JP7657456B2 - Water-in-oil emulsion cosmetics - Google Patents

Description

The present invention relates to a water-in-oil emulsion cosmetic that has excellent storage stability and is less likely to dry out when applied to the skin. More specifically, the present invention relates to a water-in-oil emulsion cosmetic that contains a silylated peptide-silane compound copolymer or a silylated amino acid-silane compound copolymer, a specific surfactant, and a specific oil.

Water-in-oil emulsion cosmetics are prepared using oil, water, and an emulsifier, but conventional emulsifiers used in water-in-oil emulsion cosmetics tend to cause stickiness when applied to the skin, and there has been a demand for water-in-oil emulsion cosmetics that are non-sticky and have an excellent feel when used. In addition, compared to oil-in-water emulsion cosmetics, water-in-oil emulsion cosmetics have the disadvantage that the dispersed phase (aqueous phase) is more likely to coalesce and separate over time, making it difficult to obtain stable water-in-oil emulsion cosmetics, and a solution to this problem has been sought. Therefore, there has been a demand for a water-in-oil emulsifier that can produce water-in-oil emulsion cosmetics that do not cause a sticky feeling when applied to the skin and have excellent stability over time.

The present inventors therefore developed a silylated peptide-silane compound copolymer or a silylated amino acid-silane compound copolymer, which is obtained by condensation polymerization in an aqueous solution of one or more silylated peptides or silylated amino acids having two hydroxyl groups directly bonded to silicon atoms, and one or more silane compounds which generate two or more hydroxyl groups directly bonded to silicon atoms upon hydrolysis, as a water-in-oil emulsifier, and proposed a water-in-oil emulsion cosmetic that is less sticky and has good stability over time (Patent Documents 1, 2, and 3).

However, in water-in-oil emulsion cosmetics that contain silylated peptide-silane compound copolymer or silylated amino acid-silane compound copolymer as an emulsifier, depending on the type of oil, there is a problem that the viscosity changes during storage, which in turn changes the feel when applied to the skin. In addition, when the cosmetic is spread thinly on the skin, the dispersed phase (aqueous phase) coalesces and water droplets appear (referred to as "water-dropping"), which may impair the feel when applied.

JP 2001-048732 A JP 2004-331616 A JP 2017-132713 A

The present invention aims to solve the problems of the past and provide a water-in-oil emulsion cosmetic that contains a silylated peptide-silane compound copolymer or a silylated amino acid-silane compound copolymer as an emulsifier, which does not separate or float oilily during storage, has little change in viscosity, and is excellent in stability, and is also unlikely to cause water runoff when applied to the skin, resulting in an excellent feel when used.

As a result of intensive research in light of the above-mentioned circumstances, the present inventors have discovered that a water-in-oil emulsion cosmetic containing component (A): a silylated peptide-silane compound copolymer or a silylated amino acid-silane compound copolymer, component (B): a silicone surfactant or a nonionic surfactant, and component (C): an oil selected from the group consisting of ester oil, silicone oil, and hydrocarbon oil, provides a cosmetic that is less water-repellent when applied to the skin, has an excellent feel when used, and further has excellent storage stability, thereby completing the present invention.

The first aspect of the present invention is a water-in-oil emulsion cosmetic,
(A) a compound represented by the following general formula (I):

[In the formula, R ¹ represents a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, R ² represents a residue of a side chain of a basic amino acid having an amino group at the end of the side chain excluding the terminal amino group, R ³ represents an amino acid side chain other than the side chain constituting R ² , A is a bond representing at least one group selected from _{the group consisting of -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -(CH 2 ) 3 OCH 2 CH ( OH ) CH 2 -} , -(CH ₂ ) ₃ S-, -(CH ₂ ) 3 NH- and -(CH 2 ) ₃ OCOCH ₂ CH ₂ -, x is 0 to 50, y is 1 to 100 and x+y is 1 to 100 (wherein x and y only represent the number of amino acids and do not represent the order of the amino acid sequence. In addition, when two R ¹ may be the same or different.) with a silylated peptide or silylated amino acid represented by the following general formula (II):
R ⁴ _m Si(OH) _p Y _(4-pm) (II)
[wherein m is an integer of 0 to 2, p is an integer of 2 to 4, m+p≦4, R ⁴ is an organic group in which a carbon atom is directly bonded to a silicon atom, m R ^4s may be the same or different, and (4−p−m) Ys are alkoxy groups or hydrogen atoms],
(B) a silicone surfactant or a nonionic surfactant,
(C) an oil selected from ester oil, silicone oil, and hydrocarbon oil;
and further characterized in that the mass ratio (B)/(A) of the component (B) to the component (A) is 0.01 or more and 1.0 or less.

The second aspect of the present invention is the water-in-oil type emulsion cosmetic composition according to the first aspect of the present invention, further comprising one or more components selected from the group consisting of glycerin, diglycerin, glyceryl ascorbic acid, and salts thereof as component (D).
By incorporating component (D), the temporal stability of the water-in-oil emulsion cosmetic of the present invention is not impaired, and it is possible to impart preferable skin care effects when applied to the skin, such as moisturizing effects, antioxidant effects, melanin production inhibitory effects, and collagen production promoting effects. The second aspect of the present invention corresponds to this preferable embodiment.

The third aspect of the present invention is the water-in-oil emulsion cosmetic of the second aspect of the present invention, characterized in that the component (D) contains bisglyceryl ascorbic acid. From the viewpoint of the high usability when incorporated into the cosmetic, the component (D) is preferably bisglyceryl ascorbic acid, particularly 2,3-di-O-glyceryl ascorbic acid, and it is preferable for the cosmetic to contain these. The third aspect of the present invention corresponds to this preferred embodiment.

A fourth aspect of the present invention is the water-in-oil type emulsion cosmetic composition according to any one of the first to third aspects of the present invention, characterized in that component (B) is selected from the group consisting of polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, cetyl PEG/PPG-10/1 dimethicone, polyglyceryl-6 polyricinoleate, and polyglyceryl-2 dipolyhydroxystearate.
By selecting the above-mentioned component (B) as the surfactant, it is possible to provide a water-in-oil emulsion cosmetic which is particularly excellent in terms of storage stability and the small amount of water that is removed when applied to the skin. The fourth aspect of the present invention corresponds to this preferred embodiment.

The fifth aspect of the present invention is a water-in-oil emulsion cosmetic according to any one of the first to fourth aspects of the present invention, characterized in that component (C) is selected from the group consisting of caprylic/capric triglyceride, decamethylcyclopentasiloxane, dimethicone, squalane and mineral oil. By selecting the oil agent of component (C) from the above, the water-in-oil emulsion cosmetic of the present invention exhibits a more excellent feeling when used, which is preferable. The fifth aspect of the present invention corresponds to this preferable embodiment.

The present invention relates to a water-in-oil emulsion cosmetic comprising a silylated peptide-silane compound copolymer or a silylated amino acid-silane compound copolymer, a specific surfactant, and a specific oil, and is a cosmetic with excellent stability and minimal change in viscosity during storage. In addition, when applied to the skin, it exhibits excellent usability with minimal water removal.
Furthermore, when the water-in-oil emulsion cosmetic of the present invention contains component (D): one or more selected from the group consisting of glycerin, diglycerin, glyceryl ascorbic acid, and salts thereof, the water-in-oil emulsion cosmetic is provided with favorable skin care effects when applied to the skin, such as moisturizing effects, antioxidant effects, melanin production inhibitory effects, and collagen production promoting effects, without compromising stability, and is also less sticky.

The components constituting the water-in-oil emulsion cosmetic of the present invention are component (A): silylated peptide-silane compound copolymer or silylated amino acid-silane compound copolymer, component (B): silicone surfactant or nonionic surfactant, and component (C): oil selected from the group consisting of ester oil, silicone oil, and hydrocarbon oil, and further component (D): one or more selected from the group consisting of glycerin, diglycerin, glyceryl ascorbic acid, and salts thereof, and the form of the water-in-oil emulsion cosmetic of the present invention are specifically described below.

[Component (A): Silylated peptide-silane compound copolymer or silylated amino acid-silane compound copolymer]
The silylated peptide-silane compound copolymer or silylated amino acid-silane compound copolymer of component (A) can be synthesized by the methods disclosed in Patent Documents 1 and 3.

Specifically, the copolymer can be synthesized by condensation polymerization of one or more silylated peptides or silylated amino acids represented by the general formula (I) with one or more silane compounds represented by the general formula (II) in an aqueous solution. The reaction molar ratio of the silylated peptides or silylated amino acids to the silane compounds is usually in the range of (silylated peptides or silylated amino acids):(silane compounds)=1:20 to 1:80.
After the above-mentioned polycondensation, a compound represented by the following general formula (III):
R ⁵ ₃ Si(OH) (III)
[wherein the three ^R5 's are organic groups in which a carbon atom is directly bonded to a silicon atom, and the three ^R5 's may be the same or different] is further added in an aqueous solution to a silane compound represented by the following formula:
As the component (A), one selected from the silylated peptide-silane compound copolymer and the silylated amino acid-silane compound copolymer may be used alone, or two or more of them may be used in combination.

The silylated peptide represented by the general formula (I) is a peptide in which a group represented by the formula R ¹ Si(OH) ₂ A- is bonded to an amino group, and examples of the peptide include natural peptides, synthetic peptides, protein hydrolysates, etc. Among these, protein hydrolysates are preferred because of their ease of availability and ease of control of the number average molecular weight of the peptide portion.

The protein hydrolysate is a peptide obtained by partially hydrolyzing a protein with an acid, an alkali, an enzyme, or a combination thereof. Examples of the protein source include animal proteins, vegetable proteins, and proteins derived from microorganisms. Examples of animal proteins include collagen (including its modified form, gelatin), keratin, silk (fibroin or sericin), casein, conchiolin, elastin, protamine, egg yolk protein and egg white protein of chicken eggs, etc. Examples of vegetable proteins include proteins contained in soybeans, wheat, rice (rice bran), sesame, peas, corn, potatoes, etc. Examples of proteins derived from microorganisms include yeast fungi of the genera Saccharomyces, Candida, and Endomycopsis, yeast proteins isolated from yeast fungi called brewer's yeast and sake yeast, proteins isolated from mushrooms (basidiomycetes) and chlorella, and spirulina protein derived from seaweed.

From the viewpoint of industrial availability, the silylated peptide of the silylated peptide-silane compound copolymer is preferably silylated hydrolyzed silk or silylated hydrolyzed collagen.

The silylated amino acid represented by the general formula (I) is an amino acid in which a group represented by the formula R ₁ Si(OH) ₂ A- is bonded to the amino group of an amino acid, and the amino acid is not particularly limited and may be any amino acid that is normally used in cosmetics. Any of acidic amino acids such as aspartic acid, glutamic acid, and cystic acid, neutral amino acids such as glycine, alanine, serine, threonine, methionine, cysteine, valine, leucine, isoleucine, phenylalanine, tyrosine, proline, hydroxyproline, tryptophan, asparagine, and glutamine, and basic amino acids such as arginine, lysine, histidine, and ornithine may be used.

From the viewpoint of high stability of the water-in-oil emulsion cosmetic of the present invention, the silylated amino acid of the silylated amino acid-silane compound copolymer is preferably silylated serine, silylated alanine, silylated arginine, silylated glycine, silylated proline or silylated glutamic acid.

To obtain the water-in-oil emulsion cosmetic of the present invention, a commercially available product containing a silylated peptide-silane compound copolymer may be used to incorporate component (A). An example of such a commercially available product is Protesil WO ((hydrolyzed silk/PG propylmethylsilanediol) crosspolymer + hydrogenated polyisobutene + water) manufactured by Seiwa Kasei Co., Ltd.

The content of component (A) is not particularly limited, but is preferably 0.4 to 3.5% by mass, and more preferably 0.8 to 2.5% by mass, relative to the total mass of the emulsified cosmetic. If the content is less than this, the emulsifier may not be sufficiently effective, and if the content is greater than this, sufficient effects commensurate with the cost will not be seen.

[Component (B): Silicone Surfactant or Nonionic Surfactant]
The silicone surfactant or nonionic surfactant of component (B) contained in the water-in-oil emulsion cosmetic of the present invention is not particularly limited as long as it is one that is usually used in cosmetics.

Examples of the silicone surfactant include PEG-11 methyl ether dimethicone, PEG/PPG-20/22 butyl ether dimethicone, PEG-9 dimethicone, PEG-3 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-32 methyl ether dimethicone, cetyl PEG/PPG-10/1 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, methylpolysiloxane, cetyl methylpolysiloxane, ... Examples include polyether-modified silicones such as polysiloxane-poly(oxyethylene-oxypropylene)methylpolysiloxane copolymer, poly(oxyethylene-oxypropylene)methylpolysiloxane copolymer, and (dimethicone/(PEG-10/15)) crosspolymer; polyglycerin-modified silicones such as polyglyceryl-3 polydimethylsiloxyethyl dimethicone and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone; and dimethylsiloxane-methylcetylsiloxane copolymer.

Examples of the nonionic surfactants include polyglycerin fatty acid esters such as polyglyceryl-2 dipolyhydroxystearate, PEG-30 dipolyhydroxystearate, polyglyceryl-6 polyricinoleate, polyglyceryl-6 laurate, and polyglyceryl-2 isostearate; alkyl glucosides such as decyl glucoside, caprylyl/capryl glucoside, cetearyl glucoside, arachidyl glucoside, (C12-20) alkyl glucoside, coconut oil alkyl glucoside, myristyl glucoside, heptyl glucoside, and lauryl glucoside; sorbitan monolaurate, sorbitol, and sorbitol. Examples include sorbitan fatty acid esters such as sorbitan monopalmitate; glycerin fatty acid esters and their alkylene oxide adducts, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene alkylphenols, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene alkylphenyl formaldehyde condensates, polyoxyethylene sterols and derivatives thereof, polyoxyethylene lanolin and derivatives thereof, polyoxyethylene beeswax derivatives, sucrose fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, etc.

Among the silicone surfactants of component (B), polyether-modified silicone or polyglycerin-modified silicone is preferred from the viewpoint of small change in viscosity during storage, and among these, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, cetyl PEG/PPG-10/1 dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone are preferred. As the nonionic surfactant, polyglycerin fatty acid ester is preferred, and among these, polyglyceryl-2 dipolyhydroxystearate and polyglyceryl-6 polyricinoleate are preferred.
The surfactant of component (B) may be used alone or in combination of two or more.

The content of component (B) is not particularly limited, but is preferably 0.05 to 2% by mass, and more preferably 0.1 to 1.5% by mass, relative to the total mass of the emulsion cosmetic. If the content is less than this, the storage stability of the emulsion cosmetic may decrease, and if it is increased, sufficient effects commensurate with the increased content may not be obtained.

The mass ratio of component (B) to component (A) [component (B)/component (A)] is 1.0 or less, and more preferably 0.7 or less, from the viewpoint of storage stability of the water-in-oil emulsion cosmetic. If the mass ratio of component (B) to (A) is greater than this range, the feeling of use when applied to the skin may be impaired, or it may be difficult to prepare a stable water-in-oil emulsion cosmetic. On the other hand, the mass ratio [component (B)/component (A)] is 0.01 or more, and more preferably 0.1 or more. If the mass ratio is less than this range, the effect of adding component (B) is often not fully obtained.

[Component (C): Oil]
The oil agent of component (C) contained in the water-in-oil emulsion cosmetic of the present invention is selected from ester oil, silicone oil, and hydrocarbon oil, and among these, any oil that is usually used in cosmetics can be used without any particular limitation.

Ester oils include diisopropyl adipate, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, alkyl glycol monoisostearate, isocetyl isostearate, isostearyl isostearate, isopropyl isostearate, propylene glycol isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, erythrityl triethylhexanoate, 2-ethylhexyl hydroxystearate, hexa(hydroxystearic acid/stearic acid/rosin acid)dipentaerythritol ... Taethrityl, dipentaerythrityl tetra(hydroxystearate/isostearate), dipentaerythrityl hexahydroxystearate, glyceryl (ethylhexanoate/stearic acid/adipic acid), pentaerythritol tetra-2-ethylhexanoate, pentaerythrityl tetraoctanoate, pentaerythrityl tetraisostearate, cetyl 2-ethylhexanoate, oleyl oleate, octyldodecyl oleate, ethyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, palmitate Isopropyl phosphate, cetyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, dipentaerythritol fatty acid esters, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, octyldodecyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, 2-ethylhexyl methoxycinnamate, diisostearyl malate, dipentaerythrityl hexa(behenic acid/benzoic acid/ethylhexanoic acid), alkyl benzoate (C12-15), glycol triisooctanoate Ceryl, glyceryl triisostearate, glyceryl (diisostearate/hydrogenated rosin acid), diglyceryl diisostearate, diglyceryl triisostearate, diglyceryl tetraisostearate, decaglyceryl decaisostearate, glyceryl triisopalmitate, glyceryl trimyristate, diglyceryl myristate isostearate, tritridecyl trimellitate, tri(caprylic acid/capric acid), glyceryl tri-2-ethylhexanoate, tri(caprylic acid/capric acid/myristic acid/stearic acid), N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di(phytostearyl/2-octyldodecyl) N-lauroyl-L-glutamate, etc.

Examples of silicone oils include dimethyl silicone oils such as methyl polysiloxane, dimethyl polysiloxane (dimethicone), and highly polymerized methyl polysiloxane; methyl phenyl silicone oils such as methyl phenyl polysiloxane; cyclic silicone oils such as methyl cyclo polysiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, and dodecamethyl cyclohexasiloxane; amino-modified silicones such as aminopropyl methyl siloxane-dimethyl siloxane copolymer, aminoethyl aminopropyl methyl siloxane-dimethyl siloxane copolymer, and aminoethyl aminopropyl methyl siloxane-dimethyl siloxane copolymer; modified silicones such as carboxy-modified silicone, alkoxy-modified silicone, fatty acid-modified silicone, alcohol-modified silicone, aliphatic alcohol-modified silicone, epoxy-modified silicone, fluorine-modified silicone, and alkyl-modified silicone; methyl hydrogen polysiloxane, dimethiconol, and the like.

Examples of hydrocarbon oils include (C13-15) alkanes, (C15-19) alkanes, (C18-21) alkanes, (C21-28) alkanes, mineral oils, liquid paraffin, light isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomers, squalane, synthetic squalane, vegetable squalane, hydrogenated polyisobutene, hydrogenated (tetradecenyl/methylpentadecene), isododecane, polybutene, polyisobutene, isohexadecane, (C13,14) isoparaffin, and petrolatum.

Of the above-mentioned component (C), tri(caprylic/capric acid)glyceryl, decamethylcyclopentasiloxane, dimethicone, mineral oil, and squalane are preferably used from the viewpoint of good skin compatibility and non-stickiness when applied to the skin.
The oil agent of component (C) may be used alone or in combination of two or more.

The content of the component (C) is not particularly limited, but is preferably 10 to 30% by mass, and more preferably 15 to 25% by mass, relative to the total mass of the emulsion cosmetic. If the content is less than this, the storage stability of the emulsion cosmetic may decrease, and if it is more than this, it may affect the feel when used, such as increasing stickiness.

[Component (D): one or more selected from the group consisting of glycerin, diglycerin, glyceryl ascorbic acid, and salts thereof]
(Glycerin, diglycerin)
The glycerin and diglycerin of component (D) contained in the water-in-oil emulsion cosmetic of the present invention are not particularly limited as long as they are components normally used in cosmetics, and commercially available products can be used. Specific examples include concentrated glycerin for cosmetics and diglycerin 801 manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.

The content of glycerin and diglycerin is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass, based on the total mass of the cosmetic. If the content is less than this range, the moisturizing effect may be insufficient when applied to the skin, and if the content is more than this range, the stability over time of the cosmetic may decrease.

(Glyceryl ascorbate and its salts)
The glyceryl ascorbic acid as component (D) contained in the water-in-oil emulsion cosmetic of the present invention is an ascorbic acid derivative in which one or more glyceryl groups are added to the 2-, 3-, 5-, or 6-position of ascorbic acid, and specific examples include the compounds shown below.
In the following examples, glyceryl refers to a group represented by HOCH ₂ -CH(OH)-CH ₂ - or HOCH ₂ -CH(CH ₂ OH)-,
Alkyl refers to a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a behenyl group, or the like.
Alkenyl refers to a vinyl group, an allyl group, a butenyl group, an isobutenyl group, a crotyl group, an octenyl group, a decenyl group, a dodecenyl group, etc.
Acyl refers to a formyl group, an acetyl group, a propionyl group, a butyryl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonyl group, a decanoyl group, an undecanoyl group, a dodecanoyl group, a tetradecanoyl group, a hexadecanoyl group, an eicosanoyl group, a hexadecenoyl group, an octadecenoyl group, an octadecatrienoyl group, an icosatetraenoyl group, an isooctanoyl group, an isopalmitoyl group, an isostearoyl group, a 2-propylpentanoyl group, a 2-butylhexanoyl group, a 2-pentylheptanoyl group, and the like.

Glyceryl ascorbic acid includes 2-O-glyceryl ascorbic acid, 3-O-glyceryl ascorbic acid, 5-O-glyceryl ascorbic acid, 6-O-glyceryl ascorbic acid, 2,3-di-O-glyceryl ascorbic acid, 2,3,5,6-tetra-O-glyceryl ascorbic acid, 2-O-diglyceryl ascorbic acid, 3-O-diglyceryl ascorbic acid, 2,3-di-O-diglyceryl ascorbic acid, 2-O-glyceryl-3-O-alkyl ascorbic acid, 2-O -Alkyl-3-O-glyceryl ascorbic acid, 2-O-alkyl glyceryl ascorbic acid, 3-O-alkyl glyceryl ascorbic acid, 2-O-glyceryl-5-O-acylascorbic acid, 2-O-glyceryl-6-O-acylascorbic acid, 2-O-glyceryl-3-O-alkenyl ascorbic acid, 2-O-alkenyl-3-O-glyceryl ascorbic acid, 2-O-alkenyl glyceryl ascorbic acid, 3-O-alkenyl glyceryl ascorbic acid, etc.

Among the above examples, glyceryl ascorbic acid that is easily available industrially and can fully exert the effects of the present invention is preferably 2-O-glyceryl ascorbic acid, 3-O-glyceryl ascorbic acid, or bisglyceryl ascorbic acid, and among these, bisglyceryl ascorbic acid such as 2,3-di-O-glyceryl ascorbic acid is more preferable.

Examples of salts of glyceryl ascorbic acid include metal salts such as potassium salts and sodium salts, and ammonium salts such as triethanolamine salts, 2-amino-2-methyl-1,3-propanediol salts, and 2-amino-2-methyl-1-propanol salts.

Commercially available products can be used as glyceryl ascorbic acid. For example, Amitose DGA manufactured by Seiwa Kasei Co., Ltd. can be used as 2,3-di-O-glyceryl ascorbic acid.

In the water-in-oil emulsion cosmetic of the present invention, one selected from the group consisting of glycerin, diglycerin, glyceryl ascorbic acid, and salts thereof may be used alone, or two or more may be used in combination.

The content of glyceryl ascorbic acid or its salt is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, based on the total mass of the cosmetic. If the content of glyceryl ascorbic acid or its salt is less than this range, it will be difficult to obtain the desired skin care effect. On the other hand, if the content is more than this range, the effect will not be commensurate with the increased amount.

The water-in-oil emulsion cosmetic of the present invention may contain water in addition to the above-mentioned components (A) to (D). Furthermore, other components, such as those normally used in cosmetics, may be included as appropriate depending on the intended use, so long as the effects and stability of the water-in-oil emulsion cosmetic are not impaired.

For example, other ingredients that are typically used in cosmetics, such as surfactants other than component (B), oily ingredients other than component (C), moisturizers, polymeric compounds such as thickeners, whitening agents, texture improvers, drugs, UV absorbers, proteins, protein hydrolysates or derivatives thereof, amino acids or derivatives thereof, antioxidants, sequestering agents, pH adjusters, preservatives, pigments, colorants, and fragrances, can be appropriately blended as other ingredients.

Examples of surfactants other than component (B) include anionic surfactants such as higher fatty acid soaps, alkyl sulfates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl ether phosphates, alkyl ether carboxylates, acyl methyl taurines, N-acyl-N-methyl-β-alanines, N-acyl glycines, N-acyl glutamates, polyoxyethylene alkyl carboxylates, alkyl phenyl ether sulfonates, alkyl sulfosuccinic acids and their salts, N-acyl sarcosines and their salts, polyoxyethylene coconut oil fatty acid monoethanolamide sulfates, lauroyl oat amino acids and their salts, and cocoyl apple amino acids and their salts;
alkylamine salts such as monoalkylamine salts, dialkylamine salts, and trialkylamine salts; fatty acid amide alkylamines such as stearamidoethyl diethylamine and stearamidopropyl dimethylamine; alkyl quaternary ammonium salts such as monoalkyl quaternary ammonium salts, dialkyl quaternary ammonium salts, trialkyl quaternary ammonium salts, and benzalkonium quaternary ammonium salts; cyclic quaternary ammonium salts such as alkylpyridinium salts; cationic surfactants such as benzethonium chloride,
Examples of amphoteric surfactants include alkyl dimethyl amino acetate betaine, alkyl amido amino acetate betaine, fatty acid amido propyl dimethyl amino acetate betaine, 2-alkyl-N-carboxy-N-hydroxy imidazolinium betaine, alkyl glycine salts, carboxymethyl glycine salts, N-acyl aminoethyl-N-2-hydroxyethyl glycine salts, alkyl amino propionate salts, alkyl imino dipropionate salts, and alkyl hydroxy sulfobetaine.

Other oily components than component (C) include vegetable oils, waxes, higher fatty acids, higher alcohols, and fats and oils.

Examples of vegetable oils include macadamia nut oil, eucalyptus oil, coconut oil, avocado oil, safflower oil, olive oil, palm oil, palm kernel oil, kukui nut oil, shea butter, cocoa butter, almond oil, sunflower oil, rosehip oil, olive squalane, camellia oil, kiwi fruit seed oil, camellia oil, apricot kernel oil, sesame oil, soybean oil, jojoba oil, castor oil, hazelnut oil, meadowfoam oil, peppermint oil, argan oil, carrot oil, lavender oil, sugar squalane, damask rose flower wax, centifolia rose flower wax, jasmine flower wax, camellia oil, and hydrogenated versions of these oils (e.g., hydrogenated castor oil, hydrogenated jojoba oil, hydrogenated palm oil, hydrogenated avocado oil, hydrogenated soybean oil, etc.).

Examples of waxes include carnauba wax, candelilla wax, beeswax, rice bran wax, shellac wax, spermaceti, lanolin, lanolin acetate, isopropyl lanolinate, lanolin alcohol, sunflower seed wax, etc.

Higher fatty acids include isostearic acid, oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc.

Examples of higher alcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, cetearyl alcohol, myristyl alcohol, octanol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, octyldodecanol, hexyldecanol, arachidyl alcohol, (C14-22) alcohol, (C20-22) alcohol, coconut alcohol, glyceryl monocetyl ether, decyltetradecanol, and batyl alcohol.

Examples of fats and oils include Theobroma grandiflorum seed fat, mango seed fat, cacao fat, palm oil, palm kernel oil, coconut oil, shea butter, Shorea sthenoptera fat, African mango kernel fat, avocado fat, sal seed fat, Astrocaryum murumuru fat, Astrocaryum murumuru seed fat, Astrocaryum tucuma seed fat, Garcinia indica seed fat, Tritilia emetica seed fat, Bassia latifolia seed fat, Garcinia indica seed fat, hydrogenated cacao fat, (macadamia seed oil/hydrogenated macadamia seed oil) esters, milk fat, etc.

Examples of moisturizing agents include glycerin, ethoxydiglycol, propylene glycol, maltitol, sorbitol, 1,3-butylene glycol, sodium lactate, polyethylene glycol, sodium pyrrolidone carboxylate, and sodium hyaluronate.

There are no particular limitations on the polymeric compounds such as thickeners, so long as they are used in ordinary cosmetics, and examples thereof include acrylic acid-based thickeners; cellulose-based thickeners such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxyethylcellulose, stearoxyhydroxypropylmethylcellulose, nitrocellulose, and sodium cellulose sulfate; xanthan gum, hydroxypropylxanthan gum, gum arabic, tragacanth gum, carbro gum, guar gum, Caesalpinia spinosa gum, and dextran. Natural thickeners such as stanol; silicone gels such as dimethicone/vinyl dimethicone crosspolymer, dimethicone/phenylvinyl dimethicone crosspolymer, and vinyl dimethicone/lauryl dimethicone crosspolymer; thickeners such as polyvinyl alcohol, polymeric dimethylpolysiloxane, pectin, agar, quince seed, starch, algae colloid, succinoglucan, collagen, gelatin, casein, albumin, carboxymethyl starch, sodium alginate, polyvinyl methyl ether, sodium polyacrylate, polyethylene acrylate, and cationic polymers, as well as other polymer compounds.

Examples of the acrylic acid-based thickeners include polyacrylamide, (hydroxyethyl acrylate/sodium acryloyldimethyl taurate) copolymer, (sodium acrylate/sodium acryloyldimethyl taurate) copolymer, (acrylamide/ammonium acrylate) copolymer, (sodium acrylate/acryloyldimethyl taurate/dimethylacrylamide) crosspolymer, polyacrylate-13, polyacrylate crosspolymer-6, (acrylamidopropyltrimonium chloride/acrylates) copolymer, (ammonium acryloyldimethyl taurate/vinylpyrrolidone). ) copolymer, (ammonium acryloyldimethyltaurate/beheneth-25 methacrylate) crosspolymer, (ammonium acryloyldimethyltaurate/steareth-25 methacrylate) crosspolymer, (acrylates/alkyl acrylate (C10-30)) crosspolymer, (acrylates/steareth-20 methacrylate) copolymer, (acrylates/beheneth-25 methacrylate) copolymer, (acrylates/steareth-20 itaconate) copolymer, steareth-10 allyl ether/acrylates copolymer, carboxyvinyl polymer, etc.

Skin whitening agents include ellagic acid, chamomile extract, licorice extract, rucinol, rosemary extract, arbutin, tranexamic acid, potassium 4-methoxysalicylic acid, ascorbic acid, and ascorbic acid derivatives such as ascorbic acid glucoside and magnesium ascorbyl phosphate.

Texture improvers include amylopectin (amylose), acylated amino acids, polymethylmethacrylate, boron nitride, silica, alumina, aluminum hydroxide, metal soap, silicone powder, polymethylmethacrylate, dimethylsilylated silica, etc.

Examples of the drug include skin roughness prevention agents and anti-inflammatory agents. Examples of skin roughness prevention agents and anti-inflammatory agents include dipotassium glycyrrhizinate, stearyl glycyrrhetinate, methyl salicylate, pyridoxine hydrochloride, allantoin, sea salt, mulberry bark extract, aloe extract, gardenia extract, chamomile extract, licorice extract, mukurosawa extract, apricot kernel extract, scutellaria extract, sweet tea extract, loquat extract, ginkgo extract, hypericum extract, yarrow extract, safflower extract, spruce extract, salvia extract, white birch extract, chinpi extract, peach kernel extract, chinan extract, althea extract, and arnica extract. , carrot extract, peony extract, cnidium extract, gentian extract, cordyceps extract, phellodendron bark extract, inchinko extract, geranium herb extract, peach leaf extract, kumazasa extract, coix seed extract, horse chestnut extract, hawthorn extract, coptis japonica extract, lychee extract, calendula extract, peppermint extract, comfrey extract, butcher's broom extract, mallow extract, centaurea cyanus extract, and toge pear extract. Other examples include hair growth agents, acne agents, dandruff and itching agents, and agents to prevent underarm odor.

Examples of ultraviolet absorbers include benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate, dihydroxydimethoxybenzophenone-sodium sulfonate, 2,4-dihydroxybenzophenone, and tetrahydroxybenzophenone; para-aminobenzoic acid derivatives such as para-aminobenzoic acid, ethyl para-aminobenzoate, glyceryl para-aminobenzoate, amyl para-dimethylaminobenzoate, and octyl para-dimethylaminobenzoate; methoxycinnamic acid derivatives such as ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate (ethylhexyl methoxycinnamate), sodium paramethoxycinnamate, potassium paramethoxycinnamate, and glyceryl di-paramethoxycinnamate mono-2-ethylhexanoate; octyl salicylate, Salicylic acid derivatives such as phenyl salicylate, homomenthyl salicylate, dipropylene glycol salicylate, ethylene glycol salicylate, myristyl salicylate, and methyl salicylate; urocanic acid, ethyl urocanate, 4-tert-butyl-4'-methoxydibenzoylmethane (t-butyl methoxydibenzoylmethane), 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, methyl anthranilate, octocrylene (2-cyano-3,3-diphenylprop-2-enoate-2-ethylhexyl), 2-(4-diethylamino-2-hydroxybenzoyl)hexyl benzoate (diethylamino hydroxybenzoyl hexyl benzoate), ethylhexyl triazone, and bisethylhexyloxyphenol methoxyphenyl triazine, and microcapsules containing the above-mentioned ultraviolet absorbers can also be used.

Examples of proteins, protein hydrolysates and derivatives thereof include whey protein, casein protein, silk protein, wheat protein, rice protein, pea protein, soybean, sesame, collagen, keratin, conchiolin, marine collagen, and other proteins, as well as their hydrolysates or acylated, silylated, cationized, and alkyl esterified derivatives of protein hydrolysates.

Examples of amino acids or derivatives thereof include glycine, alanine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, asparagine, aspartic acid, glutamine, glutamic acid, cystine, cysteine, methionine, tryptophan, proline, histidine, taurine, and other amino acids or salts thereof, as well as acylated, alkylated, esterified, and glycerylated derivatives thereof.

Antioxidants include sodium pyrosulfite, vitamin E or its derivatives, tannin, BHT (butylhydroxytoluene), etc.

Sequestering agents include sodium edetic acid, phosphoric acid, citric acid, phytic acid, etidronic acid, sodium glutamic acid diacetate, etc.

Examples of pH adjusters include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, sodium bicarbonate, and ammonium bicarbonate.

Preservatives include 1,2-alkanediols such as 1,2-pentanediol and 1,2-hexanediol; paraoxybenzoic acid alkyl esters such as methylparaben and propylparaben; glyceryl monoalkyl ethers such as ethylhexylglycerin; benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, levulinic acid, benzyl alcohol, etc.

The above-mentioned ingredients typically used in cosmetics can be used alone or in combination of two or more.

The water-in-oil emulsion cosmetic of the present invention can be used in the form of a liquid, emulsion, paste, cream, gel, etc. Among these, emulsion and cream forms are preferred.
The water-in-oil emulsion cosmetic of the present invention can be widely applied to various cosmetics, and can be used as a beauty essence, milky lotion, makeup base, emollient cream, cleansing cream, hand cream, body cream, foundation, sunscreen milky lotion, sunscreen cream, etc. Among them, it is preferably used as an emollient cream, hand cream, and foundation.

The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. Note that all values shown in the tables of the examples are in mass % relative to the total mass of the cosmetic.

Examples 1 to 7 and Comparative Examples 1 and 2: Creams Creams were prepared by mixing the components (A) to (C) shown in Table 1, adding the other components while stirring with a disper (1,400 rpm), and further stirring for 5 minutes with a disper (3,000 rpm).
The viscosity (25°C) of each of the prepared creams was measured immediately after preparation using a Brookfield LVT viscometer. In addition, the stability and drainage were evaluated using the methods described below. The results are shown in Table 1.

[Stability evaluation]
The creams prepared in Examples 1 to 7 and Comparative Examples 1 and 2 were stored in thermostatic chambers at 25° C. and 50° C. for 4 weeks, and the change in viscosity and emulsion stability were measured and evaluated according to the following criteria. The viscosity measurements were performed using a Brookfield LVT viscometer.
Stability:
⊚: Viscosity change was within ±15% from immediately after preparation. ◯: Viscosity change was between ±15% and ±25% from immediately after preparation. Δ: Viscosity change was within ±25% from immediately after preparation.
×: Oil phase and water phase were separated

[Evaluation of drainage]
The creams prepared in Examples 1 to 7 and Comparative Examples 1 and 2 were stored at 50° C. for 4 weeks, and then applied thinly to the outer side of the forearm and spread out, and visually observed to see whether water was removed.
Draining:
◯: No water leakage occurred.
△: A slight water leak occurred.
×: Water leakage was clearly observed.

In Table 1,
*1 is Protesil WO (trade name, containing 40% by weight of (hydrolyzed silk/PG propylmethylsilanediol) crosspolymer, 50% by weight of hydrogenated polyisobutene, and 10% by weight of water) manufactured by Seiwa Kasei Co., Ltd.
*2: Protesil WO (hydrolyzed silk/PG propylmethylsilanediol) crosspolymer is replaced with silylated alanine-silane compound copolymer.
*3 is KF-6104 manufactured by Shin-Etsu Chemical Co., Ltd.
*4 is KF-6105 manufactured by Shin-Etsu Chemical Co., Ltd.
*5 is KF-6038 manufactured by Shin-Etsu Chemical Co., Ltd.
*6 is KF-6048 manufactured by Shin-Etsu Chemical Co., Ltd.
*7 is Nikko Chemicals' NIKKOL Hexaglyn PR-15,
*8 is DEHYMULS PGPH (all trade names) manufactured by BASF.

Examples 8 to 10: Creams The component (b) shown in Table 2 was mixed while being heated in advance, cooled, and then the component (a) was added. Then, the component (c) was added while stirring with a disper (1,400 rpm), and further stirred with a disper (3,000 rpm) for 5 minutes to prepare a cream.
The viscosity of the prepared creams immediately after preparation was measured in the same manner as in Table 1, and the stability and drainage were also evaluated according to the same criteria as in Table 1. The results are shown in Table 2.

In Table 2, *1, 3, and 7 are the same as those in Table 1.
*9 is KSG-16 manufactured by Shin-Etsu Chemical Co., Ltd.
*10 is KSG-43 manufactured by Shin-Etsu Chemical Co., Ltd.
*11 is KSG-44 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd.

As is clear from the results in Tables 1 and 2, in creams prepared using component (C) as an oil and component (A) as an emulsifier, Examples 1 to 10, which contain a surfactant as component (B), have the same or higher stability at 25°C and 50°C as Comparative Examples 1 and 2, which do not contain component (B), and are clearly superior in terms of resistance to water drainage.

Examples 11 to 15 and Comparative Examples 3 and 4: Moisturizing creams Components (A) to (C) shown in Table 3 were mixed, and component (D) and other components were added while stirring with a disper (1,400 rpm), and the mixture was further stirred for 5 minutes with a disper (3,000 rpm) to prepare moisturizing creams.
The viscosity of the prepared moisturizing cream immediately after preparation was measured in the same manner as in Tables 1 and 2, and the stability was evaluated by storing the cream in a thermostatic chamber at 50° C. for 8 weeks and using the same evaluation criteria as in Tables 1 and 2. Furthermore, the suppression of stickiness was evaluated using the following method and evaluation criteria. The results are shown in Table 3.

[Evaluation of stickiness suppression]
The moisturizing creams and control aqueous solutions prepared in Examples 11 to 15, Comparative Examples 3 and 4 were applied to the inside of the forearm in an amount of 30 mg in an area of 1 cm x 5 cm, spread for 2 minutes, and then dried for 2 minutes. After drying, a dynamic friction coefficient measuring device (product name: Trinity Lab Handy Lab Tester Type: TL701) was used to measure the adhesion (stress) when a load of 100 g was applied to the applied area and then pulled up. Water was added to the component (D) of each Example and Comparative Example to make 100% by mass to obtain the control aqueous solution for each Example and Comparative Example, and the adhesion of the Example or Comparative Example to the Control Example was evaluated according to the following criteria.

⊚: The adhesion strength of the moisturizing cream was lower than that of the control example, and the change in adhesion strength was 50% or more. ◯: The adhesion strength of the moisturizing cream was lower than that of the control example, and the change in adhesion strength was 50% or less.
×: The adhesion of the moisturizing cream is higher than that of the control.

In Table 3, *1, *3, and *7 are the same as those in Tables 1 and 2.
*12 is Amitose DGA (product name, containing 50% bisglyceryl ascorbic acid, 25% glycerin, and 25% water) manufactured by Seiwa Kasei Co., Ltd.

It is clear from the results in Table 3 that Examples 11 to 15, in which component (A) was blended together with components (B), (C), and (D), had storage stability at 50°C equal to or greater than that of Comparative Examples 3 and 4, in which component (A) was not blended.
Glycerin, diglycerin, and glyceryl ascorbic acid are blended into cosmetics to impart moisturizing properties to the cosmetics. The moisturizing creams of Examples 11 to 15 and Comparative Examples 3 and 4 have excellent moisturizing properties, which are believed to be achieved by blending glycerin, diglycerin, and glyceryl ascorbic acid as component (D).

Furthermore, Examples 11 to 15, in which glycerin, diglycerin, or glyceryl ascorbic acid was blended as component (D), also had an excellent effect of suppressing stickiness, and the results in Table 3 show that Examples 11, 12, 14, and 15, in which diglycerin or glyceryl ascorbic acid was blended, were particularly excellent in the effect of suppressing stickiness. From these results, it can be said that when components (A), (B), and (C) are blended, the stickiness problem is suppressed and storage stability is also excellent, even when component (D) glycerin, diglycerin, or glyceryl ascorbic acid is blended.

Claims (4)

A water-in-oil emulsion cosmetic preparation comprising the following components (A), (B), and (C), wherein the mass ratio (B)/(A) of component (B) to component (A) is 0.01 or more and 1.0 or less:
(A) General formula (I):

[In the formula, R ¹ represents a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, R ² represents a residue of a side chain of a basic amino acid having an amino group at the end of the side chain excluding the terminal amino group, R ³ represents an amino acid side chain other than R ² , A is a bond representing at least one group selected _from the group consisting of -CH ₂ -, -CH ₂ CH ₂ -, _{-CH 2} CH ₂ CH _{2 -} , -(CH _{2 ) 3} OCH 2 CH(OH)CH 2 -, -(CH ₂ ) ₃ S-, -(CH ₂ ) ₃ NH- and -(CH 2 ) 3 OCOCH ₂ CH ₂ -, x is 0 to 50, y is 1 to 100, and x + y is 1 to 100 (however, x and y only represent the number of amino acids and do not represent the order of the amino acid sequence. In addition, when two R ¹ may be the same or different.) with a silylated peptide or silylated amino acid represented by the following general formula (II):
R ⁴ _m Si(OH) _p Y _(4-pm) (II)
(Wherein, m is an integer of 0 to 2, p is an integer of 2 to 4, m+p≦4, R ⁴ is an organic group in which a carbon atom is directly bonded to a silicon atom, and m R ^4s may be the same or different. (4-p-m) Ys are alkoxy groups or hydrogen atoms.) (B) A silicone surfactant or a nonionic surfactant selected from the group consisting of polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, cetyl PEG/PPG-10/1 dimethicone, polyglyceryl-6 polyricinoleate, and polyglyceryl-2 dipolyhydroxystearate (C) An oil agent selected from ester oils, silicone oils, and hydrocarbon oils The water-in-oil emulsion cosmetic according to claim 1, further comprising component (D): one or more selected from the group consisting of glycerin, diglycerin, glyceryl ascorbic acid and salts thereof. The water-in-oil emulsion cosmetic according to claim 2, characterized in that the component (D) is bisglyceryl ascorbic acid. 4. The water-in-oil emulsion cosmetic according to claim 1, wherein the component (C) is selected from the group consisting of caprylic/capric triglyceride, decamethylcyclopentasiloxane, dimethicone, mineral oil, and squalane.