JP7583570B2 - Oil-in-water emulsified solid cosmetic - Google Patents

Description

The present invention relates to an oil-in-water emulsified solid cosmetic product.

Emulsion cosmetics are a formulation that has been used in cosmetics because they can efficiently spread oil-soluble active ingredients, such as emollient oils, UV absorbers, oil-soluble drugs, etc., onto the skin, and because of their ease of use, they are widely used not only in skin care cosmetics but also in makeup cosmetics. Among them, oil-in-water emulsion cosmetics have a continuous phase composed of aqueous components, so when used as cosmetics, they have the characteristics of being light and smooth to spread on, providing a refreshing feel, and improving the adhesion of the cosmetics to the skin and the durability of the cosmetics.

Agar is sometimes blended into such oil-in-water emulsion cosmetics to impart a fresh, cool feel to the touch, or to give the cosmetics a solid form. However, the inclusion of agar can sometimes reduce the adhesion of the cosmetics to the skin and the cosmetic lasting power. To solve this problem, Patent Document 1 blends polyethylene glycol into an oil-in-water solid cosmetic blended with agar. Patent Document 1 states that the inclusion of polyethylene glycol improves adhesion to the skin and the cosmetic lasting power.

JP 2003-95862 A

When agar is blended into an oil-in-water cosmetic to ensure shape retention, the cosmetic hardens. As a result, when consumers try to remove the cosmetic with their fingers or an applicator, the cosmetic becomes difficult to remove (the cosmetic comes off poorly), and it becomes difficult to adhere an appropriate amount of cosmetic to fingers or applicators. Conversely, if the amount of agar blended is reduced in an attempt to improve the removal of the cosmetic, problems arise in that shape retention is not maintained after long-term storage. In other words, in oil-in-water emulsion cosmetics containing agar, there is a trade-off between shape retention, which maintains the solid shape, and the ease of removal of the cosmetic.

The present invention aims to provide an oil-in-water emulsified solid cosmetic that maintains its solid form even after long-term storage and allows for easy removal of the cosmetic.

Another object of the present invention is to provide an oil-in-water emulsion solid cosmetic that spreads smoothly when applied to the skin. Furthermore, another object of the present invention is to provide an oil-in-water emulsion solid cosmetic that has high adhesion to the skin when applied and has a sustained effect.

The present invention comprises the following components (A) to (D):
(A) a polymer comprising: (a) a structural unit derived from a monomer selected from the group consisting of (meth)acrylic acid and an alkyl (meth)acrylate; and (b) a structural unit derived from a monomer selected from the group consisting of polyoxyethylene alkyl ether itaconate and polyoxyethylene alkyl ether (meth)acrylate;
(B) agar,
The present invention is an oil-in-water emulsion solid cosmetic preparation comprising (C) an oil agent and (D) water.

According to the present invention, it is possible to provide an oil-in-water emulsion solid cosmetic that maintains its solid form even after long-term storage and allows good cosmetic removal. In addition, according to the present invention, it is possible to provide an oil-in-water emulsion solid cosmetic that spreads smoothly when applied to the skin. Furthermore, according to the present invention, it is possible to provide an oil-in-water emulsion solid cosmetic that exhibits high adhesion to the skin when applied and that provides sustained effects.

The following describes the embodiments of the present invention. Note that the present invention is not limited to the following embodiments. In this specification, the range "X to Y" includes X and Y and means "X or more and Y or less." Furthermore, unless otherwise specified, operations and measurements of physical properties are performed under conditions of room temperature (20 to 25°C) and relative humidity of 45 to 55% RH.

The first embodiment of the present invention is an oil-in-water emulsified solid cosmetic comprising the following components (A) to (D): (A) a polymer containing a structural unit (a) derived from a monomer selected from the group consisting of (meth)acrylic acid and an alkyl (meth)acrylate, and a structural unit (b) derived from a monomer selected from the group consisting of polyoxyalkylene alkyl ether itaconate and polyoxyalkylene alkyl ether (meth)acrylate, (B) agar, (C) an oil, and (D) water.

As described above, in solid cosmetics, there is a trade-off between the cosmetic's ability to retain its shape and its ability to come off (i.e., its ability to adhere appropriately to applicators, etc.), and it is difficult to achieve both. On the other hand, the configuration of this embodiment improves the ease of removal while maintaining the solid shape. Furthermore, the cosmetic of this embodiment spreads smoothly when applied to the skin, has high adhesion to the skin, and exerts its effects for a long period of time (good cosmetic wear).

The detailed mechanism by which the cosmetic composition of this embodiment exerts the above-mentioned effects is unknown, but is thought to be as follows. Note that the following mechanism does not limit the scope of the present invention in any way.

Agar has a network structure in which polymer chains are intricately entangled, and therefore agar may be blended to maintain the solid state of cosmetics. However, when a certain amount or more of agar is blended into cosmetics to give a shape to the solid cosmetic, the network structure of the agar becomes stronger, and the cosmetic becomes harder, which makes it difficult to remove. On the other hand, component (A) in this embodiment has a polyoxyalkylene alkyl ether chain in its structure. This polyoxyalkylene alkyl ether chain interacts with component (B), and component (A) reduces the solidifying power of component (B) (becoming slightly creamy), so that the cosmetic is easy to remove despite being a solid cosmetic, and spreads smoothly when applied to the skin. In addition, the gel structure formed by components (A) and (B) is maintained on the skin, improving the feeling of adhesion to the skin and also providing excellent cosmetic durability. On the other hand, the oil droplets (emulsion droplets) formed by component (C) are held in the lipophilic portion (alkyl chain) of component (A), and the gel structure composed of components (A) and (B) suppresses the movement of the oil droplets, preventing them from coalescing, improving emulsion stability and allowing the emulsion to maintain a solid form even after long-term storage.

In addition, because component (A) has a polyoxyalkylene alkyl ether chain in its structure, the polyoxyethylene alkyl ether chain portion can hold water well together with component (B), imparting a fresh feeling when the cosmetic is applied to the skin and allowing the cosmetic to spread smoothly on the skin.

In addition, the solid state of the solid cosmetic product in this invention is clearly distinguished from the gel-like, semi-solid state that has fluidity when turned on its side, and refers to a state that does not flow even when turned on its side. Specifically, the solid cosmetic product is preferably 0.1 g or more when the measurement sample is filled into a polypropylene jar container with a diameter of 75 mm and a height of 52 mm so as not to leave any air spaces, the container is capped, and the container is left overnight in a thermostatic chamber at 30°C, after which the weight is measured by a load measuring machine (manufactured by FUDOH) under the conditions of a 2 cm diameter spherical adapter, 2 cm/min, and 10 mm needle penetration.

The components that make up this embodiment are described below.

(Component (A): A polymer including a structural unit (a) derived from a monomer selected from the group consisting of (meth)acrylic acid and an alkyl (meth)acrylate, and a structural unit (b) derived from a monomer selected from the group consisting of a polyoxyalkylene alkyl ether itaconate and a polyoxyalkylene alkyl ether (meth)acrylate (hereinafter simply referred to as a polymer of component (A))
The polymer of component (A) is obtained by copolymerizing a monomer (a) selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid alkyl esters, and a monomer (b) selected from the group consisting of itaconate polyoxyalkylene alkyl ethers and (meth)acrylic acid polyoxyalkylene alkyl ethers. Preferably, it is obtained by copolymerizing a monomer selected from the group consisting of acrylic acid and (meth)acrylic acid alkyl esters, and a monomer selected from the group consisting of itaconate polyoxyalkylene alkyl ethers and (meth)acrylic acid polyoxyalkylene alkyl ethers. The bonding mode is not particularly limited, and may be any of block bonding, random bonding, and the like. In addition, it may contain other monomers, and may have a crosslinked structure. When other monomers are contained, the other monomers are preferably less than 10 mol% (lower limit 0 mol%), more preferably 5 mol% or less (lower limit 0 mol%), and even more preferably 1 mol% or less (lower limit 0 mol%) based on the total monomers. Here, the contents of the structural unit (a) and the structural unit (b) correspond to the amounts of the monomers (a) and (b) added in the production stage.

The content ratio of the structural unit (a) and the structural unit (b) is not particularly limited, and for example, the molar ratio of the structural unit (a):structural unit (b) is 1:100 to 100:1.

Specific examples of the polymer of component (A) include (meth)acrylic acid/alkyl (meth)acrylate/polyoxyethylene alkyl ether (meth)acrylate copolymers, (meth)acrylic acid/alkyl (meth)acrylate/polyoxyethylene alkyl ether itaconate copolymers, etc. Also, the polymer may be a crosspolymer (crosslinked product), and examples of the crosspolymer include (meth)acrylic acid/alkyl (meth)acrylate/polyoxyethylene alkyl ether (meth)acrylate crosspolymers, (meth)acrylic acid/alkyl (meth)acrylate/polyoxyethylene alkyl ether itaconate crosspolymers, etc.

In this specification, (meth)acrylic acid refers to both acrylic acid and methacrylic acid.

In the alkyl (meth)acrylate ester, the alkyl group of the alkyl ester preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and even more preferably 1 to 8 carbon atoms. Examples of alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate.

The number of moles of polyoxyalkylene added in the polyoxyalkylene alkyl ether itaconate/polyoxyalkylene alkyl ether (meth)acrylate is preferably 10 to 30, more preferably 12 to 25, and even more preferably 20 to 25. Examples of polyoxyalkylene include polyoxyethylene and polyoxypropylene, with polyoxyethylene being preferred. In the polyoxyalkylene alkyl ether itaconate and polyoxyalkylene alkyl ether (meth)acrylate, the alkyl group of the alkyl ether preferably has 12 to 24 carbon atoms, and even more preferably has 16 to 22 carbon atoms. More preferred examples of the itaconic acid polyoxyalkylene alkyl ether/(meth)acrylic acid polyoxyalkylene alkyl ether include esters of acrylic acid and polyoxyethylene (20) stearyl ether, esters of methacrylic acid and polyoxyethylene (20) stearyl ether, esters of acrylic acid and polyoxyethylene (25) behenyl ether, esters of methacrylic acid and polyoxyethylene (25) behenyl ether, and esters of itaconic acid and polyoxyethylene (20) stearyl ether crosspolymer. The numbers in parentheses indicate the number of moles of ethylene oxide added.

More specifically, the polymer of component (A) may be (meth)acrylic acid/(meth)acrylic acid alkyl ester/(meth)acrylic acid polyoxyethylene alkyl ether copolymers such as acrylates/polyoxyethylene methacrylate (20) cetyl ether copolymer, acrylates/polyoxyethylene methacrylate (20) stearyl ether copolymer, acrylates/polyoxyethylene methacrylate (25) behenyl ether copolymer; acrylates/polyoxyethylene itaconate (20) cetyl ether copolymer, acrylates/polyoxyethylene itaconate (20) stearyl ether copolymer, etc. Examples of such crosspolymers include (meth)acrylic acid/(meth)acrylic acid alkyl ester/polyoxyethylene alkyl ether itaconate copolymers; (meth)acrylic acid/(meth)acrylic acid alkyl ester/polyoxyethylene alkyl ether (meth)acrylic acid crosspolymers such as acrylates/polyoxyethylene (20) stearyl ether methacrylate crosspolymers; and (meth)acrylic acid/(meth)acrylic acid alkyl ester/polyoxyethylene alkyl ether itaconate crosspolymers such as acrylates/polyoxyethylene (20) stearyl ether itaconate crosspolymers. The numbers in parentheses indicate the number of moles of ethylene oxide added.

Among these, from the viewpoints of shape retention and ease of application of the cosmetic, it is preferable that component (A) be an acrylates/polyoxyethylene stearyl ether methacrylate copolymer, an acrylates/polyoxyethylene behenyl ether methacrylate copolymer, an acrylates/polyoxyethylene stearyl ether itaconate copolymer, or an acrylates/polyoxyethylene stearyl ether itaconate crosspolymer.

Commercially available products of acrylates/polyoxyethylene (20) methacrylate stearyl ether copolymer (acrylates/steareth-20 methacrylate copolymer) include, for example, trade name: Accurin (registered trademark) 22 (manufactured by Rohm and Haas Co.), and commercially available products of acrylates/polyoxyethylene (25) methacrylate behenyl ether copolymer (acrylates/beheneth-25 methacrylate copolymer) include, for example, trade name: Accurin 28 (manufactured by Rohm and Haas Co.), and trade name: NOVETHIX (registered trademark). L-10 (manufactured by Lubrizol Corporation), an example of a commercially available product of acrylates/polyoxyethylene (20) itaconate stearyl ether copolymer (acrylates/steareth-20 itaconate copolymer) is, for example, trade name: STRUCTURE (registered trademark) 2001 (manufactured by Akzo Nobel), and an example of a commercially available product of acrylates/polyoxyethylene (20) methacrylate stearyl ether crosspolymer is, for example, trade name: Accurin 88 (manufactured by Rohm and Haas Company).

Component (A) may be used alone or in combination of two or more types.

The amount of component (A) in the cosmetic is preferably 0.001% by mass or more, more preferably 0.005% by mass or more in consideration of cosmetic durability and stability, and even more preferably 0.01% by mass or more in consideration of removal of the cosmetic, spreadability on the skin, and adhesion of the cosmetic to the skin, and is particularly preferably 0.05% by mass or more since the effects of the present invention are further enhanced. Furthermore, the amount of component (A) in the cosmetic is preferably 4% by mass or less in consideration of adhesion to the skin, and is particularly preferably 2% by mass or less.

Component (A) is usually neutralized with a basic substance before use. Examples of basic substances used in this case include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, and triisopropanolamine; inorganic bases such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide; and basic amino acids such as L-arginine. These basic substances may be added in an amount sufficient to neutralize component (A), and the amount of basic substance added is, for example, 20 to 150% by mass relative to component (A).

(Component (B): Agar)
The agar of component (B) is a natural polymer, and any agar can be used regardless of its place of origin. In addition, the agar may be so-called low-strength agar (disclosed in JP-A-5-317008) in which the molecules are cut by acid treatment in order to adjust the jelly strength. The jelly strength of component (B) is not particularly limited, but is preferably 20 to 2000 g/ ^cm2 , and more preferably 30 to 1000 g/ ^cm2 . Here, the jelly strength refers to the maximum mass that can be withstood per 1 ^cm2 of the surface of a gel obtained by dissolving agar in water by heating to a concentration of 1.5% by mass (hereinafter simply referred to as "%)" and leaving it at 20°C for 15 hours to solidify (Nihon Kansui method).

As the agar of component (B), for example, commercially available products such as Ina Agar PS-84, Z-10, AX-30, AX-100, AX-200, T-1, S-5, M-7, UP-16, UP-37, CS-16A, CS-420, CS-670, and XY-908 (all manufactured by Ina Food Industry Co., Ltd.) can be used.

The content of component (B) agar is not particularly limited, but in consideration of the adhesion to the skin and the stability of the cosmetic, it is preferably 0.01% by mass or more of the total cosmetic, and more preferably 0.05% by mass or more. In addition, the content of component (B) agar is not particularly limited, but in consideration of the ease of removal of the cosmetic, it is preferably 10% by mass or less of the total cosmetic, and more preferably 5% by mass or less.

The content mass ratio (A)/(B) of component (A) to component (B) is preferably 0.001 or more in consideration of cosmetic retention and stability, more preferably 0.002 or more in consideration of removal of the cosmetic, spreadability on the skin, and adhesion of the cosmetic to the skin, and even more preferably 0.01 or more since the effects of the present invention are enhanced. The content mass ratio (A)/(B) of component (A) to component (B) is preferably 15 or less in consideration of the effects of the present invention, more preferably 10 or less in consideration of adhesion to the skin, and even more preferably 5 or less in consideration of adhesion to the skin, cosmetic retention, and shape retention. In a preferred embodiment of the present invention, the content mass ratio (A)/(B) of component (A) to component (B) is 0.001 to 15.

(Component (C): Oil)
In this specification, the oil agent refers to an oil-soluble compound that is insoluble (slightly soluble) in water, for example, a substance having a solubility in water (1013.25 hPa, 20° C.) of less than 2 g/100 g H ₂ O.

Oils include hydrocarbons such as isododecane, isohexadecane, light isoparaffin, liquid paraffin (mineral oil), squalane, squalene, α-olefin oligomer, polybutene, liquid isoparaffin, heavy liquid isoparaffin, polyisobutylene, and hydrogenated polyisobutene, rapeseed oil, avocado oil, almond oil, apricot kernel oil, perilla oil, orange oil, olive oil, kiwi seed oil, grape seed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, safflower oil, sage oil, soybean oil, tea seed oil, corn oil, rapeseed oil, evening primrose oil, camellia oil, persic oil, pearl barley oil, peanut oil, sunflower oil, sunflower seed oil, grape seed oil, meadowfoam oil, and other oils. animal and vegetable oils such as ginger oil, rosemary oil, jojoba oil, jojoba seed oil, macadamia nut oil, lavender oil, rosehip oil, and mink oil; glyceryl tri-2-ethylhexanoate (triethylhexanoin), isotridecyl isononanoate, isononyl isononanoate, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, tri(caprylic/capric acid)glyceryl, glyceryl diisostearate, glyceryl triisostearate, decaglyceryl decaisostearate (polyglyceryl-10 decaisostearate), polycapric acid Propylene glycol, neopentyl glycol dicaprate, polyglyceryl triisostearate, diisostearyl malate, neopentyl glycol diethylhexanoate, polyglyceryl-10 decaisostearate, pentaerythritol tetraisostearate, pentaerythritol tetra-2-ethylhexanoate (pentaerythrityl tetraethylhexanoate), dipentaerythritol pentaisostearate, dipentaerythrityl hexa(hydroxystearic acid/stearic acid/rosin acid), dialkyl carbonate, tritridecyl trimellitate, bisethoxydiglycol cyclohexane-1,4-dicarboxylate, dimer dilinoleyl hydrogenated rosin condensate , alkyl benzoate (C12-15), polyhydroxystearic acid and other esters; fatty acids such as oleic acid and isostearic acid; higher alcohols such as oleyl alcohol, 2-octyldodecanol, 2-decyltetradecanol, isostearyl alcohol, and 2-hexyldecanol; dimethylpolysiloxane (dimethicone), methylhydrogenpolysiloxane, methyltrimethicone, methylphenylpolysiloxane (diphenylsiloxyphenyltrimethicone), cyclopentasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, tetramethyltetrafluoroethylene ... Silicone oils such as phenylcyclotetrasiloxane, tetramethyltetratrifluoropropylcyclotetrasiloxane, pentamethylpentatrifluoropropylcyclopentasiloxane, polyether-modified dimethylpolysiloxane, oleyl-modified dimethylpolysiloxane, polyvinylpyrrolidone-modified dimethylpolysiloxane, and alkyl-modified dimethylpolysiloxane; fluorine-based oils such as perfluoropolyether, perfluorodecane, and perfluorooctane; lanolin derivatives such as lanolin acetate, lanolin fatty acid isopropyl, and lanolin alcohol; 2-ethylhexyl paramethoxycinnamate, ethylhexyl salicylate, 2-[4-(diethylamino)-2-hydroxyethyl]-2-propanediol, and the like. ultraviolet absorbers such as hexyl hydroxybenzoylbenzoate, methylene bisbenzotriazolyl tetramethylbutylphenol, bisethylhexyloxyphenol methoxyphenyl triazine, and polysilicone-15; carotenes such as zeaxanthin, canthaxanthin, astaxanthin, fucoxanthin, lutein, α-carotene, β-carotene, γ-carotene, δ-carotene, and lycopene, and derivatives thereof; vitamin E such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, α-tocotrienol, β-tocotrienol, γ-tocotrienol, δ-tocotrienol, and tocopherol acetate, or derivatives thereof; oil-soluble components such as conductors, retinol or derivatives thereof, oil-soluble derivatives of ascorbic acid such as ascorbyl palmitate and ascorbyl tetrahexyldecanoate, and ceramides; cocoa butter, shea butter, castor oil, hydrogenated castor oil, hydrogenated coconut oil, petrolatum, hydrogenated castor oil monostearate, hydrogenated castor oil monohydroxystearate, cholesteryl hydroxystearate, dipentaerythritol fatty acid esters, N-lauroyl-L-glutamic acid di(phytosteryl, 2-octyldodecyl), N-lauroyl-L-glutamic acid di(octyldodecyl/cholesteryl/behenyl), N-lauroyl-L-glutamic acid di(octyldodecyl/phytosteryl/behenyl), oils such as phytosteryl, macadamia nut oil fatty acid phytosteryl, dimer dilinoleic acid (phytosteryl/isostearyl/cetyl/stearyl/behenyl); waxes such as paraffin wax, ceresin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and beeswax; fatty acids such as stearic acid and behenic acid; higher alcohols such as cetostearyl alcohol, behenyl alcohol, and jojoba alcohol; cetyl palmitate, polyethylene glycol distearate, glyceryl tribehenate, cholesterol, phytosterol, stearyl-modified polysiloxane, hardened oil, and palm oil.

As the oil, it is preferable to use at least a liquid oil, as this provides a fresh feeling and smooth spreadability. The liquid oil in the oil is preferably 70% by mass or more (upper limit 100% by mass), more preferably 80% by mass or more (upper limit 100% by mass), and even more preferably 90% by mass or more (upper limit 100% by mass). In addition, it is preferable to include at least an ester oil as the oil, as this makes it easier to achieve the desired cosmetic effect (fresh feeling, adhesion to the skin). Note that a liquid oil refers to an oil that is liquid (has fluidity) at 25°C.

The content of component (C) is preferably 5% by mass or more. In the present application, by including component (A), the stability of the formulation is high even when a relatively large amount of oil is blended, and the desired cosmetic effect (fresh feel, adhesion to skin) is easily obtained. The content of component (C) is more preferably 10% by mass or more. In addition, in consideration of emulsion stability, the content of component (C) is preferably 50% by mass or less, and in consideration of adhesion to skin, the content is more preferably 30% by mass or less.

(Component (D): Water)
The oil-in-water emulsified solid cosmetic preparation of the present invention usually contains water as component (D). Water as component (D) is used as a solvent and constitutes the balance of the above-mentioned components and other components constituting the oil-in-water emulsified solid cosmetic preparation. It is preferable that the water does not contain impurities, and from this viewpoint, it is preferable to use RO water, deionized water, distilled water, purified water, etc.

The content of component (D) is preferably 20% by mass or more and 90% by mass or less.

(Component (E): Nonionic surfactant having an HLB of 10.0 or more)
In this embodiment, in consideration of the storage stability of the preparation, it is preferable to further include a nonionic surfactant having an HLB of 10.0 or more as component (E). A nonionic surfactant having an HLB of 10.0 or more has a relatively large hydrophilic portion and is easily inserted into the gel structure formed by components (A) and (B), which is considered to improve the dispersibility of emulsion droplets. It is more preferable to further include a nonionic surfactant having an HLB of 12.0 or more, since this further improves stability. The HLB of the nonionic surfactant is usually 20.0 or less, and may be 18.0 or less.

Component (E) is not particularly limited, and examples thereof include polyoxyethylene sugar fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene hardened castor oil (hydrogenated castor oil), glycerin fatty acid esters and their alkylene glycol adducts, polyglycerin fatty acid esters and their alkylene glycol adducts, propylene glycol fatty acid esters and their alkylene glycol adducts, polyalkylene glycol fatty acid esters, polyoxyalkylene alkyl ethers, glycerin alkyl ethers, polyoxyethylene alkylphenyl ethers, alkylene glycol adducts of lanolin, polyether-modified silicones, etc., and one or more selected from these can be used. Among these, nonionic surfactants having an HLB of 10.0 or more are preferably nonionic surfactants having a sugar skeleton, since they are compatible with component (B). Examples of nonionic surfactants having a sugar skeleton include polyoxyethylene sugar fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, sucrose fatty acid esters, sugar fatty alcohol ethers, etc. Among these, polyoxyethylene sugar fatty acid esters and polyoxyethylene sorbitan fatty acid esters are more preferred as component (E).

Polyoxyethylene sugar fatty acid esters are polyethylene glycol derivatives of sugar fatty acid esters. Sugar fatty acid esters are compounds obtained by reacting saturated or unsaturated fatty acids having 12 to 22 carbon atoms with sugars or alkyl sugars containing an alkyl group having 1 to 8 carbon atoms. Examples of sugars include glucose, sucrose, galactose, fructose, lactose, mannose, maltose, trehalose, melibiose, raffinose, and ribose. Among them, the sugar fatty acid ester is preferably a fatty acid ester of glucose or an alkyl glucose. The alkyl glucose is an ether of glucose having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, more preferably methyl glucose. A preferred ester can contain a mixture of mono-, di-, tri-, and tetraester derivatives, with at least 50% by weight of mono- and diester derivatives and usually not more than 95% by weight of monoester derivatives based on the total weight of the mixture. Specific examples of sugar fatty acid esters include alkyl glucose palmitates such as methyl glucose palmitate or ethyl glucose palmitate, and alkyl glucose sesquistearate such as methyl glucose sesquistearate. Polyoxyethylene sugar fatty acid esters are preferably polyethylene glycol derivatives of fatty acid esters of glucose or alkyl glucose. The number of moles of polyoxyethylene added is preferably 5 to 30, and more preferably 10 to 25. More specifically, examples of polyoxyethylene sugar fatty acid esters include polyoxyethylene (20) methyl glucose sesquistearate (commercially available products include, for example, GLUCAMATE (registered trademark) SSE-20 (manufactured by Lubrizol)).

Specific examples of polyoxyethylene sorbitan fatty acid esters include polyoxyethylene (POE) (6) sorbitan monooleate (commercially available products include, for example, NIKKOL (registered trademark) TO-106V manufactured by Nikko Chemicals Co., Ltd. (HLB 10.0)), polyoxyethylene (POE) (20) sorbitan monooleate (polysorbate 80, commercially available products include, for example, NIKKOL (registered trademark) TO-10V manufactured by Nikko Chemicals Co., Ltd. and Rheodol (registered trademark) TW-O120V manufactured by Kao Corporation), and polyoxyethylene (POE) (40) sorbitan monooleate (PEG-40 sorbitan oleate, commercially available products include, for example, EMALEX ET-8040 Polyoxyethylene (20) sorbitan trioleate (polysorbate 85, a commercially available product is, for example, NIKKOL (registered trademark) TO-30V manufactured by Nikko Chemicals Co., Ltd. (HLB 11.0)), polyoxyethylene (20) sorbitan monolaurate (polysorbate 20 (a commercially available product is, for example, Rheodol (registered trademark) TW-L 120 manufactured by Kao Corporation)), polyoxyethylene (POE) (60) sorbitan monostearate (polysorbate 60, a commercially available product is, for example, NIKKOL (registered trademark) TS-10V manufactured by Nikko Chemicals Co., Ltd. (HLB 14.9)), polyoxyethylene (POE) (20) sorbitan tristearate (polysorbate 65, a commercially available product is, for example, NIKKOL (registered trademark) TS-30V (HLB 10.5) manufactured by Nikko Chemicals Co., Ltd.), polyoxyethylene (POE) (20) sorbitan isostearate (commercially available products include, for example, NIKKOL (registered trademark) TI-10V manufactured by Nikko Chemicals Co., Ltd. (HLB 15.0)), etc.

Specific examples of polyoxyethylene sorbitol fatty acid esters include POE (6) sorbitol monolaurate (commercially available products include, for example, NIKKOL (registered trademark) GL-1 manufactured by Nikko Chemicals), POE (60) sorbitol tetrastearate (commercially available products include, for example, NIKKOL (registered trademark) GS-460 manufactured by Nikko Chemicals), POE (30) sorbitol tetraoleate (commercially available products include, for example, NIKKOL (registered trademark) GS-430NV manufactured by Nikko Chemicals), POE (40) sorbitol tetraoleate (commercially available products include, for example, NIKKOL (registered trademark) GS-430NV manufactured by Nikko Chemicals), and POE (60) sorbitol tetraoleate (commercially available products include, for example, NIKKOL (registered trademark) GS-460V manufactured by Nikko Chemicals). (manufactured by Nikko Chemicals Co., Ltd.)

Sucrose fatty acid esters are ester compounds consisting of straight-chain or branched fatty acids having 6 to 22 carbon atoms and sucrose. Specific examples of fatty acids include caproic acid, caprylic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, caproleic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, and linoleic acid, as well as mixed fatty acids such as coconut oil fatty acid, palm kernel oil fatty acid, and palm oil fatty acid. Among these, fatty acid compositions mainly composed of lauric acid, myristic acid, isostearic acid, oleic acid, coconut oil fatty acid, palm kernel oil fatty acid, and palm oil fatty acid are more preferred, and lauric acid is the most preferred. In addition, the degree of ester substitution with sucrose can include mono-fatty acid sucrose with a substitution degree of 1, di-fatty acid sucrose with a substitution degree of 2, and tri-fatty acid sucrose with a substitution degree of 3. Of these, it is more preferable that the main component is a mono-fatty acid sucrose with a degree of substitution of 1, and sucrose monostearate is the most preferable.

The numbers in parentheses indicate the number of moles of ethylene oxide added.

Component (E) may be used alone or in combination of two or more types.

HLB indicates the molecular weight of the hydrophilic group portion of the total molecular weight of a nonionic surfactant, and is calculated using Griffin's formula.

The amount of component (E) to be added is 0.01 to 10% by mass, 0.05 to 5% by mass, or 0.1 to 2% by mass of the cosmetic, taking into consideration the stability of the formulation, the ease of removal of the cosmetic, and smooth spreadability.

The total HLB of the nonionic surfactants contained in the cosmetic is preferably 14.2 or more, and more preferably 15.0 or more. The total HLB is the arithmetic mean of the HLB values of each nonionic surfactant based on its blending ratio (mass%).

Total HLB=Σ(HLB _A × A(%)/100)
HLB _A indicates the HLB value of nonionic surfactant A.

A (%) indicates the blending ratio of nonionic surfactant A having an HLB value of _A in the nonionic surfactants.

(powder)
In this embodiment, it is preferable to further include a powder. By adding the powder, the powder penetrates into the gel structure of the component (B) agar and the component (A), and the transfer of the cosmetic is further improved. In addition, by adding the powder, the adhesiveness of the cosmetic to the skin is further improved, and the stickiness of the oil agent can be further reduced.

Powders (or surface-treated powders, if surface-treated) are not particularly limited by shape (plate-like, spindle-like, needle-like, etc.), particle size (aerosol-like, fine particles, pigment-grade, etc.), particle structure (porous, non-porous, etc.), etc., and examples include inorganic powders, glittering powders, organic powders, colored pigments, composite powders, polyethylene terephthalate-aluminum-epoxy laminated powder, polyethylene terephthalate-polymethyl methacrylate laminated powder, etc.

Inorganic powders include carbon black, magnesium carbonate, calcium carbonate, chromium oxide, chromium hydroxide, aluminum silicate, magnesium silicate, magnesium aluminum silicate, titanium oxide, zinc oxide, aluminum oxide, cerium oxide, magnesium oxide, zirconium oxide, iron oxide, mica, synthetic mica, sericite, synthetic sericite, talc, kaolin, silicon carbide, barium sulfate, boron nitride, silica, and glass powder.

Examples of glittering powders include bismuth oxychloride, titanium mica (titanium oxide coated mica), iron oxide treated mica, iron oxide treated titanium mica, organic pigment treated titanium mica, silicon dioxide/titanium oxide coated mica, titanium oxide coated glass powder, iron oxide/titanium oxide coated glass powder, and aluminum powder.

Examples of organic powders include metal soap powders such as zinc laurate, zinc myristate, zinc stearate, magnesium laurate, magnesium myristate, and magnesium stearate, N-acyl lysine, nylon, polymethylsilsesquioxane, crosslinked organopolysiloxane polymers, polystyrene, polyurethane, polyethylene, polypropylene, polymethacrylic acid esters such as polymethylmethacrylate, complexes of polymethylmethacrylate and polyisoprene, polyacrylic acid esters, acrylonitrile-methacrylic acid copolymer powder, and polytetrafluoroethylene. Examples of crosslinked organopolysiloxane polymers include partially crosslinked methylpolysiloxanes such as (dimethicone/vinyl dimethicone) crosspolymer, partially crosslinked methylphenylpolysiloxanes such as (dimethicone/phenyl dimethicone) crosspolymer, partially crosslinked polyether modified silicones such as dimethicone copolyol crosspolymer, partially crosslinked alkyl modified silicones, partially crosslinked alkyl polyether modified silicones such as (lauryl dimethicone-PEG) crosspolymer, and the like. For example, the INCI names include (dimethicone/vinyl dimethicone) crosspolymer, (dimethicone/phenyl vinyl dimethicone) crosspolymer, (dimethicone/vinyl diphenyl dimethicone/methicone) crosspolymer, (dimethicone/lauryl dimethicone) crosspolymer, (diphenyl dimethicone/vinyl diphenyl dimethicone/silsesquioxane) crosspolymer, (vinyl dimethicone/methicone silsesquioxane) crosspolymer, and the like.

Examples of colored pigments include inorganic red pigments such as red iron oxide (red iron oxide), iron hydroxide, and iron titanate, inorganic brown pigments such as gamma-iron oxide, inorganic yellow pigments such as yellow iron oxide and ochre, inorganic black pigments such as black iron oxide and carbon black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate, inorganic blue pigments such as iron blue and ultramarine, lakes made from tar-based dyes using aluminum or the like, lakes made from natural dyes, and synthetic resin powders made by combining these powders. Examples of tar dyes include Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, and Orange No. 207.

Examples of composite powders include titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated titanium mica, zinc oxide-coated titanium mica, barium sulfate-coated titanium mica, organic pigment-treated titanium mica, silicon dioxide-titanium oxide-coated mica, titanium oxide-coated glass powder, iron oxide-titanium oxide-coated glass powder, titanium oxide-containing silicon dioxide, and zinc oxide-containing silicon dioxide.

In particular, the effects of the present invention are more pronounced in makeup cosmetics that contain a relatively large amount of powder, so it is preferable that the powder is a colored powder.

Examples of colored powders include white powders such as titanium oxide; inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate; inorganic brown pigments such as gamma-iron oxide; inorganic yellow pigments such as yellow iron oxide and ocher; inorganic black pigments such as black iron oxide and carbon black; inorganic purple pigments such as mango violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate; inorganic blue pigments such as iron blue and ultramarine; tar-based color pigments or laked tar-based color pigments; natural color pigments or laked natural color pigments; pearl pigments such as titanium oxide-coated mica, iron oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, iron oxide-coated mica titanium, and natural color-coated mica titanium; metal powder pigments such as aluminum powder, copper powder, and stainless steel powder; or composite powders made by combining these powders.

The powder may be surface treated.

Surface treatments include fluorine compound treatment, phospholipid treatment, amino acid treatment, N-acyl amino acid treatment, silica treatment, alumina treatment, aluminum hydroxide treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, silane treatment, oil treatment, polyacrylic acid treatment, metal soap treatment, acrylic resin treatment, metal oxide treatment, etc. These surface treatments may be used alone or in combination of two or more.

Among these surface treatments, fluorine compound treatment, phospholipid treatment, amino acid treatment, and N-acylamino acid treatment are preferred. That is, a preferred embodiment of the present invention further includes component (F) one or more selected from the group consisting of fluorine compound-treated powder, phospholipid-treated powder, amino acid treatment, and N-acylamino acid-treated powder. These surface treatments improve the dispersibility of the powder in the gel structure formed by components (A) and (B), and further improve the ease of cosmetic application, fresh feel, adhesion to the skin, and cosmetic durability.

Examples of fluorine compounds used in the fluorine compound treatment include perfluoroalkyl phosphoric acid and its salts, perfluoropolyether, fluoroalkoxysilane, perfluoroalkylalkoxysilane (e.g., perfluorooctyltriethoxysilane), perfluoropolyether alkyl phosphoric acid and its salts, and perfluoroalkylsilane. Among these, perfluoroalkylalkoxysilane is preferred, and perfluorooctyltriethoxysilane is more preferred, as these are more likely to produce the effects of the present invention.

Examples of phospholipids used in the phospholipid treatment include soybean-derived phospholipids, soybean-derived hydrogenated phospholipids, egg yolk-derived phospholipids, egg yolk-derived hydrogenated phospholipids, and hydrogenated lysophospholipids.

Examples of amino acids used in amino acid processing include proline, hydroxyproline, alanine, glycine, sarcosine, lysine, aspartic acid, glutamic acid, and salts thereof.

Specific examples of N-acyl amino acids in the N-acyl amino acid treatment include lauroyl glutamic acid, myristoyl glutamic acid, stearoyl glutamic acid, oleyl glutamic acid, coconut oil fatty acid acyl glutamic acid, lauroyl aspartic acid, myristoyl aspartic acid, oleyl aspartic acid, coconut oil fatty acid aspartic acid, dilauroyl glutamic acid lysine, lauroyl lysine, palmitoyl sarcosine, and salts thereof.

The amount of the surface treatment agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 10% by mass, relative to the untreated powder.

The average particle size of the surface-treated powder is preferably 0.1 to 100 μm, and more preferably 0.1 to 50 μm. In this specification, the average particle size is measured using a tabletop scanning electron microscope (proX PREMIUM, manufactured by Jasco International) at an acceleration voltage of 5 to 15 kV and a magnification of 1,000 to 25,000 times, and calculated from 50 particles in an arbitrary field of view of the obtained image data.

Conventional methods can be used for the surface treatment. For example, a surface treatment agent and powder particles to be treated are added to a solvent, and the powder particles are stirred in a ball mill or the like. The powder particles are then dried as necessary, washed with water, and filtered repeatedly to remove impurities, and then dried and pulverized to obtain the desired surface-treated powder. In addition, several types of compounds that are surface treatment agents can be used for surface treatment at the same time, or one compound can be used for surface treatment beforehand, and then another compound can be used for surface treatment.

The powders may be used alone or in combination of two or more types.

The lower limit of the powder content is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 15% by mass or more, based on the oil-in-water emulsified solid cosmetic. It is believed that the presence of a certain amount of powder causes the network structure, mainly composed of components (A) and (B), to collapse appropriately, resulting in a formulation that has both elasticity and smooth spreadability. The upper limit of the powder content is not particularly limited, but is preferably 50% by mass or less, based on the oil-in-water emulsified solid cosmetic. From the viewpoint of the ease of removal of the cosmetic and imparting elasticity to the cosmetic, the powder content is more preferably 5 to 35% by mass, based on the oil-in-water emulsified solid cosmetic, and is even more preferably 15 to 25% by mass, because the effects of the present invention are more effectively exhibited. Note that, when the "powder" in the powder content is surface-treated, the powder content is the total content of the surface-treated powder.

(Other ingredients)
In addition to the above-mentioned components, the oil-in-water emulsified solid cosmetic preparation of the present embodiment may appropriately contain surfactants other than component (E), water-soluble polymers other than components (A) and (B), ultraviolet absorbers, preservatives, antioxidants, alcohols, cosmetic ingredients, antibacterial agents, sterols, fragrances, chelating agents (such as EDTA), and the like, as long as the effects of the present invention are not impaired.

The oil-in-water emulsified solid cosmetic of this embodiment can be applied to makeup cosmetics such as foundation, concealer, eye color (eye shadow), eyeliner, eyebrow, mascara, blush, lipstick, and lip gloss; lip cream, sunscreen cosmetics, makeup base, and skin care cosmetics including serum and emulsion, and is preferably a makeup cosmetic such as foundation, eye color, makeup base, sunscreen cosmetics, and blush, which are expected to exhibit the effects of the present application more effectively. Methods of use include using the cosmetic with hands or fingers, and using a puff or sponge by impregnating the cosmetic.

The oil-in-water emulsified solid cosmetic of this embodiment can be produced by any known emulsification method without any particular limitations. Specific examples include dispersion emulsification, phase inversion emulsification, and phase inversion temperature emulsification. As a production method, for example, component (C) is added to components (B) and (D) to emulsify, component (A) is added thereto, the mixture is heated to melt, degassed, poured into a dish or jar, and cooled to room temperature to solidify.

The effects of the present invention will be explained using the following examples and comparative examples. In the examples, the terms "parts" and "%" may be used, but unless otherwise specified, they represent "parts by mass" or "% by mass." Furthermore, unless otherwise specified, each operation is carried out at room temperature (25°C).

Examples 1 to 23 and Comparative Examples 1 to 7: Make-up Cosmetics Make-up cosmetics having the formulations shown in Table 1 below were prepared.

(Production method)
1. Mix component (8) and a portion of purified water (component (32)) and dissolve at 90°C.
2. At about 80°C, add a mixture of components (9) to (11) and components (12) to (18) to step 1, and emulsify.
3. At about 80°C, add the mixture of components (1) to (7) and a portion of purified water (component (32)) to step 2 and mix.
4. At around 80°C, a mixture of triethanolamine (component (19)) and a portion of purified water (component (32)) is added to 3. to neutralize.
5.4. Cool to below 40°C.
6. Add a mixture of some of components (20) and (21), and then add a mixture of components (22) to (31) and some of component (20) to 5. and disperse the powder.
7.6. is degassed.
8.7. is melted at 90°C, then filled into a jar and cooled to room temperature to solidify.

Evaluation 1: Appropriate amount of product applied to fingers (removal)
A panel of 20 experts conducted a usability test on each sample, and each panelist rated each sample on a four-point scale using the absolute evaluation method described below. The average score was calculated from the total scores of all panelists, and the sample was judged according to the following criteria. Specifically, each sample was filled in a jar and when touched with a finger, it was evaluated as to whether the amount of sample adhering to the sample was appropriate for practical use.
(Evaluation Criteria)
(Score): (Evaluation)
3: The amount of product applied to the finger is appropriate.
2: The amount of product on the finger is slightly too much or slightly too little.
1: Too much or not enough product on the finger.
0: Too much product adheres to fingers, or none adheres to fingers at all.
<Criteria>
(Average score): (Judgment)
2.5 points or more: ◎
2 points or more and less than 2.5 points: ○
1 point or more but less than 2 points: △
Less than 1 point: ×
Evaluation 2: Spreadability after application of cosmetic to skin A use test was conducted for each sample by a panel of 20 experts, who rated each sample on a four-point scale using the absolute evaluation below, and the average score was calculated from the total score of all panelists, and judgment was made according to the following criteria. Specifically, each sample was applied to the skin using a urethane cosmetic application mat, and then the spreadability of the cosmetic was evaluated.
(Evaluation Criteria)
(Score): (Evaluation)
3: Good,
2: Normal,
1: slightly poor,
0: Poor.
<Criteria>
(Average score): (Judgment)
2.5 points or more: ◎
2 points or more and less than 2.5 points: ○
1 point or more but less than 2 points: △
Less than 1 point: ×.

Evaluation 3: Adhesion A test was conducted for each sample by a panel of 20 experts, who each evaluated the sample on a four-point scale using the absolute evaluation method described below, and the average score was calculated from the total score of all the panelists, and the sample was evaluated according to the following criteria. Specifically, each sample was applied to the face, and the panelists evaluated whether they felt the cosmetic adhered to the skin after application to the skin.
(Evaluation Criteria)
(Score): (Evaluation)
3: Good,
2: Normal,
1: slightly poor,
0: Poor.
<Criteria>
(Average score): (Judgment)
2.5 points or more: ◎
2 points or more and less than 2.5 points: ○
1 point or more but less than 2 points: △
Less than 1 point: ×.

Evaluation 4: Makeup Lastingness Each sample was tested by a panel of 20 experts, who rated it on a four-point scale using the absolute evaluation below, and the average score was calculated from the total scores of all the panelists, and judged according to the following criteria. Specifically, an appropriate amount of each sample was applied to the skin, and the makeup lastingness (= duration of the makeup effect) was evaluated as to whether it was sufficient.
(Evaluation Criteria)
(Score): (Evaluation)
3: The makeup lasts well and the cosmetic effect feels sustained for a long time. 2: The makeup lasts well and the cosmetic effect is felt sufficiently, but slightly insufficient. 1: The makeup lasts poorly and the cosmetic effect does not last long enough. 0: It does not adhere to the skin and does not exert any cosmetic effect.
<Criteria>
(Average score): (Judgment)
2.5 points or more: ◎
2 points or more and less than 2.5 points: ○
1 point or more but less than 2 points: △
Less than 1 point: ×.

Evaluation 5: Stability 5-1. Stability (separation)
Each sample was stored at 40° C. for 3 months and then visually evaluated.
(Evaluation Criteria)
◎: No change from immediately after
○: The texture of the sample surface is deteriorated.
△: A small amount of oil droplets are seeping out onto the sample surface.
×: The sample is separated into two layers.

5-2. Stability (shape retention)
Each sample was filled into a jar, which was then stored in an upside-down position at 40° C. for three months, and then visually evaluated.
(Evaluation Criteria)
◎: No change from immediately after
○: The sample surface is slightly softened and part of the sample surface is slightly moving.
△: The sample moved slightly, leaving a gap between the container and the sample. ×: The sample moved and leaked out of the container.

The evaluation results are shown in Table 1.

From the above results, the makeup cosmetics of Examples 1 to 23 achieved good results in all areas including removal, spreadability, adhesion to skin, makeup durability, and stability (separation, shape retention). On the other hand, Comparative Examples 1 to 5, which did not contain component (A) or used other water-soluble polymers instead, showed poor results in all areas except shape retention. Comparative Example 6, which did not contain component (B), showed a significant decrease in shape retention after storage, and also a significant decrease in adhesion to skin.

Example 24: Oil-in-water emulsified solid cosmetic (foundation)
(Ingredients) (Content)
1. (Acrylates/Beheneth-25 Methacrylate) Copolymer (Component A) (*1)
0.3%
2. Agar (ingredient B) (*4) 1.0%
3. PG dicaprylate (ingredient C) 5.0%
4. Squalane (ingredient C) 2.0%
5. Hydrogenated polyisobutene (component C) 1.0%
6. Ethylhexyl methoxycinnamate (ingredient C) 6.0%
7. Diethylaminohydroxybenzoylhexyl benzoate (Component C)
1.5%
8. Bisethylhexyloxyphenol methoxyphenyl triazine (component C)
1.5%
9. Cetostearyl alcohol (ingredient C) 1.0%
10. PEG-80 hydrogenated castor oil (ingredient E) (HLB: 15.0) (*12)
0.3%
11. PEG-20 methylglucose sesquistearate (ingredient E) (HLB: 15.0) (*6) 0.2%
12. PEG-40 hydrogenated castor oil (ingredient E) (HLB: 12.5) (*13)
0.5%
13. Di (C12-15) pareth-8 phosphate (ingredient E) (HLB: 11.5) (*14)
0.2%
14. Polyglyceryl-2 diisostearate (HLB: 4.0) (*15)
0.3%
15. Triethanolamine 0.3%
16. 1,3-butylene glycol 8.0%
17. Glycerin 2.0%
18. Fragrance 0.1%
19. Methylparaben 0.1%
20. Titanium oxide treated with 0.5% lecithin and 3% aluminum hydroxide (ingredient F)
(Average particle size: 0.25 μm) 8.0%
21. Dimethicone, aluminum hydroxide, hydrated silica-treated titanium dioxide (average particle size: 0.030 μm) (* 16) 5.0%
22. 0.5% lecithin treated red iron oxide (ingredient F) 0.3%
23. Lecithin 0.5% treated yellow iron oxide (ingredient F) 2.0%
24. Lecithin 0.5% treated black iron oxide (ingredient F) 0.2%
25. Talc treated with 1% lecithin (ingredient F) (average particle size: 10.5 μm)
3.0%
26. Zinc oxide (average particle size 0.3 μm) 5.0%
27. Purified water (ingredient D) Remaining amount (*12) NIKKOL HCO-80 (manufactured by Nikko Chemicals Co., Ltd.)
(*13) NIKKOL HCO-40 (manufactured by Nikko Chemicals Co., Ltd.)
(*14) NIKKOL DDP-8 (manufactured by Nikko Chemicals Co., Ltd.)
(*15) Cosmo 42V (manufactured by Nisshin Oillio Co., Ltd.)
(*16) SMT-500SAM (manufactured by Teika Co., Ltd.)
(Production method)
A. Component 2 and a portion of purified water (component 27) were heated to 90°C to obtain a dissolution product.
B. Components 3 to 14 were heated at 80° C. to obtain a mixture.
C. At about 80°C, the mixture obtained in B was added to the dissolved material obtained in A and emulsified.
D. At about 80°C, a mixture of component 1 and a portion of purified water (component 27) was added to the emulsion obtained in C and mixed, and then a mixture of component 15 and a portion of purified water (component 27) was further added and neutralized.
E. The mixture obtained in D was cooled to about 40° C., and then a mixture of a part of Component 16 and Components 17 to 19 was added, and further a mixture of Components 20 to 26 and a part of Component 16 was added to obtain a powder dispersion.
F. The dispersion obtained in E was degassed, heated to about 90° C. and dissolved, and then the dissolved material was poured into a container and cooled to room temperature to obtain a solid foundation.

Example 25: Oil-in-water emulsified solid cosmetic (foundation)
(Ingredients) (Content)
1. (Acrylates/Beheneth-25 Methacrylate) Copolymer (Component A) (*1)
0.5%
2. (Acrylates/steareth-20 methacrylate) copolymer (component A) (*2)
0.3%
3. Agar (ingredient B) (*4) 1.0%
4. Agar (ingredient B) (*17) 0.3%
5. Agar (ingredient B) (*18) 0.2%
6. Isotridecyl isononanoate (component C) 2.0%
7. Cetyl ethylhexanoate (ingredient C) 2.0%
8. Diisostearyl malate (ingredient C) 1.0%
9. Dimethicone (ingredient C) 1.5%
10. Diphenylsiloxyphenyl trimethicone (ingredient C) 0.5%
11. (Dimethicone/vinyl dimethicone) crosspolymer 0.5%
12. Ethylhexyl methoxycinnamate (ingredient C) 3.0%
13. Polysilicone-15 (component C) 2.0%
14. Vaseline (ingredient C) 0.3%
15. Dipentaerythrityl hexa(hydroxystearic acid/stearic acid/rosin acid) (ingredient C) 0.2%
16. Tocopherol acetate (ingredient C) 0.1%
17. Behenyl alcohol (ingredient C) 0.5%
18. Stearic acid (ingredient C) 0.5%
19. PEG-30 Phytosterol (ingredient E) (HLB: 18.0) (*19)
0.4%
20. Polysorbate 60 (component E) (HLB: 14.9) (* 20)
0.4%
21. Methyl glucose sesquistearate (HLB: 6.6) (*21)
0.2%
22. Glyceryl stearate (HLB: 4.0) (* 22) 0.5%
23. Triethanolamine 1.3%
24. 1,3-butylene glycol 5.0%
25. DPG 5.0%
26. Mixture of jasmine flower extract, grape leaf extract, peppermint leaf extract, bifidobacterium culture lysate, satozakura flower extract, polyquaternium-51, multiflora rose fruit extract, rugosa rose flower extract, rosa robur extract, water-soluble collagen, royal jelly extract, angelica root extract, rosa centifolia flower extract, damask rose flower water, rosemary leaf extract, maltitol fruit extract, acetyl glutamic acid, theanine, glycine, hydrolyzed hyaluronic acid, and sodium hyaluronate (mixture of beauty ingredients)
1.0%
27. Fragrance 0.1%
28. Phenoxyethanol 0.1%
29. Titanium oxide treated with 3% perfluorooctyltriethoxysilane and 3% aluminum hydroxide (component F) (average particle size: 0.25 μm) 10.0%
30. Red iron oxide treated with 3% perfluorooctyltriethoxysilane (ingredient F)
0.2%
31. Yellow iron oxide treated with 3% perfluorooctyltriethoxysilane (component F)
1.5%
32. Black iron oxide treated with 3% perfluorooctyltriethoxysilane (ingredient F)
0.1%
33. Perfluorooctyltriethoxysilane 3% treated sericite (component F) (average particle size 12.5 μm) 3.0%
34. Hydrogen dimethicone 0.75% treated zinc oxide (average particle size 0.3 μm)
3.0%
35. (Vinyl dimethicone/methicone silsesquioxane) crosspolymer (*23)
1.0%
36. Polymethyl methacrylate (*24) 0.5%
37. Remaining purified water

(*17) Z-10 (Ina Food Industry Co., Ltd.)
(*18) UP-16 (Ina Food Industry Co., Ltd.)
(*19) NIKKOL BPS-30 (manufactured by Nikko Chemicals Co., Ltd.)
(*20) NIKKOL TS-10V (manufactured by Nikko Chemicals Co., Ltd.)
(*21) Glucate SS (manufactured by Lubrizol)
(*22) NIKKOL MGS-AV (manufactured by Nikko Chemicals Co., Ltd.)
(*23) KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(*24) Matsumoto Microsphere M101 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.)
(Production method)
A. Components 3 to 5 and a portion of purified water (component 37) were heated to 90°C to obtain a solution.
B. Components 6 to 22 were heated at 80° C. to obtain a mixture.
C. At about 80°C, the mixture obtained in B was added to the dissolved material obtained in A and emulsified.
D. At about 80°C, a mixture of components 1 and 2 and a portion of purified water (component 37) was added to the emulsion obtained in C and mixed, and then a mixture of component 23 and a portion of purified water (component 37) was further added and neutralized.
E. After cooling the mixture obtained in D to about 40° C., a part of Component 24 and a mixture of Components 25 to 28 were added, and further a mixture of Components 29 to 36 and a part of Component 24 was added to obtain a powder dispersion.
F. The dispersion obtained in E was degassed, heated to about 90° C. and dissolved, and then the dissolved material was poured into a container and cooled to room temperature to obtain a solid foundation.

Example 26: Oil-in-water emulsified solid cosmetic (cheek)
(Ingredients) (Content)
1. (Acrylates/steareth-20 methacrylate) copolymer (component A) (*2)
0.5%
2. Agar (ingredient B) (*4) 1.2%
3. Mineral oil (ingredient C) 5.0%
4. Pentaerythrityl tetraethylhexanoate (component C) 3.5%
5. Tridecyl trimellitate (ingredient C) 1.0%
6. Olive oil (ingredient C) 0.3%
7. Beeswax (ingredient C) 0.2%
8. Sunflower seed oil (ingredient C) 0.1%
9. Paraffin (component C) 0.1%
10. Microcrystalline wax (ingredient C) 0.1%
11. Ceramide 2 (ingredient C) 0.01%
12. Ceramide 3 (ingredient C) 0.01%
13. Polysorbate 80 (ingredient E) (HLB: 15.0) (*5) 0.8%
14. Polyglyceryl-10 myristate (ingredient E) (HLB: 14.0) (*25)
0.5%
15. Polyglyceryl-10 stearate (ingredient E) (HLB: 12.0) (*26)
0.5%
16. Sorbitan sesquiisostearate (HLB: 4.5) (* 27)
0.3%
17. Triethanolamine 0.5%
18. 1,3-butylene glycol 8.0%
19. Diglycerin 1.0%
20. Mixture of water-soluble collagen, sodium acetylated hyaluronate, ascorbic acid, royal jelly extract, and orange flower water (mixture of beauty ingredients) 0.5%
21. Xanthan gum 0.1%
22. Fragrance 0.1%
23. Phenoxyethanol 0.2%
24. Bengala (*28) 0.3%
25. Red No. 226 0.05%
26. Red No. 202 0.04%
27. Yellow No. 4 0.01%
28. Iron oxide coated mica (*29) 0.1%
29. Titanium oxide coated mica (*30) 0.1%
30. Lauroyl lysine 2% treated mica (ingredient F) (average particle size 18 μm)
2.0%
31. Synthetic phlogopite treated with 2% lauroyl lysine (ingredient F) (average particle size 12.5 μm)
1.0%
32. Barium sulfate (average particle size 32.5 μm) 0.5%
33. Silica (*31) 0.3%
34. Purified water remaining amount (*25) NIKKOL Decaglyn 1-M (manufactured by Nikko Chemicals Co., Ltd.)
(*26) NIKKOL Decaglyn 1-SV (manufactured by Nikko Chemicals Co., Ltd.)
(*27) Cosmoll 182V (manufactured by Nisshin Oillio Co., Ltd.)
(*28) R-516P (manufactured by Titanium Industries Co., Ltd.)
(*29) CLOIZONNE CERISE FLAMBE 550Z (manufactured by BASF)
(*30) COSMETICA SUPER WHITE N-8000S (manufactured by CQV)
(*31) God Ball D11-796C (manufactured by Suzuki Oil Industries Co., Ltd.)
(Production method)
A. Component 2 and a portion of purified water (component 34) were heated to 90°C to obtain a dissolution product.
B. Components 3 to 16 were heated at 80° C. to obtain a mixture.
C. At about 80°C, the mixture obtained in B was added to the dissolved material obtained in A and emulsified.
D. At about 80° C., a mixture of component 1 and a portion of purified water was added to the emulsion obtained in C and mixed, and then a mixture of component 17 and a portion of purified water was further added thereto to neutralize.
E. After cooling the mixture obtained in D to about 40° C., a portion of Component 18 and a mixture of Components 19 to 23 were added, and further a mixture of Components 24 to 33 and a portion of Component 18 was added to obtain a powder dispersion.
F. The dispersion obtained in E was degassed, heated to about 90° C. to dissolve, and then the dissolved material was filled into a container and cooled to room temperature to obtain a solid teak.

Example 27: Oil-in-water emulsified solid cosmetic (eye shadow)
(Ingredients) (Content)
1. (Acrylates/steareth-20 itaconate) copolymer (component A) (*3)
0.2%
2. Agar (ingredient B) (*32) 1.0%
3. Tri(caprylic/capric acid)glyceryl (ingredient C) 6.0%
4. Cyclopentasiloxane (ingredient C) 2.0%
5. Isododecane (component C) 2.0%
6. Dimer dilinoleic acid (phytosteryl/isostearyl/stearyl/behenyl) (ingredient C) 0.2%
7. Di(phytosteryl/octyldodecyl) lauroyl glutamate (ingredient C)
0.1%
8. Ascorbyl tetrahexyldecanoate (ingredient C) 0.01%
9. Polysorbate 80 (ingredient E) (HLB: 15.0) (*5) 1.0%
10. PEG-20 glyceryl isostearate (ingredient E) (HLB: 13.0) (*33) 0.5%
11. Steareth-2 (HLB: 8.0) (*34) 0.3%
12. Sodium methyl stearoyl taurate (*35) 0.3%
13. Triethanolamine 0.2%
14. 1,3-butylene glycol 10.0%
15. Ethanol 5.0%
16. Hydroxypropyl methylcellulose (*36) 0.1%
17. Alcaligenes polysaccharides 0.1%
18. Fragrance 0.1%
19. Red iron oxide treated with 3% perfluorooctyltriethoxysilane (ingredient F)
0.2%
20. Yellow iron oxide treated with 3% perfluorooctyltriethoxysilane (component F)
0.5%
21. Black iron oxide treated with 3% perfluorooctyltriethoxysilane (ingredient F)
0.05%
22. Perfluorooctyltriethoxysilane 3% treated sericite (component F) (average particle size 12.5 μm) 3.0%
23. Titanium oxide/tin oxide coated borosilicate (Ca/Al) (*37)
1.0%
24. Titanium oxide/silica-coated mica (*38) 3.0%
25. Titanium oxide/iron oxide coated mica (*39) 1.0%
26. (Fluoride/hydroxide/oxide)/(Mg/K/silicon) (*40) 3.0%
27. Remaining purified water (*32) AX-200 (Ina Food Industry Co., Ltd.)
(*33) EMALEX GWIS-120 (manufactured by Nippon Emulsion Co., Ltd.)
(*34) NIKKOL BS-2 (manufactured by Nikko Chemicals Co., Ltd.)
(*35) NIKKOL SMT (manufactured by Nikko Chemicals Co., Ltd.)
(*36) Metrose 60SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(*37) Microglass Metashine MT1080RS (manufactured by Nippon Sheet Glass Co., Ltd.)
(*38) TIMIRON SPLEMDID RED (Merck)
(*39) TIMICA RADIANT GOLD 222G (manufactured by BASF)
(*40) Micromica MK-200K (manufactured by Katakura Co-op Agri Co., Ltd.)
(Production method)
A. Component 2 and a portion of purified water (component 27) were heated to 90°C to obtain a dissolution product.
B. Components 3 to 12 were heated at 80° C. to obtain a mixture.
C. At about 80°C, the mixture obtained in B was added to the dissolved material obtained in A and emulsified.
D. At about 80°C, a mixture of component 1 and a portion of purified water (component 27) was added to the emulsion obtained in C and mixed, and then a mixture of component 13 and a portion of purified water (component 27) was further added and neutralized.
E. After cooling the mixture obtained in D to about 40° C., a portion of Component 14 and a mixture of Components 15 to 18 were added, and further a mixture of Components 19 to 26 and a portion of Component 14 was added to obtain a powder dispersion.
F. The dispersion obtained in E was degassed, heated to about 90° C. to dissolve, and then the dissolution was poured into a container and cooled to room temperature to obtain a solid eye shadow.

Example 28: Oil-in-water emulsified solid cosmetic (sunscreen)
(Ingredients) (Content)
1. Mixture of (Acrylates/Beheneth-25 Methacrylate) Copolymer (Component A)/PEG-20 Glyceryl Triisostearate/1,3-Butylene Glycol/Sorbitan Sesquiisostearate/PPG-8 Ceteth-20 (Component E) (HLB: 12.5)/Water (*41)
0.8%
2. Agar (ingredient B) (*42) 0.7%
3. Ethylhexyl methoxycinnamate (ingredient C) 6.0%
4. Neopentyl glycol dicaprylate (ingredient C) 3.0%
5. Methyl trimethicone (ingredient C) 3.0%
6. Alkyl benzoate (C12-15) (component C) 2.0%
7. Diethylaminohydroxybenzoylhexyl benzoate (Component C)
2.0%
8. Bisethylhexyloxyphenol methoxyphenyl triazine (component C)
2.0%
9. Methylenebisbenzotriazolyltetramethylbutylphenol (Component C)
1.0%
10. Cetostearyl alcohol (ingredient C) 0.5%
11. Polyhydroxystearic acid (component C) 0.3%
12. PEG-40 sorbitan oleate (ingredient E) (HLB: 16.0) (*43)
0.5%
13. Sucrose stearate (ingredient E) (HLB: 13.0) (* 44)
0.5%
14. Sorbitan palmitate (HLB: 6.7) (* 45) 0.3%
15. Triethanolamine 0.8%
16. 1,3-butylene glycol 5.0%
17. Glycerin 3.0%
18. Methyl gluceth-10 2.0%
19. Carbomer 0.1%
20. Fragrance 0.1%
21. Methylparaben 0.1%
22. Zinc oxide (average particle size: 0.02 μm) 8.0%
23. Talc treated with 1% lecithin (ingredient F) (average particle size: 9.5 μm) 3.0%
24. Boron nitride (*46) 1.0%
25. Purified water (ingredient D) Remaining amount (*41) Nikomurus SE-W (manufactured by Nikko Chemicals Co., Ltd.)
(*42) AX-200 (manufactured by Ina Food Industry Co., Ltd.)
(*43) EMALEX ET-8040 (manufactured by Nippon Emulsion Co., Ltd.)
(*44) TEGO Care SE 121 MB (manufactured by Evonik Japan)
(*45) NIKKOL SP-10V (manufactured by Nikko Chemicals Co., Ltd.)
(*46) CCS102-JA Boron Nitride Powder (manufactured by Momentive Performance Materials Japan, Inc.)
(Production method)
A. Component 2 and a portion of purified water (component 25) were heated to 90°C to obtain a dissolution product.
B. Components 3 to 14 were heated at 80° C. to obtain a mixture.
C. At about 80°C, the mixture obtained in B was added to the dissolved material obtained in A and emulsified.
D. At about 80°C, a mixture of component 1 and a portion of purified water (component 25) was added to the emulsion obtained in C and mixed, and then a mixture of component 15 and a portion of purified water (component 25) was further added and neutralized.
E. The mixture obtained in D was cooled to about 40° C., and then a mixture of a portion of Component 16 and Components 17 to 21 was added, and further a mixture of Components 22 to 24 and a portion of Component 16 was added to obtain a powder dispersion.
F. The dispersion obtained in E was degassed, heated to about 90° C. and dissolved, and the dissolved material was then poured into a container and cooled to room temperature to obtain a solid sunscreen.

Example 29: Oil-in-water emulsified solid cosmetic (cream)
(Ingredients) (Content)
1. (Acrylates/Beheneth-25 Methacrylate) Copolymer (Component A) (*1)
0.3%
2. Agar (ingredient B) (*47) 1.0%
3. Mineral oil (ingredient C) 5.0%
4. Jojoba seed oil (ingredient C) 2.5%
5. Meadowfoam oil (ingredient C) 1.0%
6. Macadamia nut oil (ingredient C) 0.5%
7. Grape seed oil (ingredient C) 0.5%
8. Hydrogenated coconut oil (ingredient C) 0.3%
9. Isohexadecane (component C) 0.2%
10. Polysorbate 20 (ingredient E) (HLB: 16.7) (*7) 0.8%
11. Polysorbate 80 (ingredient E) (HLB: 14.0) (*4) 0.4%
12. Sorbitan stearate (ingredient E) (HLB: 4.5) (* 48)
0.2%
13. Sorbitan oleate (component E) (HLB: 4.3) (* 49)
0.1%
14. Triethanolamine 0.3%
15. 1,3-butylene glycol 10.0%
16. DPG 3.0%
17. (Sodium acrylate/sodium acryloyldimethyltaurate) copolymer
0.2%
18. Acetyl glucosamine, polyquaternium-51, polymethacryloyloxyethyl phosphorylcholine, Artemisia capillaris flower extract, clove extract, royal jelly extract, water-soluble collagen, glycylglycine, hydrolyzed elastin, sodium acetylated hyaluronate, avocado extract, hibiscus flower extract, wakame extract, sake lees extract, sodium PCA, and mixture of mussel glycogen (mixture of beauty ingredients)
0.5%
19. Fragrance 0.2%
20. Phenoxyethanol 0.1%
21. Sodium lauroyl aspartate 1% treated mica (ingredient F) (average particle size: 19 μm) 2.0%
22. Nylon-12 (*50) 0.5%
23. Polymethylsilsesquioxane (*51) 0.5%
24. Purified water (ingredient D) Remaining amount (*47) UP-37 (manufactured by Ina Food Industry Co., Ltd.)
(*48) NIKKOL SS-10V (manufactured by Nikko Chemicals)
(*49) NIKKOL SO-10V (manufactured by Nikko Chemicals)
(*50) Ganz Pearl GPA-550 (manufactured by Aica Kogyo Co., Ltd.)
(*51) Tospearl 2000B (manufactured by Momentive Performance Materials Japan)
(Production method)
A. Component 2 and a portion of purified water were heated to 90°C to obtain a solution.
B. Components 3 to 13 were heated at 80° C. to obtain a mixture.
C. At about 80°C, the mixture obtained in B was added to the dissolved material obtained in A and emulsified.
D. At about 80°C, a mixture of component 1 and a portion of purified water (component 24) was added to the emulsion obtained in C and mixed, and then a mixture of component 14 and a portion of purified water (component 24) was further added and neutralized.
E. After cooling the mixture obtained in D to about 40° C., a portion of Component 15 and a mixture of Components 16 to 20 were added, and further a mixture of Components 21 to 23 and a portion of Component 15 was added to obtain a powder dispersion.
F. The dispersion obtained in E was degassed, heated to about 90° C. and dissolved, and then the dissolved material was filled into a container and cooled to room temperature to obtain a solid cream.

The oil-in-water emulsion solid cosmetics of Examples 24 to 29 achieved good results in all areas, including removal, spreadability, adhesion to the skin, cosmetic durability, and stability (separation and shape retention).

Claims (6)

The following components (A) to (D):
(A) a polymer comprising: (a) a structural unit derived from a monomer selected from the group consisting of (meth)acrylic acid and an alkyl (meth)acrylate; and (b) a structural unit derived from a monomer selected from the group consisting of a polyoxyalkylene alkyl ether itaconate and a polyoxyalkylene alkyl ether (meth)acrylate;
(B) agar,
An oil-in-water emulsion solid cosmetic preparation comprising (C) an oil agent and (D) water ,
The blending amount of the component (A) is 0.001 to 4 mass %, and the blending amount of the component (B) is 0.01 to 10 mass %. 2. The oil-in-water emulsion solid cosmetic preparation according to claim 1, wherein the blending amount of the component (C) is 3 to 50 mass % . The oil-in-water emulsion solid cosmetic according to claim 1 or 2 further comprises component (E) a nonionic surfactant having an HLB of 10.0 or more. The oil-in-water emulsion solid cosmetic according to claim 3, wherein the component (E) is a nonionic surfactant having a sugar skeleton. The oil-in-water emulsion solid cosmetic according to any one of claims 1 to 4, wherein the mass ratio (A)/(B) of the component (A) to the component (B) is 0.001 to 15. The oil-in-water emulsified solid cosmetic preparation according to any one of claims 1 to 5, further comprising one or more components selected from the group consisting of a fluorine compound-treated powder, a phospholipid- treated powder , an amino acid-treated powder, and an N-acylamino acid-treated powder.