aqueous phase contains water; and (C) the powder phase contains a hydrophilic clay powder and a hydrophilic spherical powder.

(A) Oil phase The oil phase contains a hydrocarbon oil and/or a silicone oil. The hydrocarbon oil and/or the silicone oil is preferably a combination of a volatile oil and a non-volatile oil. The combination of a volatile oil and a non-volatile oil can further improve phase separation and improve usability. The combination of a volatile oil and a non-volatile oil may be any combination of a volatile hydrocarbon oil and a non-volatile hydrocarbon oil, a volatile hydrocarbon oil and a non-volatile silicone oil, a non-volatile hydrocarbon oil and a volatile silicone oil, or a non-volatile hydrocarbon oil and a non-volatile silicone oil.

Here, the volatile oil means a component having a boiling point in the range of 60 to 260° C. at normal pressure.
The volatile oil may be selected from hydrocarbon oils having 8 to 16 carbon atoms, especially branched alkanes having 8 to 16 carbon atoms (also known as isoparaffins or isoalkanes), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and oils sold, for example, under the trade names ISOPARS® or PERMETHYLS®.

Further mention may be made as volatile hydrocarbon oils of linear alkanes having 9 to 17 carbon atoms, such as dodecane (12 carbon atoms) and tetradecane (14 carbon atoms), which are commercially available under the references PARAFOL® 12-97 and PARAFOL® 14-97 (Sasol), respectively, and also alkanes obtainable, for example, according to the method described in International Application WO 2007/068371 A1, such as the mixture of undecane (11 carbon atoms) and tridecane (13 carbon atoms), which is commercially available under the reference CETIOL® UT (Cognis).

From the viewpoint of smooth feel and phase separation, it is preferable to use a volatile hydrocarbon oil containing a tertiary carbon atom or a volatile hydrocarbon oil having 9 to 13 carbon atoms in the main chain, and among these, it is preferable to select at least two types selected from undecane, tridecane, and isohexadecane.

As volatile oils, it is also possible to use volatile silicones, for example or volatile linear or cyclic silicone oils, in particular those having a viscosity of less than or equal to 8 centistokes (cSt) (8×10 ⁻⁶ m ² /s), in particular those having 2 to 10 silicon atoms, especially 2 to 7 silicon atoms, which silicones may optionally contain alkyl or alkoxy groups having 1 to 10 carbon atoms. As volatile silicone oils that may be used in the present invention, particular mention may be made of dimethicones with a viscosity of 5 cSt and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

More preferred volatile silicone oils include linear or cyclic silicone oils having from 2 to 7 silicon atoms, which optionally contain alkyl or alkoxy groups having from 1 to 10 carbon atoms.
Of the volatile silicone oils, dodecamethylpentasiloxane is preferred.
Among the volatile fluorinated oils that may be mentioned are, for example, nonafluoromethoxybutane or perfluoromethylcyclopentane, and mixtures thereof.

Non-volatile oils are those that remain on the skin at room temperature and atmospheric pressure, more specifically, non-volatile oils have an evaporation rate of less than 0.01 mg/cm ² /min.
The non-volatile oils may in particular be chosen from non-volatile hydrocarbon oils, silicone oils.

An example of an animal-derived hydrocarbon oil is perhydrosqualene.
Hydrocarbon oils of plant origin include, for example, phytosterols, such as oleic acid esters of phytosterols, isostearic acid esters of phytosterols, and lauroyl/octyldodecyl/glutamic acid esters of phytosterols (Ajinomoto Co., Inc., ELDEW PS203), triglycerides composed of esters of glycerol and fatty acids, particularly those in which the fatty acids can have a chain length of C4 to C36, especially C18 to C36 (these oils can be linear or branched, saturated or unsaturated). In particular heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppy seed oil, pumpkin oil, millet oil, barley oil, quinoa oil, rye oil, kukui oil, passion flower oil, shea butter, aloe oil, sweet almond oil, peach kernel oil, peanut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camelina oil, canola oil, carrot oil, safflower oil, flax oil, rapeseed oil, cottonseed oil, palm oil oils, pumpkin seed oil, wheat germ oil, jojoba oil, lily oil, macadamia oil, corn oil, meadowfoam oil, St. John's wort oil, monoi oil, hazelnut oil, apricot kernel oil, walnut oil, olive oil, evening primrose oil, palm oil, blackcurrant seed oil, kiwi seed oil, grape seed oil, pistachio oil, pumpkin oil, winter squash oil, musk rose oil, sesame oil, soybean oil, sunflower oil, castor oil and watermelon oil, as well as mixtures thereof, or caprylic/capric triglycerides, such as those sold by the company STEARINERIE DUBOIS or under the names MIGLYOL 810®, 812® and 818® by the company DYNAMIT NOBEL.

Straight-chain or branched hydrocarbons of mineral or synthetic origin include, for example, liquid paraffin and its derivatives, petrolatum, polydecene, polybutene, hydrogenated polyisobutene, e.g. Parleam.

It may be a synthetic ether having 10 to 40 carbon atoms;
Synthetic esters are, for example, oils of the formula R1COOR2, in which R1 represents the residue of a linear or branched fatty acid containing 1 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched hydrocarbon chain, having 1 to 40 carbon atoms, with the proviso that the sum of the number of carbon atoms in the R1 chain and the number of carbon atoms in the R2 chain is 10 or more. The esters may in particular be chosen from esters of fatty alcohols and acids, such as cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate or isopropyl isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoic acid esters, in particular isostearyl heptanoate; alcohol or polyhydric alcohol esters of octanoic acid, decanoic acid or ricinoleic acid, such as propylene dioctanoate. glycol, cetyl octanoate, tridecyl octanoate, 4-diheptanoic acid and 2-ethylhexyl palmitate, alkyl benzoates, polyethylene glycol diheptanoate, propylene glycol 2-diethylhexanoate and mixtures thereof, C12 to C15 alkyl benzoates, hexyl laurate, neopentanoic acid esters such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate or octyldodecyl neopentanoate, isononanoic acid esters such as isononyl isononanoate, isotridecyl isononanoate and octyl isononanoate, hydroxylated esters such as isostearyl lactate and diisostearyl malate.

Fatty alcohols that are liquid at room temperature and contain branched and/or unsaturated carbon chains having 12 to 26 carbon atoms are also preferred. Examples include 2-octyldodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol.

It may also be a C12 to C22 higher fatty acid, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof.
Also included are dialkyl carbonates, in which the two alkyl chains may be the same or different, such as dicaprylyl carbonate sold under the name CETIOL CC® by the company COGNIS.

Silicone oils include, for example, non-volatile linear or cyclic polydimethylsiloxanes (PDMS); polydimethylsiloxanes containing alkyl, alkoxy or phenyl groups having 2 to 24 carbon atoms pendant or at the end of the silicone chain; phenylated silicones such as phenyltrimethicone, phenyldimethicone, phenyltrimethylsiloxydiphenylsiloxane, diphenyldimethicone, diphenylmethyldiphenyl-trisiloxane or (2-phenylethyl)trimethylsiloxysilicate, and mixtures thereof.

The oil phase is preferably 15 to 25% by mass, more preferably 17 to 23% by mass, and even more preferably 19 to 21% by mass, of the total cosmetic. When the oil phase is 15% by mass or more of the total cosmetic, good phase separation can be achieved, and the barrier function against external factors and the function as a moisturizing pack can also be improved. Furthermore, when the oil phase is 25% by mass or less of the total cosmetic, good phase separation can be achieved, and stickiness and shine when applied to the skin can be suppressed.

(B) Aqueous Phase The aqueous phase contains water. The water may be ion-exchanged water or purified water.
The aqueous phase preferably contains sodium chloride. By containing sodium chloride, the phase interface can be made clear and the separation speed can be adjusted. The blending amount is preferably 0.1 to 1 mass % relative to the total amount of the cosmetic, and more preferably 0.2 to 0.8 mass %. By making it 0.1 mass % or more, the interface can be made clear and the separation speed can be increased, and by making it 1 mass % or less, stickiness due to sodium chloride can be suppressed.

The aqueous phase may further contain a lower alcohol. By adding a lower alcohol, not only can the powder phase be wetted, but the specific gravity of the liquid itself can be reduced, and caking on the liquid surface of the powder can be suppressed. It can also provide a refreshing feel when used.

The amount of the lower alcohol is preferably 1.0 to 45.0% by mass, and more preferably 20 to 38% by mass, relative to the total amount of the multi-layered cosmetic. By making the blending amount 1.0% by mass or more, it is possible to ensure sufficient wetting of the powder and also to sufficiently suppress caking. On the other hand, by making the blending amount 45.0% by mass or less, it is possible to ensure good multi-phase separation and is also preferable from the standpoint of stability.

(C) Powder phase The multi-layered cosmetic of the present invention contains hydrophilic clay powder and hydrophilic spherical powder. By containing both hydrophilic clay powder and hydrophilic spherical powder, the multi-layered cosmetic in a phase-separated state can be made uniformly dispersed by shaking, and can be returned to the original separated state after standing still. In addition, the hydrophilic clay powder swells and is easily changed in shape, and by combining it with spherical powder, the height (sedimentation volume) of the powder phase when left standing can be obtained, which is aesthetically beautiful, and in addition, by combining powders with different properties, namely hydrophilic clay powder and hydrophilic spherical powder, caking (aggregation) of the powder phase can be suppressed.

The ratio of the amount of hydrophilic clay powder to the hydrophilic spherical powder cannot be generalized because it depends on the type and ratio of the hydrocarbon oil or silicone oil in the oil phase, and the types of hydrophilic clay powder and hydrophilic spherical powder used. For example, if the hydrophilic clay powder is bentonite and the hydrophilic spherical powder is silica, the ratio of the hydrophilic clay powder to the hydrophilic spherical powder (hydrophilic spherical powder/hydrophilic clay powder) is preferably 0.5 to 10, more preferably 1 to 8, and more preferably 1.2 to 5.

Examples of hydrophilic spherical powders used in the present invention include spherical resin powders whose powder surfaces have been hydrophilized (for example, spherical organic powders such as polyamide resin powders (nylon resin powders), spherical polyethylene, crosslinked poly(methyl meth)acrylate resin powders, spherical polyester, crosslinked polystyrene resin powders, styrene-acrylic acid copolymer resin powders, benzoguanamine resin powders, polytetrafluoroethylene powders, and dimethicone/vinyl dimethicone crosspolymers whose surfaces have been hydrophilized), water-dispersible spherical silica (water-dispersible spherical silicic anhydride), spherical starch powders and spherical cellulose powders whose powders themselves exhibit hydrophilicity. The method of hydrophilization of powders is not particularly limited, and can be carried out by, for example, polyethylene glycolization treatment.

The hydrophilic spherical powder may have a porous or non-porous surface as long as it is spherical in shape. From the viewpoint of adjusting the settling speed of the powder and facilitating the settling deposition, preferred examples of hydrophilic spherical powder include cellulose, (hexamethylene diisocyanate (HDI)/trimethylol hexyllactone) crosspolymer, silica, polymethyl methacrylate, and (methyl methacrylate/PEG methacrylate/PEG-4/3) crosspolymer.

Examples of cellulose include "Celluloflow C-25" (Chisso Corporation), (hexamethylene diisocyanate/trimethylol hexyllactone) crosspolymers such as "Plastic Powder D-400" (Toshiko Pigment Co., Ltd.), silica includes "Sunsphere L-51" (Asahi Glass Co., Ltd.) and "Silica Microbead P-1500" (JGC Catalysts and Chemicals Co., Ltd.), polymethyl methacrylate includes "Microsphere M-100" (Matsumoto Yushi Seiyaku Co., Ltd.), and (methyl methacrylate/PEG methacrylate/PEG-4/3) crosspolymers such as "Techpolymer AQUA" (Sekisui Chemical Co., Ltd.) are commercially available, and these can be suitably used.

The amount of hydrophilic spherical powder is preferably 0.01 to 3% by mass, and more preferably 0.03 to 1.5% by mass, relative to the total amount of the cosmetic. By making the amount 0.01% by mass or more, it becomes easier to adjust the settling speed and to obtain a settling volume. Furthermore, by making the amount 3% by mass or less, clogging of the nozzle and squeeze parts with powder can be prevented when a dispenser is used with the container.

As the hydrophilic clay powder, water-swellable clay minerals and kaolin are preferred. Water-swellable clay minerals are layered crystalline silicate minerals in which layers containing crystalline silicate are stacked with layers mainly containing metals such as Al and Mg, and examples of such minerals include smectite clay minerals and swelling mica. Examples of smectite clay minerals include bentonite, montmorillonite, beidellite, nontrolite, saponite, hectorite, stevensite, and taeniolite. Examples of swelling mica include fluorotetrasilicic mica. These may be either natural or synthetic. Examples of commercially available products include Kunipia, Sumecton (both manufactured by Kunimine Kogyo Co., Ltd.), Veegum (manufactured by Vanderbilt Co., Ltd.), Dimonite, fluorotetrasilicic mica (both manufactured by Topy Industries Co., Ltd.), and Laponite (manufactured by Rockwood Additive Co., Ltd.).

The amount of hydrophilic clay powder blended is preferably 0.01 to 3% by mass of the total cosmetic, and more preferably 0.03 to 1.5% by mass. A blended amount of 0.01% by mass or more makes it easier to adjust the settling speed, and a blended amount of 3% by mass or less makes it easier to produce a settling volume.

(C) The powder phase is preferably 0.3 to 15% by mass, more preferably 0.5 to 5% by mass, and even more preferably 0.8 to 1% by mass, of the total cosmetic. By having the powder phase be 0.3% by mass or more of the total cosmetic, sedimentation can be ensured to ensure aesthetics, and it is possible to provide a sebum adsorption function and prevent makeup from coming off. Furthermore, by having the powder phase be 15% by mass or less of the total cosmetic, good phase separation can be achieved and powder creasing can be prevented when applied to the skin.

It is preferable that the multi-layered cosmetic composition of the present invention does not substantially contain a surfactant, because the incorporation of a surfactant may cause an emulsification phenomenon that makes it difficult to form a clear phase boundary, and may also result in a stable, uniform emulsion composition that does not separate even when left to stand, and may not produce a multi-layered appearance.
However, when it is blended for the purpose of adjusting oil droplets on the container wall surface or in the space formed between the uppermost oil phase surface and the container, the blending amount is preferably 0.4 mass % or less based on the total amount of the cosmetic.

When using a surfactant, an anionic surfactant, a cationic surfactant, or a nonionic surfactant can be used. In particular, a nonionic surfactant is preferred.

Examples of lipophilic nonionic surfactants include sorbitan fatty acid esters (e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexyl acid, diglycerol sorbitan tetra-2-ethylhexyl acid, etc.); glycerin polyglycerin fatty acids (e.g., glycerin monocottonseed oil fatty acid, glycerin monoerucate, glycerin sesquioleate, glycerin monostearate, α,α'-glycerin oleate pyroglutamate, glycerin monostearate malate, etc.); propylene glycol fatty acid esters (e.g., propylene glycol monostearate, etc.); hydrogenated castor oil derivatives; glycerin alkyl ethers, etc.

Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (e.g., POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.); POE sorbitol fatty acid esters (e.g., POE-sorbitol monolaurate, POE-sorbitol monooleate, POE-sorbitol pentaoleate, POE-sorbitol monostearate, etc.); POE-glycerin fatty acid esters (e.g., POE-glycerin monostearate, POE-monooleates such as POE-glycerol monoisostearate, POE-glycerol triisostearate, etc.); POE-fatty acid esters (for example, POE-distearate, POE-monodioleate, ethylene glycol distearate, etc.); POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic types (for example, Pluronic POE·POP-alkyl ethers (e.g., POE·POP-cetyl ether, POE·POP-2-decyltetradecyl ether, POE·POP-monobutyl ether, POE·POP-hydrogenated lanolin, POE·POP-glycerin ether, etc.); tetraPOE·tetraPOP-ethylenediamine condensates (e.g., Tetronic, etc.); POE-castor oil hydrogenated castor oil derivatives (e.g., POE-castor oil, POE-hydrogenated castor oil, POE-hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE POE-hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE-hydrogenated castor oil maleic acid, etc.); POE-beeswax/lanolin derivatives (e.g., POE-sorbitol beeswax, etc.); alkanolamides (e.g., coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid esters; POE-alkylamines; POE-fatty acid amides; sucrose fatty acid esters; alkylethoxydimethylamine oxide; trioleyl phosphate, etc.

By blending a thickener made of a natural or synthetic polymer into the multi-layer cosmetic composition of the present invention, it is possible to adjust the usability and the speed at which the layers separate. In the present invention, when such a thickener is blended, the boundaries of a normal multi-layer cosmetic composition become unclear, but in the present invention, it is possible to provide a multi-layer cosmetic composition that is clear and beautiful. There are no limitations on the amount of thickener blended, but it is preferable that the blending amount is 0.01 to 10% by mass of the total amount of the multi-layer cosmetic composition.

The multi-layered cosmetic composition of the present invention may contain a thickener.
Examples of natural water-soluble polymers include plant-based polymers {e.g., gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed, algae colloid (cassow extract), starch (rice, corn, potato, wheat), glycyrrhizic acid}; microbial polymers (e.g., xanthan gum, dextran, succinoglucan, pullulan, etc.); and others (e.g., fish-derived collagen, fish-derived gelatin, wheat protein, silk protein, etc.).

Examples of semi-synthetic water-soluble polymers include starch-based polymers (e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); and alginic acid-based polymers (e.g., sodium alginate, propylene glycol alginate, etc.).

Examples of synthetic water-soluble polymers include vinyl polymers (e.g., polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, etc.); polyoxyethylene polymers (e.g., polyethylene glycol 20,000, 40,000, 60,000 polyoxyethylene polyoxypropylene copolymers, etc.); acrylic polymers (e.g., sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymers (e.g., polyacrylate), etc. Cationic polymers can more easily adjust sedimentation.
Examples of inorganic water-soluble polymers include aluminum magnesium silicate, bentonite, hectorite, AlMg silicate (veegum), laponite, and silicic anhydride.

The multi-layered cosmetic composition of the present invention can be blended with medicinal agents, moisturizing ingredients, anti-inflammatory agents, bactericides, preservatives, UV absorbers, antioxidants, other organic and inorganic powders, fragrances, pigments, and the like that are generally used in cosmetics, as necessary. In particular, the multi-layered cosmetic composition of the present invention can be blended with dyes to further enhance the aesthetic appeal of the oil phase and the water phase, and can also be blended with fragrances to enhance the palatability during use.

The drug component may be oil-soluble, water-soluble, or amphiphilic.Specific examples of the drug include whitening agents, moisturizing agents, anti-inflammatory agents, antibacterial agents, hormones, vitamins, various amino acids and their derivatives, enzymes, antioxidants, and hair growth agents.
Examples of whitening agents include hydroquinone derivatives such as arbutin, kojic acid, L-ascorbic acid (vitamin C) and its derivatives, pantothenyl ethyl ether, tranexamic acid and its derivatives, and various extracts such as placenta extract and plant extracts (e.g., chamomile extract, etc.).

Examples of L-ascorbic acid derivatives include L-ascorbic acid monoalkyl esters such as L-ascorbic acid monostearate, L-ascorbic acid monopalmitate, and L-ascorbic acid monooleate; L-ascorbic acid monoesters such as L-ascorbic acid monophosphate and L-ascorbic acid-2-sulfate; L-ascorbic acid dialkyl esters such as L-ascorbic acid distearate, L-ascorbic acid dipalmitate, and L-ascorbic acid dioleate; L-ascorbic acid diesters such as L-ascorbic acid diphosphate; L-ascorbic acid trialkyl esters such as L-ascorbic acid tristearate, L-ascorbic acid tripalmitate, and L-ascorbic acid trioleate; ascorbic acid triesters such as L-ascorbic acid triphosphate; and L-ascorbic acid glucosides such as L-ascorbic acid 2-glucoside. Examples of L-ascorbic acid and its derivatives include L-ascorbic acid, L-ascorbic acid phosphate, L-ascorbic acid 2-sulfate, L-ascorbic acid 2-glucoside, and salts thereof.

Tranexamic acid derivatives include dimers of tranexamic acid (e.g., trans-4-(trans-aminomethylcyclohexanecarbonyl)aminomethylcyclohexanecarboxylic acid hydrochloride, etc.), esters of tranexamic acid and hydroquinone (e.g., trans-4-aminomethylcyclohexanecarboxylic acid 4'-hydroxyphenyl ester, etc.), esters of tranexamic acid and gentisic acid (e.g., 2-(trans-4-aminomethylcyclohexylcarbonyloxy)-5-hydroxybenzoic acid and its salts, etc.), amides of tranexamic acid (e.g., trans-4-aminomethylcyclohexanecarboxylic acid methylamide and its salts, trans-4-(p-methoxybenzoyl)aminomethylcyclohexanecarboxylic acid and its salts, trans-4-guanidinomethylcyclohexanecarboxylic acid and its salts, etc.).

Anti-inflammatory agents include, for example, glycyrrhizin, glycyrrhizinate salts (eg, dipotassium glycyrrhizinate, ammonium glycyrrhizinate, etc.), allantoin, and the like.
An example of a moisturizing agent is urea.
Antibacterial agents include, for example, resorcin, sulfur, salicylic acid, and the like.
Examples of hormone agents include oxytocin, corticotropin, vasopressin, secretin, gastrin, calcitonin, hinokitiol, and ethinyl estradiol.

Examples of vitamins include vitamin A and its derivatives (e.g., retinol, vitamin A palmitate, etc.), vitamin B6, vitamin B6 derivatives such as vitamin B6 hydrochloride, nicotinic acid, nicotinic acid amide and other nicotinic acid derivatives, vitamin E and its derivatives, and β-carotene.

Examples of various amino acids and their derivatives and enzymes include L-glutamic acid, urocanic acid, trypsin, lysozyme chloride, chymotrypsin, semi-alkaline proteinase, serrapeptase, lipase, and hyaluronidase.
Examples of antioxidants include thiotaurine, glutathione, catechin, albumin, ferritin, and metallothionein.
When applied to hair growth agents, examples include β-glycyrrhetinic acid, pantothenyl ethyl ether, and minoxidil.
Cooling agents such as camphor and menthol may also be used.

To produce the multi-layered cosmetic composition of the present invention, a commonly known manufacturing method is used. For example, a powder phase that has been pre-dispersed in advance and an oil phase in which oil-soluble components have been dissolved are added to an aqueous phase in which water-soluble components have been dissolved, and then the mixture is stirred. When the multi-layered cosmetic composition of the present invention is shaken, the separated oil phase, aqueous phase, and powder phase are uniformly dispersed throughout, resulting in a single-phase composition, and when the composition is allowed to stand, it separates again and returns to the original multi-layered cosmetic composition.

The multi-layered cosmetic composition of the present invention can be used in various categories of cosmetics, specifically, as topcoat cosmetics, lotions, antiperspirants, cleansing lotions, fragrances, colognes, air fresheners, deodorant sprays, bath additives, etc.

The cosmetic of the present invention is particularly suitable for use in a mist form stored in a spray container such as a dispenser, or in a spray form stored together with a propellant, and does not cause clogging of the nozzle or squeeze portion. By storing it in a spray container such as a dispenser, it can be applied evenly, and even when used as a makeup base, makeup can be prevented from coming off or becoming smudged.

The present invention will now be described in more detail with reference to examples. The present invention is in no way limited to the following examples. The blend amounts are in mass % unless otherwise specified.

[Consideration of type and amount of oil phase]
Multi-layered cosmetics of Test Examples 1 to 12 (systems with different types and amounts of oil phase) were prepared according to the formulations shown in Table 1, and the occurrence of three-phase separation and aesthetics (balance of the three phases) were evaluated according to the following criteria.
(Possibility of three-phase separation)
The prepared multi-layered cosmetic was placed in an 80 mL PET container and stirred. The state was observed one hour after stirring and evaluated as follows.
A: Separates into oil, water, and powder phases after 1 hour of stirring. D: Does not separate into oil, water, and powder phases after 1 hour of stirring (aesthetics - balance of 3 phases)
70 g of the prepared multi-layered cosmetic was placed in an 80 mL PET container and stirred. After leaving it to stand for 1 hour, the phase ratios were calculated for the oil phase and powder phase when the total height (cm) was taken as 100%, and the aesthetics were evaluated in terms of the balance of the three phases according to the following criteria.
A: The powder phase has a height of 7/10 or more of the total, and the three phases are very well balanced. B: The powder phase has a height of 1/2 or more and less than 7/10 of the total, and the three phases are well balanced. C: The powder phase has a height of less than 1/2 of the total, and the three phases are somewhat unbalanced.

As shown in Table 1, in systems with different types and amounts of oil phase, the aesthetics in terms of three-phase separation and balance of the three phases were generally good.

[Consideration of powder type]
Multi-layered cosmetics of Test Examples 13 to 23 (systems using different types of powder) were prepared according to the formulations shown in Table 2. The occurrence of three-phase separation was evaluated according to the same criteria as in [Study on the type and amount of oil phase] above, and the aesthetics (beauty of the oil-water interface) was evaluated according to the following criteria.
(Aesthetics - cleanliness of the interface)
A: After 1 hour of stirring, the interfaces between the oil phase and the water phase, and between the water phase and the powder phase are clean. D: After 1 hour of stirring, the interfaces between the oil phase and the water phase, and between the water phase and the powder phase are unclear due to white turbidity, etc.

As shown in Table 2, it was found that the type of powder had an effect on the aesthetics in terms of three-phase separation or interface cleanliness.

[Consideration of powder amount]
Multi-layered cosmetics of Test Examples 24 to 32 (systems with different amounts of powder) were prepared according to the formulations shown in Table 3, and the height ratio of the oil phase to the powder phase after stirring for 1 hour was determined. In addition, the aesthetics were evaluated according to the same criteria as in [Study of the type and amount of oil phase] above.

As shown in Table 3, it was found that the amount of powder had an effect on aesthetics in terms of three-phase separation or three-phase balance.

[Phase separation study]
Multi-layered cosmetics of Test Examples 33 to 35 (systems containing different types of volatile hydrocarbon oils) were prepared according to the formulations shown in Table 4. The prepared multi-layered cosmetics of Test Examples 33 to 35 were stirred, and the state of phase separation was observed immediately after stirring, 2 minutes after stirring, and 30 minutes after stirring. The observation results are shown in Figure 1. Note that the photographs in Figure 1, from the left, are Test Example 33 (undecane + tridecane), Test Example 34 (isododecane), and Test Example 35 (isohexadecane).

From Figure 1 and Table 4, it was found that when the powder contained cellulose, bentonite, and silica, phase separation was rapid in Test Example 3 2 minutes after stirring, while the transparent part of the oil phase and its interface became clear in Test Examples 1 and 3 30 minutes after stirring.

[Consideration of fixer effect]
According to the formulations shown in Table 5, multi-layered cosmetic compositions of Test Examples 36 to 43 were prepared.

The multi-layered cosmetic compositions of Test Examples 36 to 43 were placed in a spray container and sprayed onto the face after makeup had been applied. When checked after 8 hours, it was found that when the multi-layered cosmetic compositions of Test Examples 36 to 43 had been applied, there was no sign of makeup coming off or powder creasing, the makeup did not fade, and the skin texture was not noticeable.

A formulation example of a multi-layer cosmetic is shown below. The multi-layer cosmetic shown below was prepared as follows. First, (1) to (4) were mixed and dissolved at room temperature to prepare the oil phase in advance. In addition, (14) to (16) were pre-dispersed to prepare the powder phase in advance. (12) and (17) were mixed and dispersed in (6) at room temperature. (7) to (11) were mixed and dissolved in (5) at room temperature, and the previously mixed and dispersed (6) solution, powder phase, and oil phase were added in that order, and a three-layer makeup lotion was obtained by propeller stirring.

Formulation example 1: After-makeup lotion ingredients
(1) Undecane 3.5
(2) Tridecane 1.5
(3) Hydrogenated polydecene 12
(4) Isohexadecane 3
(5) Ion-exchanged water 100%
(6) Ethanol 20
(7) Glycerin 2
(8) Salt: 0.2
(9) Lactic acid 0.01
(10) Sodium lactate 0.5
(11) Sodium pyrosulfite 0.003
(12) Phenoxyethanol 0.35
(13) EDTA 0.01
(14) Cellulose 0.25-0.35
(15) Bentonite 0.05 to 0.3
(16) (HDI/trimethylolhexyllactone) crosspolymer 0.3-0.33
(17) Flavoring (appropriate amount)

Formulation example 2: After-makeup lotion
(1) Undecane 3.5
(2) Tridecane 1.5
(3) Hydrogenated polydecene 12
(4) Isohexadecane 3
(5) Ion-exchanged water 100%
(6) Ethanol 20
(7) Glycerin 2
(8) Salt: 0.2
(9) Lactic acid 0.01
(10) Sodium lactate 0.5
(11) Sodium pyrosulfite 0.003
(12) Phenoxyethanol 0.35
(13) EDTA 0.01
(14) Cellulose 0.25-0.35
(15) Bentonite 0.05 to 0.3
(16) Silica 0.3
(17) Flavoring (appropriate amount)

Formulation example 3: After-makeup lotion
(1) Undecane 3.5
(2) Tridecane 1.5
(3) Hydrogenated polydecene 12
(4) Isohexadecane 3
(5) Ion-exchanged water 100%
(6) Ethanol 20
(7) Glycerin 2
(8) Salt: 0.2
(9) Lactic acid 0.01
(10) Sodium lactate 0.5
(11) Sodium pyrosulfite 0.003
(12) Phenoxyethanol 0.35
(13) EDTA 0.01
(14) Cellulose 0.25-0.35
(15) Bentonite 0.05 to 0.3
(16) Polymethyl methacrylate 0.3
(17) Flavoring (appropriate amount)

Claims (7)

A multi-layered cosmetic composition which, when left to stand, has, from the top, an oil phase (A), an aqueous phase (B), and a powder phase (C), in that order,
(A) the oil phase contains a hydrocarbon oil and/or silicone oil; (B) the aqueous phase contains water; and (C) the powder phase contains 0.01 to 3% by mass of a hydrophilic clay powder and 0.01 to 3% by mass of a hydrophilic spherical powder relative to the total amount of the cosmetic,
The hydrocarbon oil and/or silicone oil is a combination of a volatile oil and a non-volatile oil, and the volatile oil is a hydrocarbon oil containing a tertiary carbon atom or a hydrocarbon oil having a main chain carbon number of 9 to 13,
(1) The hydrophilic clay powder is bentonite and kaolin, the hydrophilic spherical powder contains at least cellulose, and does not contain talc, nylon-12 powder, and methyl methacrylate crosspolymer powder , or (2) The hydrophilic clay powder is bentonite and/or kaolin, the hydrophilic spherical powder contains cellulose, silica, and/or (hexamethylene diisocyanate/trimethylol hexyllactone) crosspolymer , and does not contain talc, nylon-12 powder, and methyl methacrylate crosspolymer powder. or (3) the hydrophilic clay powder is bentonite and/or kaolin, and the hydrophilic spherical powder is at least one selected from cellulose, (hexamethylene diisocyanate/trimethylol hexyllactone) crosspolymer, silica, polymethyl methacrylate, and (methyl methacrylate/PEG methacrylate/PEG-4/3) crosspolymer, and does not contain talc, nylon-12 powder, or methyl methacrylate crosspolymer powder.
Multi-layered cosmetics. The multi-layered cosmetic composition according to claim 1, wherein the hydrocarbon oil is at least two selected from undecane, tridecane, and isohexadecane. The multi-layered cosmetic preparation according to claim 1 or 2, wherein the aqueous phase (B) further contains sodium chloride. The multi-layered cosmetic according to any one of claims 1 to 3, wherein the (A) oil phase is 15 to 25% by mass relative to the total amount of the cosmetic, and the (C) powder phase is 0.3 to 15% by mass relative to the total amount of the cosmetic. A cosmetic product in which the multi-layer cosmetic product according to any one of claims 1 to 4 is filled in a dispenser-type container. The cosmetic according to claim 5, wherein the cosmetic is a topcoat cosmetic. The cosmetic product according to claim 5 or 6, wherein the dispenser-type container is transparent.