JP2005187465A - Emulsified skin care preparation for external use containing salt of higher fatty acid ester of ascorbic acid-2-phosphoric acid ester, method for producing the same, and method for stabilizing the salt of ester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an emulsified skin care preparation for external use (for example, a cosmetic), having improved stability of a salt of a higher fatty acid ester of ascorbic acid-2-phosphoric acid ester expressed by formula (1) (R is a higher fatty acid residue) among ascorbic acid derivatives, and to provide a method for producing the skin care preparation for external use. <P>SOLUTION: The emulsified skin care preparation for external use contains the specified salt of the higher fatty acid ester of ascorbic acid-2-phosphoric acid ester (A), an oily component (B), a surfactant (C), water (D), and a higher alcohol (E). It is preferable that the emulsified skin care preparation for external use further contains a polymer compound (F) and/or a polyhydric alcohol. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides the following formula (1)

（式（１）中、Ｒは、高級脂肪酸残基を表わす。）で表されるアスコルビン酸−２−リン酸エステルの高級脂肪酸エステルの塩を含有し、該エステル塩の安定性に優れる乳化された皮膚外用剤、その製造方法、ならびに該エステル塩の安定化方法に関する。

(In the formula (1), R represents a higher fatty acid residue) and contains a salt of a higher fatty acid ester of ascorbic acid-2-phosphate, which is emulsified with excellent stability of the ester salt. Further, the present invention relates to a skin external preparation, a method for producing the same, and a method for stabilizing the ester salt.

  Ascorbic acid and various derivatives thereof are known as compounds exhibiting effects such as whitening action, antioxidant action, and collagen synthesis promoting action, and are incorporated in pharmaceuticals, cosmetics, feeds and the like.

  In particular, among ascorbic acid derivatives, a compound in which the hydroxyl group at the 2-position of ascorbic acid is converted to a phosphate ester and the hydroxyl group at the 6-position is converted to a higher fatty acid ester (hereinafter also referred to as a higher fatty acid ester of ascorbic acid-2-phosphate). .) And its salts are difficult to oxidize, stable and amphiphilic, so have high affinity to living bodies, and can be rapidly transferred to living tissues such as skin, and can be applied to pharmaceuticals, cosmetics, feeds, etc. Expected.

  However, when this higher fatty acid ester of ascorbic acid-2-phosphate ester and / or its salt is formulated as an external preparation for skin, their stability is impaired, and there is a problem that they are decomposed in the agent. It was.

  Conventionally, emulsified cosmetics that enhance the storage stability of skin external preparation compositions containing ascorbic acid derivatives (ascorbic acid phosphate ester salt and / or ascorbic acid sulfate ester salt) and have a good feeling of use have been known. (See Patent Document 1). However, Patent Document 1 does not describe any effect of enhancing the stability of the higher fatty acid ester of ascorbic acid-2-phosphate represented by the above formula (1) and the salt itself.

  In addition, in the preparation for external use on the skin containing a salt of a higher fatty acid ester of ascorbic acid-2-phosphate, the present inventors adjusted the pH to 7 to 9 to prepare the ester salt agent. An external preparation for skin and cosmetics that have improved the stability and solubility have been already proposed (see Patent Document 2). However, depending on the dosage form of the external preparation for skin, further stabilization may be required for the salt of the higher fatty acid ester of ascorbic acid-2-phosphate present in the agent.

As a result of intensive studies in view of the above circumstances, the present inventors have found that a salt of a higher fatty acid ester of ascorbic acid-2-phosphate ester represented by the above formula (1), an oil component, a surfactant, and water According to the emulsified skin external preparation, which may further contain a high molecular compound and / or a polyhydric alcohol, if necessary, of the ascorbic acid-2-phosphate ester in the agent It has been found that the decomposition and reduction of salts of higher fatty acid esters are suppressed, and the present invention has been completed.
JP 2000-256173 A JP 2003-176217 A

  Among the ascorbic acid derivatives, the present invention is represented by the following formula (1):

（式（１）中、Ｒは、高級脂肪酸残基を表わす。）で表されるアスコルビン酸−２−リン酸エステルの高級脂肪酸エステルの塩の安定性を高めた、乳化された皮膚外用剤（たとえば化粧料）、該皮膚外用剤の製造方法を提供することを課題としている。

(In the formula (1), R represents a higher fatty acid residue.) An emulsified skin external preparation having improved stability of a salt of a higher fatty acid ester of ascorbic acid-2-phosphate represented by ( For example, cosmetics), and to provide a method for producing the skin external preparation.

  Another object of the present invention is to provide a method for stabilizing a salt of a higher fatty acid ester of ascorbic acid-2-phosphate represented by the above formula (1).

That is, the present invention relates to the following matters.
[1] The following formula (1)

（式（１）中、Ｒは高級脂肪酸残基を表わす。）で示されるアスコルビン酸−２−リン酸エステルの高級脂肪酸エステルの塩（Ａ）と、油性成分（Ｂ）と、界面活性剤（Ｃ）と、水（Ｄ）と、高級アルコール（Ｅ）とを含有することを特徴とする乳化された皮膚外用剤。

(In formula (1), R represents a higher fatty acid residue) Ascorbic acid-2-phosphate salt of higher fatty acid ester (A), oil component (B), surfactant ( C), water (D), and higher alcohol (E), The emulsified skin external preparation characterized by the above-mentioned.

[2] The emulsified skin external preparation according to [1], further comprising a polymer compound (F).
[3] The emulsified skin external preparation according to [1] or [2], further comprising a polyhydric alcohol (G).

[4] The emulsified skin external preparation according to any one of [1] to [3], wherein R in the formula (1) is a fatty acid residue having 8 to 22 carbon atoms. .
[5] The emulsification according to the above [4], wherein R in the formula (1) is a residue of lauric acid, myristic acid, palmitic acid, stearic acid, 2-hexyldecanoic acid or isostearic acid Topical skin preparation.

[6] The emulsified skin external preparation described in [5] above, wherein R in the formula (1) is a residue of palmitic acid.
[7] The emulsified skin external preparation according to the above [5], wherein R in the formula (1) is a residue of 2-hexyldecanoic acid.

  [8] Any of [1] to [7] above, wherein the salt (A) of the higher fatty acid ester of ascorbic acid-2-phosphate is Na salt, K salt, Mg salt or Zn salt The emulsified skin external preparation according to claim 1.

  [9] Any of [1] to [8] above, wherein the salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate is contained in an amount of 0.01 to 20% by mass. The emulsified skin external preparation according to claim 1.

[10] At least a dispersion obtained by mixing the oil component (B), the surfactant (C), and the higher alcohol (E),
Following formula (1)

（式（１）中、Ｒは高級脂肪酸残基を表わす。）で表されるアスコルビン酸−２−リン酸エステルの高級脂肪酸エステルの塩（Ａ）を水（Ｄ）に溶解して得られた水溶液とを、
任意の順で混合し、乳化させることを特徴とする乳化された皮膚外用剤の製造方法。

(In formula (1), R represents a higher fatty acid residue.) The salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate represented by the formula (1) was dissolved in water (D). An aqueous solution,
A method for producing an emulsified skin external preparation characterized by mixing and emulsifying in any order.

[11] The method for producing an emulsified skin external preparation as described in [10] above, wherein the aqueous solution is added to the dispersion, mixed and emulsified.
[12] The dispersion is further mixed with a polymer compound (F) and / or a polyhydric alcohol (G
) Is contained, The method for producing an emulsified skin external preparation according to [10] or [11] above.

[13] The emulsified skin external preparation as described in any one of [1] to [9] above, which is a cosmetic.
[14] The following formula (1)

（式（１）中、Ｒは高級脂肪酸残基を表わす。）で示されるアスコルビン酸−２−リン酸エステルの高級脂肪酸エステルの塩（Ａ）を安定化する方法であって、
少なくとも、油性成分（Ｂ）と、界面活性剤（Ｃ）と、水（Ｄ）と、高級アルコール（Ｅ）とを含む乳化した組成物と、
該アスコルビン酸−２−リン酸エステルの高級脂肪酸エステルの塩（Ａ）とを接触させることを特徴とする安定化方法。

(In the formula (1), R represents a higher fatty acid residue), which is a method for stabilizing a salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate ester,
An emulsified composition comprising at least an oil component (B), a surfactant (C), water (D), and a higher alcohol (E);
A stabilizing method comprising contacting the salt (A) of a higher fatty acid ester of the ascorbyl 2-phosphate ester.

[15] The stabilization method according to [14], wherein the emulsified composition further contains a polymer compound (F) and / or a polyhydric alcohol (G).

  According to the emulsified skin external preparation of the present invention, the stability of a higher fatty acid ester salt of ascorbic acid-2-phosphate in the agent can be improved, and its decomposition and reduction can be prevented. Therefore, the emulsified skin preparation for external use of the present invention can be usefully used for all applications of the preparation for skin preparation including cosmetics.

  In addition, according to the method for producing an emulsified skin external preparation of the present invention, an emulsified skin external preparation containing a salt of a higher fatty acid ester of ascorbyl 2-phosphate ester and having excellent stability of the ester salt. An agent can be provided.

  Moreover, according to the method for stabilizing a salt of a higher fatty acid ester of ascorbic acid-2-phosphate of the present invention, decomposition and reduction of the ester salt can be effectively suppressed.

Hereinafter, the present invention will be specifically described.
<Emulsified skin external preparation, method for producing the same>
The emulsified skin external preparation of the present invention comprises at least a salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate represented by the formula (1), an oil component (B), and a surface activity. Emulsification which contains an agent (C), water (D) and a higher alcohol (E), and may further contain a polymer compound (F) and / or a polyhydric alcohol (G) as required. It is the composition of the finished state.

First, each of these components will be described, and then the emulsified skin external preparation of the present invention and the production method thereof will be described.
(A) Salt of higher fatty acid ester of ascorbic acid-2-phosphate
The skin external preparation of the present invention contains a salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate.

  The higher fatty acid ester of ascorbic acid-2-phosphate is a compound represented by the above formula (1), in which ascorbic acid-2-phosphate and a higher fatty acid form an ester, more specifically Specifically, the hydroxyl group at the 6-position of the ascorbic acid-2-phosphate ester and the higher fatty acid residue form an ester bond. The higher fatty acid corresponds to the higher fatty acid residue defined as R in the above formula (1), and is not particularly limited, but a fatty acid having 8 to 22 carbon atoms is preferable. Examples include lauric acid, myristic acid, palmitic acid, stearic acid, 2-hexyldecanoic acid, and isostearic acid. Among these, palmitic acid and 2-hexyldecanoic acid are preferable. Therefore, R in the above formula (1) is preferably a fatty acid residue corresponding to these fatty acids.

  The salt of higher fatty acid ester of ascorbic acid-2-phosphate used in the present invention is a compound in which a phosphate group of the higher fatty acid ester of ascorbic acid-2-phosphate and a base form a salt. It is. Preferred examples of the salt of the higher fatty acid ester of ascorbic acid-2-phosphate include Na salt, K salt, Mg salt, Zn salt and the like. Among these, Na salt is more preferable.

  Specifically, as salts of higher fatty acid esters of ascorbic acid-2-phosphate, for example, ascorbic acid-2-phosphate-6-laurate sodium, ascorbic acid-2-phosphate-6-myristin Acid sodium, sodium ascorbyl-2-phosphate-6-palmitate, sodium ascorbyl-2-phosphate-6-stearate, sodium ascorbyl-2-phosphate-6-isostearate, ascorbic acid-2- Examples include phosphoric acid-6- (2-hexyldecanoic acid) sodium.

These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.
In the emulsified skin external preparation of the present invention, the salt of the higher fatty acid ester of ascorbic acid-2-phosphate is 0.01 to 20% by mass, more preferably 0.05 to 12% in the total amount of the skin external preparation. It is used so as to be contained in an amount of mass%.

  In such an amount, when the salt of a higher fatty acid ester of ascorbic acid-2-phosphate is contained in an emulsified skin external preparation, the transition to the skin is rapid, and the efficacy required for the skin external preparation It is preferable because the effect can be exhibited.

(B) Oil component
The skin external preparation of this invention contains an oil-based component (B).
The oily component used in the present invention is a component having a melting point of usually 100 ° C. or lower and does not substantially mix or dissolve with water. The oily component is not particularly limited as long as it is usually blended into a skin external preparation or the like as an emulsion base, and the following can be exemplified.

  Specifically, for example, ozokerite, α-olefin oligomer, light isoparaffin, light liquid isoparaffin, squalene, squalane, synthetic squalane, vegetable squalane, ceresin, paraffin, polyethylene powder, polybutene, microcrystalline wax, liquid isoparaffin, liquid paraffin , Hydrocarbons such as mineral oil and petrolatum;

Jojoba oil, carnauba wax, candelilla wax, rice bran wax, shellac, lanolin, mink sebum wax, whale wax, sugar cane wax, sperm whale oil, beeswax, montan wax and other natural waxes, avocado oil, almond oil, olive oil, extra virgin olive oil, Sesame oil, rice bran oil, rice oil, rice germ oil, corn oil, safflower oil, soybean oil, corn oil, rapeseed oil, persic oil, palm kernel oil, palm oil, castor oil, sunflower oil, high oleic sunflower oil, Grape seed oil, cottonseed oil, palm oil, hydrogenated palm oil, beef tallow, hardened oil, horse oil, mink oil, egg yolk oil, egg yolk fat oil, rosehip oil, cucumber nut oil, evening primrose oil, wheat germ oil, peanut oil, camellia oil Oil, sasanqua oil, cacao butter, molasses, beef bone fat, beef leg oil, pork fat, horse fat, sheep fat, sheabata , Macadamia nut oil, natural fats and oils of meadowfoam oil, and the like;

  Methylpolysiloxane (hereinafter also referred to as dimethicone), methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, Decamethyltetrasiloxane, tetradecamethylhexasiloxane, highly polymerized methylpolysiloxane, dimethylsiloxane / methyl (polyoxyethylene) siloxane / methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxyethylene) siloxane Polymer, dimethylsiloxane / methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane / methylcetyloxysiloxane copolymer Coalescence, dimethyl siloxane-methyl stearoxysiloxane copolymer, polyether-modified silicones, alcohol-modified silicones, alkyl-modified silicones, silicone oils such as amino-modified silicone;

Isopropyl myristate, butyl myristate, isopropyl palmitate, ethyl stearate, butyl stearate, ethyl oleate, ethyl linoleate, isopropyl linoleate, cetyl caprylate, hexyl laurate, isooctyl myristate, decyl myristate, myristic acid Myristyl, cetyl myristate, octadecyl myristate, cetyl palmitate, stearyl stearate, decyl oleate, oleyl oleate, cetyl ricinoleate, isostearyl laurate, isotridecyl myristate, isocetyl myristate, isostearyl myristate, myristic acid Octyldodecyl, 2-ethylhexyl palmitate, isocetyl palmitate, isostearyl palmitate, 2-ethyl stearate Hexyl, isocetyl stearate, isodecyl oleate, octyldodecyl oleate, octyldodecyl ricinoleate, ethyl isostearate, isopropyl isostearate, cetyl 2-ethylhexanoate, cetostearyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, Hexyl isostearate,

Ethylene glycol dioctanoate, ethylene glycol dioleate, propylene glycol dicaprylate, di (capryl / capric) propylene glycol, propylene glycol dicaprate, propylene glycol dioleate, neopentyl glycol dicaprate, neopentyl glycol dioctanoate, glyceryl tricaprylate Glyceryl tri-2-ethylhexanoate (hereinafter also referred to as trioctanoin), tri (caprylic / capric acid) glyceryl, tri (caprylic / capric / stearic acid) glyceryl, glyceryl triundecylate, glyceryl triisopalmitate Glyceryl triisostearate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, tetra-2-ethyl Pentaerythrityl hexanoate, pentaerythrityl tetramyristate, pentaerythrityl tetraisostearate, diglyceryl tetraisostearate, octyldodecyl neopentanoate, isocetyl octoate, isostearyl octoate, 2-ethylhexyl isoperargonate, dimethyloctane Hexyldecyl acid, octyldodecyl dimethyloctanoate, 2-ethylhexyl isopalmitate, isocetyl isostearate, isostearyl isostearate, octyldodecyl isostearate, lauryl lactate, myristyl lactate, cetyl lactate, octyldodecyl lactate, triethyl citrate, citric acid Acetyl triethyl, acetyl tributyl citrate,

Trioctyl citrate, triisocetyl citrate, trioctyldodecyl citrate, diisostearyl malate, 2-ethylhexyl hydroxystearate, di-2-ethylhexyl succinate, diisopropyl adipate, diisobutyl adipate, dioctyl adipate, diheptyl adipate Undecyl, diethyl sebacate, diisopropyl sebacate, dioctyl sebacate, cholesteryl stearate, cholesteryl isostearate, cholesteryl hydroxystearate, cholesteryl oleate, dihydrocholesteryl oleate, phytosteryl isostearate, phytosteryl oleate, 12-stearoyl hydroxystearin Isocetyl acid, stearyl 12-stearoyl hydroxystearate, 12-stea Isostearyl ylhydroxystearate, polyoxyethylene acetate (3) polyoxypropylene (1) cetyl ether, polyoxyethylene acetate (3) polyoxypropylene (1) isocetyl ether, isononyl isononanoate, octyl isononanoate, isononanoic acid Examples include esters such as tridecyl and isotridecyl isononanoate.

These components may be used individually by 1 type, or may be used in combination of 2 or more types.
The oil component includes at least the component (B), the component (A) described above, and the components (C), (D), and (E) described below, and, if necessary, the component (F) described below and / or (
G) may be used in an amount suitable for emulsifying the system that may contain the component to obtain a skin external preparation, and preferably 0.01 to 50 mass in the total amount of the emulsified skin external preparation of the present invention. %, More preferably 0.1 to 20% by mass.

(C) Surfactant
The skin external preparation of the present invention contains a surfactant (C).
The surfactant used in the present invention is not particularly limited as long as it is usually blended with a skin external preparation.

  Specifically, for example, coconut oil fatty acid potassium, coconut oil fatty acid sodium, coconut oil fatty acid triethanolamine, potassium laurate, sodium laurate, triethanolamine laurate, potassium myristate, sodium myristate, isopropanolamine myristate , Potassium palmitate, sodium palmitate, isopropanolamine palmitate, potassium stearate, sodium stearate, triethanolamine stearate, potassium oleate, sodium oleate, sodium castor oil fatty acid, zinc undecylenate, zinc laurate, myristic Zinc acid, magnesium myristate, zinc palmitate, zinc stearate, calcium stearate, magnesium stearate, stearic acid Minium, calcium myristate, magnesium myristate, aluminum dimyristate, aluminum isostearate, polyoxyethylene lauryl ether acetic acid, sodium polyoxyethylene lauryl ether acetate, polyoxyethylene tridecyl ether acetic acid, sodium polyoxyethylene tridecyl ether acetate , Sodium stearoyl lactate, sodium isostearoyl lactate,

Lauroyl sarcosine sodium, coconut oil fatty acid sarcosine, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, lauroyl sarcosine, lauroyl sarcosine potassium, lauroyl sarcosine triethanolamine, oleoyl sarcosine, myristoyl sarcosine sodium, stearoyl glutamate sodium, coconut oil Fatty acid acyl glutamic acid, coconut oil fatty acid potassium potassium glutamate, coconut oil fatty acid acyl glutamic acid sodium, coconut oil fatty acid acyl glutamic acid triethanolamine, lauroyl acyl glutamic acid, lauroyl acyl glutamic acid potassium, lauroyl acyl glutamic acid sodium, lauroyl acyl glutamic acid triethanolamine, myristoyl acyl Guru Minic acid, potassium myristoyl acyl glutamate, sodium myristoyl acyl glutamate, stearoyl acyl glutamate, potassium stearoyl acyl glutamate, disodium stearoyl acyl glutamate, hardened beef tallow fatty acid acyl glutamate sodium, coconut oil fatty acid hardened tallow fatty acid sodium acyl glutamate, coconut oil methyl methyl Sodium alanine, lauroylmethylalanine, sodium lauroylmethylalanine, lauroylmethylalanine triethanolamine, sodium myristoylmethylalanine, sodium lauroylmethyltaurine,

Palm oil fatty acid methyl taurine potassium, coconut oil fatty acid methyl taurine sodium, palm oil fatty acid methyl taurine magnesium, myristoyl methyl taurine sodium, palmitoyl methyl taurine sodium, stearoyl methyl taurine sodium, oleoyl methyl taurine sodium, sodium alkane sulfonate, tetradecene sulfone Sodium sulfate, dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate, sodium coconut oil fatty acid ethyl ester sulfonate, sodium lauryl sulfate, lauryl sulfate triethanolamine, sodium cetyl sulfate, alkyl (11,13,15) triethanolamine sulfate, Alkyl (12,13) sodium sulfate, alkyl (12,13) triethanolamine sulfate, alkyl (1 , 14, 16) sulfate, alkyl (12-13) diethanolamine sulfate, alkyl (12-14) sulfate, triethanolamine alkyl (
12-15) Triethanolamine sulfate, coconut oil alkyl magnesium sulfate / triethanolamine,

Ammonium lauryl sulfate, potassium lauryl sulfate, magnesium lauryl sulfate, monoethanolamine lauryl sulfate, diethanolamine lauryl sulfate, sodium myristyl sulfate, sodium stearyl sulfate, sodium oleyl sulfate, triethanolamine oleyl sulfate, sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene Lauryl ether sulfate triethanolamine, polyoxyethylene (1) alkyl (11, 13, 15) ether sodium sulfate, polyoxyethylene (1) alkyl (11, 13, 15) ether triethanolamine sulfate, polyoxyethylene (3 ) Sodium alkyl (11-15) ether sulfate, polyoxyethylene (2) Sodium alkyl (12,13) ether sulfate, Poly Kishiechiren (3) alkyl (12-14) ether sulfate, polyoxyethylene (3) alkyl (12-15) ether sulfate,

Polyoxyethylene (2) sodium lauryl ether sulfate, polyoxyethylene (3) sodium myristyl ether sulfate, higher fatty acid alkanolamide sodium sulfate ester, lauryl phosphate, sodium lauryl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, polyoxyethylene Oleyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene lauryl ether sodium phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene cetyl ether sodium phosphate, polyoxyethylene stearyl ether phosphate, polyoxyethylene Oleyl ether phosphate, polyoxyethylene oleyl ether sodium phosphate, polyoxyethylene alkylphenyl ether Phosphoric acid, polyoxyethylene alkylphenyl ether sodium phosphate, polyoxyethylene alkylphenyl ether phosphate triethanolamine, polyoxyethylene octyl ether phosphate, polyoxyethylene (10) alkyl (12,13) ether phosphate, poly Anionic surface activity such as oxyethylene alkyl (12-15) ether phosphate, polyoxyethylene alkyl (12-16) ether phosphate, polyoxyethylene lauryl ether phosphate triethanolamine, polyoxyethylene oleyl ether phosphate diethanolamine Agent;

Dioctylamine, dimethylstearylamine, trilaurylamine, diethylaminoethylamide stearate, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharin, stearyltrimethylammonium chloride, alkyl chloride (20-22) Trimethylammonium, lauryltrimethylammonium bromide, alkyl (16,18) trimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium saccharin, alkyl (28) trimethylammonium chloride, di (polyoxyethylene) oleylmethylammonium chloride (2EO) ), Dipolyoxyethylene stearylmethylammonium chloride Polyoxyethylene chloride (1) polyoxypropylene (
25) Diethylmethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride (5EO), distearyldimethylammonium chloride, dialkyl (12-15) dimethylammonium chloride, dialkyl (12-18) dimethylammonium chloride,

Dialkyl (14-18) dimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, isostearyl lauryl dimethyl ammonium chloride, benzalkonium chloride, myristyl dimethyl benzyl ammonium chloride, lauryl dimethyl (ethyl benzyl) ammonium chloride, chloride Cationic surfactants such as stearyldimethylbenzylammonium, laurylpyridinium chloride, cetylpyridinium chloride, lauroylcolaminoformylmethylpyridinium chloride, stearoylcoraminoformylmethylpyridinium chloride, alkylisoquinolium bromide, methylbenzethonium chloride, benzethonium chloride;

  2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, sodium lauryldiaminoethylglycine, sodium undecylhydroxyethylimidazolium betaine, undecyl-N-carboxymethylimidazolium betaine Coconut oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine disodium, coconut oil fatty acid acyl-N-carboxyethoxyethyl-N-carboxyethylethylenediamine disodium, coconut oil fatty acid acyl-N-carboxymethoxyethyl-N -Carboxymethylethylenediamine disodium, sodium laurylaminopropionate, sodium laurylaminodipropionate, laurylaminopropyl Triethanolamine pionate, palm oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium, lauryldimethylaminoacetic acid betaine, coconut oil alkyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, coconut oil Amphoteric surfactants such as fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine, lauric acid amidopropyl acetic acid betaine, ricinoleic acid amidopropyl betaine, stearyl dihydroxyethyl betaine, lauryl hydroxysulfo betaine;

Polyoxyethylene (10) alkyl (12,13) ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene (3, 7, 12) alkyl ( 12-14) ether, polyoxyethylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene-sec-alkyl (14) ether, polyoxyethylene isocetyl ether, polyoxyethylene cetostearyl ether, polyoxyethylene (2 , 10, 20) Isostearyl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene (20) aralkyl ether, polyoxyethylene octyldodecyl ether Polyoxyethylene behenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dinonyl phenyl ether, polyoxyethylene (1) polyoxypropylene (1,2,4,8) cetyl ether, poly Oxyethylene (5) polyoxypropylene (1,2,4,8) cetyl ether, polyoxyethylene (10) polyoxypropylene (
1,2,4,8) cetyl ether, polyoxyethylene (20) polyoxypropylene (1,2,4,8) cetyl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene (3) polyoxypropylene (34) stearyl ether,

Polyoxyethylene (4) polyoxypropylene (30) stearyl ether, polyoxyethylene (34) polyoxypropylene (23) stearyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyl tetradecyl ether, Polyethylene glycol monolaurate, ethylene glycol monostearate, polyethylene glycol monostearate, polyethylene glycol monooleate, ethylene glycol fatty acid ester, self-emulsifying ethylene glycol monostearate, diethylene glycol laurate, polyethylene glycol myristate, polyethylene glycol palmitate , Stearic acid diethylene glycol, self-emulsifying monostearic acid poly Tylene glycol (2), polyethylene glycol isostearate, ethylene glycol dioctanoate, diethylene glycol dilaurate, polyethylene glycol dilaurate, polyethylene glycol dipalmitate (150), ethylene glycol distearate, diethylene glycol distearate, polyethylene glycol distearate, dioleic acid Ethylene glycol, dioleic acid polyethylene glycol, diricinoleic acid polyethylene glycol,

Polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (6) sorbitan monostearate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene tristearate ( 20) sorbitan, polyoxyethylene monooleate (6) sorbitan, polyoxyethylene monooleate (20) sorbitan, polyoxyethylene trioleate (20) sorbitan, polyoxyethylene (20) coconut oil fatty acid sorbitan, monolauric acid Polyoxyethylene (10-80) sorbitan, polyoxyethylene sorbitan tristearate, polyoxyethylene isostearate (20) sorbitan, polyoxyethylene tristearate (1 0) sorbitan,

Polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene (10) hydrogenated castor oil, polyoxyethylene (20) hydrogenated castor oil, polyoxyethylene (40) hydrogenated castor oil, polyoxyethylene (50) hydrogenated Castor oil, polyoxyethylene (60) hydrogenated castor oil, lipophilic glyceryl monostearate, lipophilic glyceryl monooleate, glyceryl monostearate, palm oil fatty acid glyceryl, glyceryl laurate, glyceryl myristate, Glyceryl isostearate, glyceryl ricinoleate, glyceryl monohydroxystearate, glyceryl oleate, glyceryl linoleate, glyceryl erucate, glyceryl behenate, wheat germ oil fatty acid glyceride, safflower oil fatty acid glyceryl Hydrogenated soybean fatty acid glyceryl, saturated fatty acid glyceride, cottonseed oil fatty acid glyceryl, monoisostearate monomyristate glyceryl, mono-bovine fatty acid glyceride, monolanolin fatty acid glyceryl, sesquioleate glyceryl distearate, glyceryl diisostearate, glyceryl diarachiate, monolaurin Sorbitan acid, sorbitan monopalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan monooleate, sorbitan sesquistearate, sorbitan sesquioleate, sorbitan tristearate, sorbitan trioleate, coconut oil fatty acid sorbitan, isostearic acid Sorbitan, sorbitan sesquiisostearate, sorbitan distearate,

Diglyceryl isopalmitate, poly (4-10) glyceryl monolaurate, poly (10) glyceryl monomyristate, poly (2-10) glyceryl monostearate, poly (2-10) glyceryl monoisostearate, monooleic acid Poly (2-10) glyceryl, diglyceryl sesquioleate, poly (2-10) glyceryl diisostearate, poly (6-10) glyceryl distearate, diglyceryl triisostearate, poly (10) glyceryl tristearate, trio Poly (10) glyceryl oleate, poly (2) glyceryl tetraisostearate, decaglyceryl pentastearate, poly (6-10) glyceryl pentaoleate, poly (10) glyceryl heptearate, decaglycerate decastearate Sucrose fatty acid esters, coconut oil fatty acid sucrose esters, alkyl glucosides, coconut oil alkyl dimethylamine oxide, lauryl dimethylamine oxide, poly (10) glyceryl decaoleate, poly (6) glyceryl condensed ricinoleate, dextrin palmitate, etc. Nonionic surfactants such as dihydroxyethyl lauryl dimethylamine oxide, stearyl dimethylamine oxide, oleyl dimethylamine oxide, polyoxyethylene coconut oil alkyl dimethylamine oxide;

  Saponin, lecithin, soybean phospholipid, hydrogenated soybean phospholipid, soybean lysophospholipid, hydrogenated soybean lysophospholipid, egg yolk lecithin, hydrogenated egg yolk lysophosphatidylcholine, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, sphingophospholipid, sphingomyelin, ganglioside And natural surfactants such as bile acid, cholic acid, deoxycholic acid, sodium cholate, sodium deoxycholate, spicrispolic acid, rhamnolipid, trehalose lipid, sophorolipid, mannosylerythritol lipid, and the like.

These components may be used individually by 1 type, or may be used in combination of 2 or more types.
The surfactant includes at least the component (C), the components (A) and (B) described above, and the components (D) and (E) described below, and if necessary, the components (F) and / Alternatively, it may be used in an amount suitable for emulsifying the system that may contain the component (G) to obtain a skin external preparation, and is preferably 0.001 to the total amount of the emulsified skin external preparation of the present invention. It is used so as to be contained in an amount of 50% by mass, more preferably 0.01 to 30% by mass.

(D) Water
The skin external preparation of the present invention contains water. Although the water used for this invention is not specifically limited, What gave purification operations, such as purified water, ion-exchange water, distilled water, is preferable.

The water contains at least the component (D), the components (A), (B), and (C) described above and the component (E) described later, and further includes the component (F) and / or (G) described below as necessary. ) The system that may contain the component may be used in an amount suitable for emulsifying the skin external preparation, specifically, when the total amount of the emulsified skin external preparation of the present invention is 100% by mass. The remaining amount is obtained by subtracting the total amount of components other than water.

(E) Higher alcohol
The skin external preparation of the present invention contains a higher alcohol (E).
The higher alcohol means a monoalcohol having 8 to 24 carbon atoms and is not particularly limited as long as it is usually blended in a skin external preparation.

  Specific examples include isostearyl alcohol, octyldodecanol, hexyldecanol, cholesterol, phytosterol, lauryl alcohol, myristyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cetostearyl alcohol and the like.

These components may be used individually by 1 type, or may be used in combination of 2 or more types.
The higher alcohol includes at least the component (E) and the components (A), (B), (C), and (D) described above, and, if necessary, the component (F) and / or the component (G) described later. May be used in an amount suitable for obtaining a skin external preparation by emulsifying the system that may contain the total amount of the emulsified skin external preparation of the present invention, preferably 0.01 to 20% by mass, more It is preferably used so as to be contained in an amount of 0.1 to 10% by mass.

(F) Polymer compound
The skin external preparation of this invention may contain the high molecular compound (F) as needed. The polymer compound is not particularly limited as long as it is usually blended into a skin external preparation, but the average weight molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is usually 1, It is desirable to be in the range of 000 to 20,000,000, preferably 5,000 to 5,000,000.

  Specifically, for example, sodium alginate, carrageenan, agar, fur celeran, guar gum, quince seed, konjac mannan, tamarind gum, tara gum, dextrin, starch, locust bean gum, gum arabic, gati gum, caraya gum, tragacanth gum, arabinogalactan, Pectin, quince, chitosan, curdlan, xanthan gum, gellan gum, cyclodextrin, dextran, pullulan, microcrystalline cellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxystarch, cationized cellulose, starch Phosphate ester, cationized guar gum, carbox Methyl hydroxypropyl guar gum, hydroxypropyl guar gum, albumin, casein, hydrolyzed elastin, water-soluble elastin, hydrolyzed collagen, soluble collagen, hyaluronic acid, sodium hyaluronate,

Chondroitin sulfate, chondroitin sulfate sodium, wheat peptide, soybean peptide, gelatin, alge colloid, sodium polyacrylate, polyacrylate amide, carboxyvinyl polymer, polyethyleneimine, highly polymerized polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl ether, poly Acrylamide, acrylic acid polymer, methacrylic acid polymer, maleic acid polymer, vinylpyridine polymer, ethylene /
Acrylic acid copolymer, vinyl pyrrolidone polymer, vinyl alcohol / vinyl pyrrolidone copolymer, nitrogen-substituted acrylamide polymer, cationized polymer, dimethylacrylammonium polymer, acrylic acid anion polymer, methacrylic acid anion polymer, acrylic acid / alkyl methacrylate (C ₁₀ ~ ₃₀₎ copolymers, polyoxyethylene / polyoxypropylene copolymers, and the like. Of these, water-soluble polymer compounds are preferable.

  The polymer compound contains at least the component (F) and the components (A) to (E) described above, and further emulsifies the system which may contain the component (G) described later as needed. What is necessary is just to use in the quantity suitable for obtaining an external preparation, Preferably it is 0.001-5 mass% in the whole amount of the emulsified skin external preparation of this invention, More preferably, it is 0.01-3.5 mass%. Used to be included in quantity.

(G) Polyhydric alcohol
The skin external preparation of this invention may contain the polyhydric alcohol (G) as needed. The polyhydric alcohol is not particularly limited as long as it has two or more alcoholic hydroxyl groups in one molecule and is usually blended in a skin external preparation.

Specifically, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polypropylene glycol, pentanediol, glycerin, diglycerin, polyglycerin, isoprene glycol, 1,3-butylene glycol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,2-pentanediol, 1 , 2-hexanediol and the like.

You may use these components individually by 1 type or in combination of 2 or more types.
The polyhydric alcohol includes at least the component (G) and the components (A) to (E) described above, and further emulsifies the system that may include the component (F) described above as necessary. What is necessary is just to use in the quantity suitable for obtaining an external preparation, Preferably it is 0.01-20 mass% in the emulsified skin external preparation whole quantity of this invention, More preferably, it is contained at 0.1-10 mass%. Used as follows.

(H) Other ingredients
In addition to the components described above, the external preparation for skin of the present invention can be blended with components that are generally used in external preparations for skin within a range that does not impair the effects of the present invention.

Examples of such components include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, γ-linolenic acid, isostearic acid, 12-hydroxystearic acid, undecylenic acid, Fatty acids such as coconut oil fatty acids;
Alkyl glyceryl ethers such as batyl alcohol, chimyl alcohol, ceralkyl alcohol, isostearyl glyceryl ether;

Sugars such as mannitol, sorbitol, xylitol, maltitol, erythritol, pentaerythritol, glucose, sucrose, fructose, lactose, maltose, xylose, trehalose;
Lower monoalcohols such as ethanol, isopropyl alcohol, 1-butanol, 2-butanol, benzyl alcohol;

  Paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, paraaminobenzoic acid derivatives such as 2-ethylhexyl paradimethylaminobenzoate, benzyl cinnamate, monoparamethoxycinnamic acid mono-2 -Glyceryl ethylhexanoate, methyl 2,4-diisopropylcinnamate, ethyl 2,4-diisopropylcinnamate, potassium paramethoxycinnamate, sodium paramethoxycinnamate, isopropyl paramethoxycinnamate, paramethoxycinnamate Cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethoxyethyl paramethoxycinnamate, ethyl paraethoxycinnamate, urocanic acid derivatives such as urocanic acid, ethyl urocanate, 2,4-dihydroxybenzophenone, 2, 2 ', 4, '-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone sodium, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- Benzophenone derivatives such as sodium 4,4′-dimethoxybenzophenone and sodium 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, ethylene glycol salicylate, 2-ethylhexyl salicylate, phenyl salicylate, benzyl salicylate, salicylic acid p -Salicylic acid derivatives such as tert-butylphenyl, homomenthyl salicylate, salicylic acid-3,3,5-trimethylcyclohexyl, 2- (2'-hydroxy-5'-methoxyphenyl) benzoto Azole, 4-tert-butyl-4'-methoxybenzoyl ultraviolet absorbers such as methane;

Kaolin, anhydrous silicic acid, magnesium aluminum silicate, sericite, talc, boron nitride, mica, montmorillonite, hemp cellulose powder, wheat starch, silk powder, corn starch, nitro dye, azo dye, nitroso dye, triphenyl Methane dyes, xanthene dyes, quinoline dyes, anthraquinone dyes, indigo dyes, pyrene dyes, phthalocyanine dyes, flavonoids, quinone, porphyrin, water-soluble anato, squid powder, caramel, guaiazulene, gardenia blue, gardenia yellow , Cochineal, shikonin, copper chlorophyllin sodium, paprika dye, safflower red, safflower yellow, lacqueric acid, riboflavin butyrate, and other natural dyes, carbon black, yellow iron oxide, black iron oxide, red rose, conger, group , Zinc oxide, chromium oxide, titanium oxide, black titanium oxide, zirconium oxide, chromium hydroxide, alumina, magnesium oxide, barium sulfate, aluminum hydroxide, calcium carbonate, lithium cobalt titanate, manganese violet, pearl pigment powder, etc. And coloring materials;

  Ashitaba extract, Acacia extract, Avocado extract, Achacha extract, Achachazul extract, Altea extract, Arnica extract, Oil-soluble Arnica extract, Almond extract, Aloe extract, Anthony extract, Ginkgo biloba extract, Nettle extract, Iris root extract, Fennel extract , Turmeric extract, Ages extract, Echinacea leaf extract, Ogon extract, Oat extract, Prunus extract, Barley extract, Okra extract, Hypericum extract, Oil-soluble Hypericum extract, Adriatic extract , Orange flower water, seaweed extract, oyster tannin, cuckoo extract, valerian extract, cattail extract, chamomile extract, oil-soluble chamomile extract, chamomile Water, oat extract, carrot extract, oil-soluble carrot extract, carrot oil, pearl millet extract, licorice extract, licorice extract powder, licorice flavonoids, cantalis tincture, raspberry extract, kiwi extract, quina extract, cucumber extract, kyonin extract, quince seed extract Gardenia extract, Kumazasa extract, Clara extract, Walnut shell extract, Grapefruit extract, Clematis extract, Brown sugar extract, Chlorella extract, Mulberry extract, Keihi extract, Gentian extract,

Gentian pepper extract, black tea extract, cornflower extract, burdock extract, oil-soluble burdock extract, wheat germ extract, hydrolyzed wheat powder, rice bran extract, rice bran ferment extract, comfrey extract, saicin extract, saffron extract, bonito extract, oil-soluble salvia extract , Hawthorn extract, salamander extract, shiitake extract, shiitake extract powder, ziama extract, shikon extract, oil-soluble shikon extract, perilla extract, linden extract, oil-soluble linden extract, citrus extract, peonies extract, juniper extract, ginger extract, oil-soluble ginger Extract, ginger tincture, ginger root extract, birch extract, oil-soluble birch extract, birch sap, honeysuckle extract, horsetail extract, oil-soluble horsetail extract, sorghini , Stevia extract, Atlantic kizuta extract, Hawthorn extract, Atlantic elder extract, Atlantic rat extract, Achillea millefolium extract, oil-soluble Achillea millefolium extract, mint extract, sage extract, oil-soluble sage extract, sage water, mallow extract, celery extract, Senkyu extract, Senkyu water, Assembly extract, Soybean extract, Taisou extract, Thyme extract, Tea extract, Tea dry extract, Tea seed extract, Clove extract, Chimpi extract, Camellia extract, Clover extract, Oil soluble Teuchigurumi extract, Duke extract, Terminaria extract, Pepper tincture, Toki extract, Oil-soluble Toki extract, Toki water, Toki-Senka extract, Oil-soluble Toki-Senka extract, Soymilk powder, Tonin extract, Spruce , Dokudami extract, tomato extract, tormentilla extract, natto extract, carrot extract, oil soluble carrot extract, garlic extract, wild rose extract, oil soluble wild rose extract, buckthorn extract, buckthorn root extract, buckthorn extract, parsley extract, leafhopper extract Concentrate, distilled mint water, hamamelis water,

Hamamelis extract, rose extract, parietalia extract, toad extract, loquat leaf extract, oil soluble loquat leaf extract, dandelion extract, butterfly extract, butcher bloom extract, butcher bloom extract powder, grape extract, grape leaf extract, grape water, hayflower Extract, loofah extract, loofah water, safflower extract, oil-soluble bodaige extract, bodaiju water, button extract, hop extract, oil-soluble hop extract, pine extract, maria thistle extract, malonie extract, oil-soluble maronie extract, muclozi extract, melissa extract, Merirot extract, peach leaf extract, oil-soluble peach leaf extract, coconut extract, cornflower extract, cornflower water, eucalyptus extract, yukinoshita extract, lily extract, yokuinin extract, oil-soluble yokuinine , Mugwort extract, mugwort water, lavender extract, lavender water, apple extract, litchi extract, lettuce extract, lemon extract, forsythia extract, rose water, rosemary extract, oil-soluble rosemary extract, roman chamomile extract, bitumen extract, etc. Plant extracts;

  Glycine, alanine, valine, leucine, isoleucine, serine, threonine, phenylalanine, tyrosine, tryptophan, cystine, cysteine, methionine, proline, hydroxyproline, aspartic acid, asparagine, glutamic acid, glutamine, arginine, histidine, lysine, γ-aminobutyric acid Amino acids and peptides such as DL-pyrrolidonecarboxylic acid, ε-aminocaproic acid, glutathione;

  Vitamin A such as retinol, retinal, retinoic acid, retinol acetate, retinol palmitate, etc., carotenoids such as α-carotene, β-carotene, γ-carotene, δ-carotene, lycopene, zeaxanthin, cryptoxanthine, echinone, astaxanthin, Vitamin B1 such as thiamine, vitamin B2 such as riboflavin, vitamin B6 such as pyridoxine, pyridoxal, pyridoxamine, vitamin B12 such as cyanocobalamin, folic acid, nicotinic acid, nicotinamide, pantothenic acid, biotins, L -Ascorbic acid, sodium L-ascorbate, L-ascorbyl stearate, L-ascorbyl palmitate, L-ascorbyl dipalmitate, L-ascorbyl tetraisopalmitate, L-ascorb Vitamin Cs such as disodium acid sulfate ester, L-ascorbyl magnesium, sodium L-ascorbyl phosphate, L-ascorbic acid-2-glucoside, vitamins D such as ergocalciferol, cholecalciferol, d-α- Vitamin E such as tocopherol, DL-α-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol succinate, β-tocopherol, γ-tocopherol, d-δ-tocopherol, ubiquinones, vitamin K, carnitine Vitamins such as ferulic acid, γ-oryzanol, α-lipoic acid, orotic acid and vitamin-like agents;

  Benzoic acid, sodium benzoate, undecylenic acid, salicylic acid, sorbic acid, potassium sorbate, dehydroacetic acid, sodium dehydroacetate, isobutyl parahydroxybenzoate, isopropyl parahydroxybenzoate, ethyl parahydroxybenzoate, butyl parahydroxybenzoate, Propyl parahydroxybenzoate (hereinafter also referred to as propylparaben), benzyl parahydroxybenzoate, methyl parahydroxybenzoate (hereinafter also referred to as methylparaben), methyl sodium parahydroxybenzoate, phenoxyethanol, Photosensitizer No. 101, Photosensitizer 201 Preservatives such as No. 1 and Photosensitive Element 401;

Antioxidants such as butylhydroxyanisole, butylhydroxytoluene, propyl gallate, erythorbic acid, sodium erythorbate, parahydroxyanisole, octyl gallate;
Metal ion sequestering agents such as trisodium ethylenediaminehydroxyethyl triacetate, edetic acid, disodium edetate, trisodium edetate, tetrasodium edetate, sodium citrate, gluconic acid, phytic acid, sodium polyphosphate, sodium metaphosphate ;
Moisturizers such as sodium lactate, sodium pyrrolidonecarboxylate, betaine, lactic acid bacteria culture, yeast extract, ceramide;

Anti-inflammatory agents such as glycyrrhizic acid, trisodium glycyrrhizinate, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, β-glycyrrhetinic acid, glyceryl glycyrrhetinate, stearyl glycyrrhetinate, lysozyme chloride, hydrocortisone, allantoin;
PH adjusters such as sodium hydroxide, potassium hydroxide, triethanolamine;
Salts such as sodium chloride, potassium chloride, magnesium chloride, sodium sulfate;
Α-hydroxy acids such as citric acid, glycolic acid, tartaric acid, lactic acid;
Whitening agents such as arbutin, α-arbutin, placenta extract;

  Angelica oil, Ylang-Ylang oil, Elemi oil, Orange oil, Chamomile oil, Roman chamomile oil, Cardamom oil, Calamus oil, Galvanum oil, Camphor oil, Carrot seed oil, Clarage sage oil, Grapefruit oil, Clove oil, Keihi oil, Coriander oil , Cypress oil, Sandalwood oil, Cedarwood oil, Citronella oil, Cinnamon leaf oil, Jasmine absolute, Juniper berry oil, Ginger extract, Spearmint oil, Sage oil, Cedar oil, Geranium oil, Thyme oil, Tea tree oil, Nutmeg oil , Near uri oil, neroli oil, pine oil, basil oil, peppermint oil, patchouli oil, palmarosa oil, fennel oil, petitgren oil, black pepper oil, frankincense oil, vetiver oil, peppermint oil, bergamot oil Zoin oil, Boad Rose oil, Marjoram oil, Mandarin oil, Myrrh oil, Melissa oil, Eucalyptus oil, Yuzu oil, Lime oil, Lavensara oil, Lavandin oil, Lavender oil, Linden oil, Lemon oil, Lemongrass oil, Rose oil, Rose Essential oils such as wood oil, rosemary oil, lobe oil;

Terpenes such as limonene, pinene, terpinene, terpinolene, myrcene, longiferin, etc .;
A fragrance | flavor etc. are mentioned. These components can be used individually by 1 type or in combination of 2 or more types.

Production of emulsified skin external preparation The skin external preparation of the present invention can be produced by the following method using the above-described components so as to have a predetermined content.

  Specifically, a dispersion obtained by mixing at least the oil component (B), the surfactant (C) and the higher alcohol (E) described above, and ascorbic acid represented by the formula (1) It can manufacture by mixing and emulsifying the aqueous solution obtained by melt | dissolving the salt (A) of the higher fatty acid ester of 2-phosphate ester in water (D).

  In this case, the mixing order of the dispersion and the aqueous solution may be mixed by adding the aqueous solution to the dispersion, or may be mixed by adding the dispersion to the aqueous solution. Of these, it is preferable to add the aqueous solution to the dispersion and mix and emulsify. If they are added and mixed in this order, they are easily dispersed uniformly.

Furthermore, the dispersion liquid may further contain a polymer compound (F) and / or a polyhydric alcohol (G) as necessary.
In the above production method, mixing means and emulsification conditions (temperature, number of stirrings, stirring speed, pressure, etc.) and the like can be appropriately selected according to conventional methods.
<Cosmetics>
Regarding the use of the emulsified external preparation for skin, the most common aspect is cosmetics. The form of the cosmetic is not limited.

  The cosmetics include skin milk, skin cream, foundation cream, massage cream, cleansing cream, shaving cream, cleansing foam, lotion, lotion, pack, shampoo, rinse, hair restorer, hair nourishing agent, hair dye, hair conditioner, Toothpaste, mouthwash, permanent wave agent, ointment, bathing agent, body soap, etc. are included in a broad sense, and any type can be used as long as it comes into contact with the skin during use. Regardless of the gender and age of the user.

  Furthermore, existing cosmetic raw materials other than the components (A) to (H) described above can be added to the cosmetic at a general concentration. For example, commentary on the 2nd edition of Cosmetic Raw Material Standards (edited by the Japan Standards Association, 1984 (Pharmaceutical Daily)), non-standard ingredients for cosmetic raw materials (supervised by the Pharmaceutical Affairs Bureau, Ministry of Health and Welfare, 1993 (Pharmaceutical Daily)), cosmetic raw material standards Supplemental specifications for external ingredients (supervised by the Pharmaceutical Affairs Bureau, Ministry of Health and Welfare, 1993 (Pharmaceutical Daily)), permission standards by cosmetic type (supervised by the Pharmaceutical Affairs Bureau, Ministry of Health, Health and Welfare, 1993 (Pharmaceutical Daily)), formulation standards by cosmetics (Ministry of Health and Welfare) Of all the cosmetic raw materials described in the Supervision of the Bureau of Public Affairs, 1997 (Pharmaceutical Daily), and the Cosmetic Raw Material Dictionary (1991 (Nikko Chemicals)), etc., the above-mentioned components (A) to (H) Other than can be used. In addition, you may use this cosmetic raw material individually by 1 type or 2 types or more.

When using the cosmetic raw material, the total amount of the cosmetic raw material and the component (H) is generally 0.01 to 90% by mass, more preferably 0.1 to 25% by mass, and still more preferably, in the total amount of the cosmetic. Is used so as to be contained in an amount of 0.3 to 10% by mass.
<Method for stabilizing salt of higher fatty acid ester of ascorbic acid-2-phosphate>
As described above, the emulsified skin external preparation of the present invention contains a salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate represented by the above formula (1). By improving the stability in the agent of A), decomposition of the salt (A) and a decrease in the abundance can be suppressed.

In other words, an emulsified composition which contains at least (B) to (E) and may further contain (F) and / or (G) as necessary, and ascorbic acid-2- A technique of contacting a salt of a higher fatty acid ester of a phosphate ester (A),
More specifically, the ester salt (A) can be stabilized by allowing the salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate to be present in the emulsified composition.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In addition, the compounding quantity in the following example represents the mass%.

  Moreover, in the following example, the residual rate (%) of the salt (A) of the higher fatty acid ester of ascorbic acid-2-phosphate in the agent is the concentration of the salt (A) in the agent immediately after preparation and 40 ° C. The salt (A) concentration in the agent after 1 month of standing was measured by high performance liquid chromatography under the following measurement conditions and calculated by the following formula.

Residual rate (%) = 100 × [concentration of salt (A) in agent after standing at 40 ° C. for 1 month (g / l) / concentration of salt (A) in agent immediately after preparation (g / l)]
<High-performance liquid chromatography measurement conditions>
Column: Shodex (registered trademark of Showa Denko KK) manufactured by Showa Denko C18P4E
Column temperature: 40 ° C
Eluent: 0.1 M dipotassium hydrogen phosphate (pH 7.0) / tetrahydrofuran = 65/35 Flow rate: 0.7 ml / min Detection: UV265 nm
[Examples 1 to 3]
In accordance with the formulations of Examples 1 to 3 in Table 1, components 1 to 17 in Table 1 are mixed and dispersed to obtain a dispersion, and components 18 to 20 in Table 1 are dissolved in component 21 in water. The aqueous solution thus obtained was added. Then, it fully stirred and emulsified, deaerated, and the emulsified skin external preparation of Examples 1-3 was obtained.

  About the obtained external preparation for skin, the content of sodium ascorbate-2-phosphate-6-palmitate in the preparation was measured by high performance liquid chromatography according to the above measurement conditions, and then allowed to stand at 40 ° C. The content of sodium ascorbate-2-phosphate-6-palmitate was measured over time by high performance liquid chromatography, and the residual rate was calculated according to the above formula.

Table 2 shows the residual rate of sodium ascorbyl-2-phosphate-6-palmitate in the preparation after standing at 40 ° C. for 1 month.
[Comparative Example 1]
According to the prescription of Comparative Example 1 in Table 1, the components described in Table 1 were mixed and dissolved to obtain a skin external preparation of Comparative Example 1.

  The amount of sodium ascorbic acid-2-phosphate-6-palmitate in the preparation was increased with time in the same manner as in Examples 1 to 3 except that the obtained skin external preparation of Comparative Example 1 was used. The residual ratio was calculated by liquid chromatography.

  Table 2 shows the residual rate of sodium ascorbyl-2-phosphate-6-palmitate in the preparation after standing at 40 ° C. for 1 month.

表２から、実施例１〜３では比較例１に比べて、アスコルビン酸−２−リン酸−６−パルミチン酸ナトリウム量の減少が抑えられていたことがわかる。

From Table 2, it can be seen that in Examples 1 to 3, a decrease in the amount of sodium ascorbic acid-2-phosphate-6-palmitate was suppressed as compared with Comparative Example 1.

[Examples 4 to 6]
In accordance with the formulations of Examples 4 to 6 in Table 3, components 1 to 17 in Table 3 are mixed and dispersed to obtain a dispersion, and components 18 to 20 in Table 3 are dissolved in water of component 21 in the dispersion. The aqueous solution thus obtained was added. Then, it fully emulsified by stirring and degassed to obtain emulsified skin external preparations of Examples 4 to 6.

  About the obtained external preparation for skin, the content of sodium ascorbyl 2-phosphate-6- (2-hexyldecanoate) in the preparation was measured by high performance liquid chromatography according to the above measurement conditions, and then statically treated at 40 ° C. Then, the content of sodium ascorbyl-2-phosphate-6- (2-hexyldecanoate) in the agent was measured over time by high performance liquid chromatography, and the residual rate was calculated according to the above formula.

Table 4 shows the residual rate of sodium ascorbyl-2-phosphate-6- (2-hexyldecanoate) in the preparation after standing at 40 ° C. for 1 month.
[Comparative Example 2]
According to the formulation of Comparative Example 2 in Table 3, the components described in Table 3 were mixed and dissolved to obtain a skin external preparation of Comparative Example 2.

  The content of sodium ascorbate-2-phosphate-6- (2-hexyldecanoate) in the preparation was changed in the same manner as in Examples 4 to 6 except that the obtained external preparation for skin of Comparative Example 2 was used. The residual ratio was calculated over time by high performance liquid chromatography.

  Table 4 shows the residual rate of sodium ascorbyl-2-phosphate-6- (2-hexyldecanoate) in the preparation after standing at 40 ° C. for 1 month.

表４から、実施例４〜６では比較例２に比べて、アスコルビン酸−２−リン酸−６−（２−ヘキシルデカン酸）ナトリウム量の減少が抑えられていたことがわかる。

From Table 4, it can be seen that in Examples 4 to 6, a decrease in the amount of sodium ascorbyl-2-phosphate-6- (2-hexyldecanoate) was suppressed as compared with Comparative Example 2.

Claims (15)

Following formula (1)

(In formula (1), R represents a higher fatty acid residue) Ascorbic acid-2-phosphate salt of higher fatty acid ester (A), oil component (B), surfactant ( C), water (D), and higher alcohol (E), The emulsified skin external preparation characterized by the above-mentioned.   The emulsified skin external preparation according to claim 1, further comprising a polymer compound (F).   Furthermore, the polyhydric alcohol (G) is contained, The emulsified skin external preparation of Claim 1 or 2 characterized by the above-mentioned.   R in said Formula (1) is a C8-C22 fatty acid residue, The emulsified skin external preparation in any one of Claims 1-3 characterized by the above-mentioned.   The emulsified skin external use according to claim 4, wherein R in the formula (1) is a residue of lauric acid, myristic acid, palmitic acid, stearic acid, 2-hexyldecanoic acid or isostearic acid. Agent.   The emulsified skin external preparation according to claim 5, wherein R in the formula (1) is a residue of palmitic acid.   The emulsified skin external preparation according to claim 5, wherein R in the formula (1) is a residue of 2-hexyldecanoic acid.   Emulsified according to any one of claims 1 to 7, wherein the salt (A) of the higher fatty acid ester of ascorbic acid-2-phosphate is Na salt, K salt, Mg salt or Zn salt. Skin external preparation.   The emulsified emulsion according to any one of claims 1 to 8, wherein the salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate is contained in an amount of 0.01 to 20% by mass. Skin external preparation. A dispersion obtained by mixing at least the oil component (B), the surfactant (C), and the higher alcohol (E);
Following formula (1)

(In formula (1), R represents a higher fatty acid residue.) The salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate represented by the formula (1) was dissolved in water (D). An aqueous solution,
A method for producing an emulsified skin external preparation characterized by mixing and emulsifying in any order.   The method for producing an emulsified skin external preparation according to claim 10, wherein the aqueous solution is added to the dispersion, mixed and emulsified. The method for producing an emulsified skin external preparation according to claim 10 or 11, wherein the dispersion further contains a polymer compound (F) and / or a polyhydric alcohol (G).   It is a cosmetic, The emulsified skin external preparation in any one of Claims 1-9 characterized by the above-mentioned. Following formula (1)

(In the formula (1), R represents a higher fatty acid residue), which is a method for stabilizing a salt (A) of a higher fatty acid ester of ascorbic acid-2-phosphate ester,
An emulsified composition comprising at least an oil component (B), a surfactant (C), water (D), and a higher alcohol (E);
A stabilizing method comprising contacting the salt (A) of a higher fatty acid ester of the ascorbyl 2-phosphate ester. In the emulsified composition, a polymer compound (F) and / or a polyhydric alcohol (G
The stabilization method according to claim 14, wherein: