JP2016069310A - External preparation for skin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an external preparation for skin in which odor is reduced, the stability of carotenoid is excellent, the generation of temporal precipitate is suppressed, and temporal stability is excellent.SOLUTION: The invention provides an external preparation for skin containing the compound represented by the following general formula (1), at least one compound selected from ascorbic acid phosphoric ester magnesium and ascorbic acid phosphate ester sodium, and carotenoid; wherein the viscosity of the external preparation for skin is 1 Pa s or more when measuring under the measurement condition of 25°C, 12 rpm, 30 s, using a Brookfield viscometer. In the general formula (1), Rrepresents a hydrocarbon group, Rand Reach independently represent a hydrocarbon group, Rrepresents a h+ monovalent hydrocarbon group which may have an urethane bond, Rrepresents a hydrocarbon group, Rrepresents a hydrogen atom or a hydroxy group; m is an integer of 2 or more, h is an integer of 1 or more, k and n are each independently an integer in a range of 0-1000, and both k and n do not become 0.SELECTED DRAWING: None

Description

  The present invention relates to an external preparation for skin.

It is known that when light is applied to the skin, singlet oxygen is generated and causes photoaging such as spots or wrinkles.
Carotenoids are components derived from natural products obtained by extraction from seaweeds, plants, and the like, and have a high singlet oxygen scavenging ability and are effective in suppressing photoaging of the skin caused by singlet oxygen.
However, carotenoids have low stability. For example, when carotenoids are blended in an external preparation for skin, they are often used in combination with carotenoid stabilizers.

As carotenoid stabilizers, ascorbic acid (vitamin C) derivatives, tocopherol (vitamin E) derivatives and the like are known.
For example, Patent Documents 1 and 2 describe that an ascorbic acid phosphate derivative is effective for stabilizing carotenoids.
Patent Document 3 describes a jelly-like serum containing astaxanthin, which is one of carotenoids, PEG-240 / decyltetradeceth-20 / HDI copolymer, and trisodium ascorbyl phosphate palmitate. Has been.

  On the other hand, Patent Document 4 describes that, in a skin whitening external preparation, a hydrophobic modified polyether urethane such as Adecanol GT-700 manufactured by ADEKA Co., Ltd. is used as an associative polymer together with a water-soluble whitening agent component. Yes.

Japanese Patent No. 5019885 Japanese Patent No. 5046756 JP2013-82705A JP 2002-284664 A

Since carotenoids are derived from natural products, they have oily odors and fishy odors due to impurities such as unsaturated fatty acids that are difficult to remove. Among carotenoids, particularly astaxanthin, lycopene, fucoxanthin and the like have a strong odor. Specifically, for example, astaxanthin has seaweed, krill-derived fishy odor, plant-derived oily odor, etc., lycopene has tomato odor, and fucoxanthin has.
Ascorbic acid derivatives, which are carotenoid stabilizers, also undergo oxidative degradation over time, producing a sweet odor due to this. The ascorbic acid phosphate derivative, which is said to be effective for stabilizing carotenoids, slowly decomposes over time, and ascorbic acid is generated, so that the odor gradually becomes stronger.

  The present inventor has a problem that when a carotenoid and an ascorbic acid derivative are combined in a topical skin preparation, a carotenoid-specific odor and an odor derived from the decomposition of the ascorbic acid derivative are combined to form a strong odor. I found it.

  The problem to be solved by the present invention is to provide an external preparation for skin having excellent aging stability, with reduced odor, excellent carotenoid stability, and suppressed generation of precipitates over time.

The above problem is solved by the following means. That is,
[1] A compound represented by the following general formula (1), at least one compound selected from magnesium ascorbate phosphate and sodium ascorbate phosphate, and carotenoid, and using a B-type viscometer, 25 An external preparation for skin, wherein the external preparation for skin has a viscosity of 1 Pa · s or more when measured under the measurement conditions of ° C, 12 rpm, and 30 s.

In the general formula (1), R ¹ represents an m-valent hydrocarbon group having ² to 36 carbon atoms, R ² and R ⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms, R ³ may have a urethane bond, represents a linear, branched, or h + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, R ⁵ represents a divalent hydrocarbon group, R ⁶ represents Represents a hydrogen atom or a hydroxy group. m is an integer greater than or equal to 2, h is an integer greater than or equal to 1, k and n represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k and n Will never be zero.

  [2] The content of one compound selected from magnesium ascorbate phosphate sodium and sodium ascorbate phosphate is 0.1% by mass or more based on the total mass of the external preparation for skin. Skin external preparation.

  [3] The compound represented by the general formula (1) is selected from the group consisting of a compound represented by the following general formula (1-1) and a compound represented by the following general formula (1-2). The skin external preparation according to [1] or [2], which is at least one compound.

In general formula (1-1), R ¹¹ represents a m1-valent hydrocarbon group having 2 to 12 carbon atoms, and R ¹² and R ¹⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms. , R ¹³ may have a urethane bond, and represents a linear, branched, or h1 + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, and R ¹⁵ represents a monovalent hydrocarbon group. m1 is an integer greater than or equal to 2, h1 is an integer greater than or equal to 1, k1 and n1 represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k1 and n1 Will never be zero.

In the general formula (1-2), R ²¹ represents a m2-valent saturated hydrocarbon group having 6 to 36 carbon atoms, and R ²² represents a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, 3-methyl. −3,5,5-trimethylcyclohexylene group, dimethylphenylene group, or tolylene group, and R ²³ represents a hydrogen atom or a methyl group. n2 represents an integer of 90 to 900, and m2 represents an integer of 1 to 5.

  [4] PEG-240 / decyltetradeceth-20 / hexamethylene diisocyanate copolymer in which the compound represented by the general formula (1) is a compound represented by the general formula (1-1), and the general formula (1) -2) The skin external application according to [3], which is at least one copolymer selected from the group consisting of bisstearyl PEG / PPG-8 / 6 (methylenediphenyl diisocyanate / PEG-400) copolymer, which is a compound represented by -2) Agent.

  [5] The external preparation for skin according to any one of [1] to [4], wherein the carotenoid is astaxanthin.

  [6] The content of the compound represented by the general formula (1) is 0.4% by mass or more with respect to the total mass of the external preparation for skin according to any one of [1] to [5]. Skin external preparation.

  [7] A skin external preparation as described in any one of [1] to [6], which is an emulsion having emulsified particles containing a carotenoid.

  ADVANTAGE OF THE INVENTION According to this invention, the skin external preparation which is excellent in stability over time by which odor is reduced, the stability of carotenoid is excellent, and the generation | occurrence | production of the precipitate with time is also suppressed is provided.

The skin external preparation of the present invention contains a compound represented by the general formula (1), one compound selected from magnesium ascorbate phosphate sodium and sodium ascorbate phosphate, and a carotenoid, and a B-type viscometer. It is a skin external preparation having a viscosity of 1 Pa · s or higher when used under the conditions of 25 ° C., 12 rpm, and 30 s.
Hereinafter, the compound represented by the general formula (1) is abbreviated as “compound (A)”, and ascorbic acid phosphate magnesium and ascorbic acid sodium phosphate are generally abbreviated as “specific stabilizer (B)” as appropriate. And explain.

Since the skin external preparation of the present invention has the above-described configuration, the odor is reduced and the skin external preparation is excellent in stability over time.
Although all the mechanisms for obtaining this effect are not clear, it is presumed as follows.

As described above, it is known that the stability of the carotenoid (C) is significantly improved in a system containing the specific stabilizer (B) and the carotenoid (C). However, the odor peculiar to carotenoid (C) and the odor derived from the decomposition of the specific stabilizer (B) combine to form a strong odor.
Regarding the reduction of odor, generally, a method of further containing a thickener in a system containing a specific stabilizer (B) and a carotenoid (C) to increase the viscosity of the system to suppress odor release. May be taken. This technique utilizes the fact that the volatile low-molecular compounds that cause odor are less likely to be volatilized from the system by increasing the viscosity of the system.
When using polysaccharides widely used in cosmetics as a thickener, the thickening efficiency is not high, and it is necessary to contain a large amount of thickener to achieve the target viscosity. Moreover, even if a large amount of thickener is used, the reduction of odor is insufficient and a stickiness problem may occur separately.
Acrylic thickeners (carbomers, etc.) widely used in cosmetics as thickeners have no salt resistance, and in systems containing salts such as the specific stabilizer (B), thickening cannot be achieved, Accordingly, the effect of reducing odor cannot be obtained.

On the other hand, in the present invention, in addition to the specific stabilizer (B) and carotenoid (C), the compound (A) is contained.
Here, the compound (A) is a urethane-based polymer modified to be hydrophobic, and is a nonionic compound. The compound (A) can be thickened even when used with a salt such as the specific stabilizer (B), and does not cause stickiness like a polysaccharide.
Further, the compound (A) has both a hydrophilic portion and a hydrophobic portion, as is clear from the structure represented by the general formula (1), and is a hydrophilic low molecular weight compound (for example, a hydrophilic odor component). And hydrophobic low molecular weight compounds (for example, hydrophobic odor components). That is, by including the compound (A) in the external preparation for skin, both the hydrophilic odor component and the hydrophobic odor component in the external preparation for skin are adsorbed on the compound (A) and do not volatilize. It is considered that the solubilized state can be maintained. As a result, it is estimated that the odor of the external preparation for skin of the present invention is suppressed.
Particularly, when the compound (A) is contained in the external preparation for skin at a certain concentration (0.4% by mass or more based on the total mass of the external preparation for skin), the viscosity of the external preparation for skin can be remarkably increased. When the viscosity of the external preparation for skin increases, volatilization and transpiration of the odor component are suppressed, and the odor of the external preparation for skin is further suppressed.
On the other hand, the specific stabilizer (B) used in the present invention is a component that is effective for stabilizing the carotenoid (C), and is a component that hardly causes crystal precipitation over time. Therefore, the external preparation for skin of the present invention is excellent in carotenoid stability and excellent in temporal stability in which the generation of precipitates with time is suppressed.

Here, the viscosity of the external preparation for skin is the viscosity when the external preparation for skin is measured using a B-type viscometer under measurement conditions of 25 ° C., 30 s, 12 rpm.
Specifically, 100 g of a measurement sample taken from the external preparation for skin was supplied to a B-type viscometer, product name: TVB-10M, manufactured by Toki Sangyo Co., Ltd., and measurement conditions were 25 ° C., 30 s, 12 rpm It was obtained by measuring.
In the present invention, three measurement samples were prepared, and the average value of all measurement samples was defined as “viscosity of external preparation for skin”.
The upper limit of the viscosity of the external preparation for skin of the present invention is preferably 100 Pa · s from the viewpoint of the feeling of use of the external preparation for skin.

Hereinafter, numerical ranges indicated using “to” in this specification indicate ranges including numerical values described before and after “to” as the minimum value and the maximum value, respectively.
Further, in the present specification, the amount of each component in the external preparation for skin includes the plurality of substances present in the external preparation for skin, unless there is a specific indication, when there are a plurality of substances corresponding to each component in the external preparation for skin. Means the total amount.

In the present invention, “stability over time” means that, after the preparation of the external preparation for skin, the change in physical properties in the system of the external preparation for skin is suppressed when time elapses. For example, in the present invention, changes in physical properties include the residual rate of carotenoid (C) in the skin external preparation system and the generation of crystal precipitates.
In the present invention, the “aqueous phase” used when obtaining an emulsion and an emulsion is used as a term for the “oil phase” regardless of the type of solvent.

Hereinafter, each component used for the skin external preparation of this invention is demonstrated in detail.
The skin external preparation of the present invention contains compound (A), specific stabilizer (B), and carotenoid (C), and may contain water and other additives as necessary.

[Compound (A)]
The skin external preparation of the present invention contains compound (A), that is, a compound represented by the following general formula (1).

In the general formula (1), R ¹ represents an m-valent hydrocarbon group having ² to 36 carbon atoms, R ² and R ⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms, R ³ represents a h + 1 valent hydrocarbon group which may have a urethane bond and may have a straight chain, a branched chain or an aromatic ring, R ⁵ represents a divalent hydrocarbon group, and R ⁶ represents Represents a hydrogen atom or a hydroxy group. m is an integer greater than or equal to 2, h is an integer greater than or equal to 1, k and n represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k and n Never reaches 0

  As apparent from the general formula (1), the compound (A) was modified to be hydrophobic, having a urethane structure and a hydrophilic alkyleneoxy group in the main chain and a hydrophobic hydrocarbon group at the terminal. This is a urethane copolymer.

R ¹ in the general formula (1) represents an m-valent hydrocarbon group having 2 to 36 carbon atoms, and preferably a divalent to octavalent hydrocarbon group. The hydrocarbon group represented by R ¹ may contain an oxygen atom between carbon atoms.

R ² and R ⁴ in the general formula (1) each independently represent a divalent hydrocarbon group having 1 to 4 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms.

R ³ in the general formula (1) may have a urethane bond and represents a linear, branched, or h + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, preferably divalent to 4 Valent hydrocarbon group. 1-10 is preferable as the hydrocarbon groups represented by R ^3.

R ⁵ in the general formula (1) represents a divalent hydrocarbon group, and the carbon number is preferably 8 to 36, more preferably 12 to 24. Examples of the divalent hydrocarbon group represented by R ⁵ include a divalent group obtained by removing one hydrogen atom from an alkyl group, an alkenyl group, an alkylaryl group, a cycloalkyl group, and a cycloalkenyl group. An alkylene group is preferred.

R ⁶ in the general formula (1) represents a hydrogen atom or a hydroxy group.
That is, when R ⁶ is a hydrogen atom, it becomes a terminal group together with the divalent hydrocarbon group of R ⁵ .

M in the general formula (1) is the same as the valence of the hydrocarbon group represented by R ¹ and is an integer of 2 or more.
H in the general formula (1) is a valence of the hydrocarbon group represented by R ³ −1 and is an integer of 1 or more.

K in the general formula (1) is the number of repetitions of the (O—R ² ) structure (degree of polymerization) and may be an integer in the range of 0 to 1000.
N in the general formula (1) is the number of repetitions (polymerization degree) of the (R ⁴ —O) structure and may be an integer in the range of 0 to 1000.
In general formula (1), both k and n are not 0.

[Compound represented by formula (1-1)]
In the present invention, the compound represented by the general formula (1) is preferably a compound represented by the following general formula (1-1) (hereinafter sometimes referred to as the compound (A-1)).

In general formula (1-1), R ¹¹ represents a m1-valent hydrocarbon group having 2 to 12 carbon atoms, and R ¹² and R ¹⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms. , R ¹³ may have a urethane bond, and represents a linear, branched, or h1 + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, and R ¹⁵ represents a monovalent hydrocarbon group. m1 is an integer greater than or equal to 2, h1 is an integer greater than or equal to 1, k1 and n1 represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k1 and n1 Will never be zero.

Here, R ¹² , R ¹³ , R ¹⁴ , m1, h1, k1, and n1 in the general formula (1-1) are R ² , R ³ , R ⁴ , m, h in the general formula (1). , K, and n, and the definitions are the same.
Preferred embodiments of the compound represented by formula (1-1) are as follows.
In the general formula (1-1), the hydrocarbon group represented by R ¹¹ preferably has 2 to 4 carbon atoms. The hydrocarbon group represented by R ¹¹ is preferably a chain or branched aliphatic hydrocarbon group, and more preferably a chain aliphatic hydrocarbon group.
The hydrocarbon group represented by R ¹³ is preferably an aliphatic hydrocarbon group.
m1 is preferably 2, and h1 is preferably 1.
k1 is preferably an integer of 1 to 500, and more preferably an integer of 100 to 300.
As n1, Preferably it is an integer of 1-200, More preferably, it is an integer of 10-100.
R ¹⁵ in the general formula (1-1) corresponds to a group represented by “R ⁵ -R ⁶ ” when R ⁶ in the general formula (1) is a hydrogen atom. When R ¹⁵ is a group represented by “R ⁵ -R ⁶ ”, R ⁵ is a preferred example as described above, and R ⁶ is preferably a hydrogen atom. Specifically, in the general formula (1-1), R ¹⁵ is an alkyl group (that is, a divalent hydrocarbon group represented by R ⁵ in the general formula (1) is a branched alkylene group; ⁶ is a hydrogen atom).

Compound (A-1) is represented by, for example, “R ¹¹ -[(O—R ¹² ) _k1 -OH] _m1 (where R ¹¹ , R ¹² , k1, and m1 are as defined above”). Polyether polyols, “R ¹³ — (NCO) _{h1 + 1} (wherein R ¹³ and h1 are as defined above)”, “HO— (R ¹⁴ —O) _n1 − R ¹⁵ (wherein R ¹⁴ , R ¹⁵ , and n1 are the same as defined above) ”is preferably obtained by a method of reacting with a polyether monoalcohol.
Here, each of the polyether polyol, polyisocyanate, and polyether monoalcohol, which are raw materials used for the reaction, may be one kind or two or more kinds.

When the compound (A-1) is obtained by the above method, the hydrocarbon group represented by R ^{11 to} R ¹⁵ in the general formula (1-1) is represented by the three raw materials “R ¹¹ -[(O— R ¹²⁾ _{k1 -OH] m1} "," ^R 13 - by _{(NCO) h1 + 1} ", and" _{^{HO- (R 14 -O) n1 -R}} 15 ", respectively, are determined.
The charging ratio of the three raw materials is not particularly limited. For example, the ratio of the isocyanate group derived from polyisocyanate to the hydroxyl group derived from polyether polyol and polyether monoalcohol is NCO: OH = 0.8. : It is preferable to be in the range of 1 to 1.4: 1.

_{^{"R 11 - [(O-R}} 12) k1 -OH] polyether polyol represented by _m1 is the m1-valent polyol, ethylene oxide, propylene oxide, butylene oxide, to an addition polymerization of alkylene oxide such as epichlorohydrin etc. Is obtained.
Therefore, the hydrocarbon group represented by R ¹¹ is determined by the structure of the m1 valent polyol used for the synthesis of the compound (A-1). The hydrocarbon group represented by R ¹² is determined by the alkylene oxide or the like that is addition-polymerized to the m1-valent polyol.

Here, the polyol is preferably a divalent to octavalent one. Specifically, for example, a dihydric alcohol such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol; glycerin, trioxyisobutane 1,2,3-butanetriol, 1,2,3-pentatriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1 , 2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4 -Pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2, -Trihydric alcohols such as pentanetriol, trimethylolethane, trimethylolpropane; pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4, Tetravalent alcohols such as 5-pentanetetrol, 1,3,4,5-hexanetetrol; pentavalent alcohols such as adnit, arabit and xylit; hexavalent alcohols such as dipentaerythritol, sorbit, mannitol and exit An octahydric alcohol such as sucrose;
In the present invention, a divalent alcohol, particularly ethylene glycol is preferred.

  As the alkylene oxide or the like to be addition-polymerized to the above-described m1 polyol, an alkylene oxide having 2 to 4 carbon atoms is preferable, and ethylene oxide is particularly preferable from the viewpoint that it is easily available and exhibits an excellent effect.

Homopolymerization may be sufficient as the form of addition polymerization, such as alkylene oxide, and the copolymerization using 2 or more types may be sufficient as it. The copolymerization may be random polymerization or block polymerization. The addition polymerization method may be a normal method.
K1 which shows a polymerization degree should just be the range of 0-1000, the range of 1-500 is preferable, and the range of 100-300 is more preferable.
Ratio of ethylene groups in the total ^{R 12} is preferably in the range of 50 wt% to 100 wt% of the total ^{R 12.}

“R ¹¹ — [(O—R ¹² ) _k1 —OH] The molecular weight of _m1 is preferably 500 to 100,000, particularly preferably 1,000 to 50,000.

Polyisocyanates represented by ^- "R ¹³ (NCO) h1 + _1" is not particularly limited as long as it has two or more isocyanate groups in the molecule.
Therefore, the hydrocarbon group represented by R ¹³ is determined by the polyisocyanate used for the synthesis of the compound (A-1).
Examples of the polyisocyanate used in the present invention include aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, phenylmethane diisocyanate, triisocyanate, and tetraisocyanate. In the present invention, aliphatic diisocyanates are preferred.

  Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene Range isocyanine DOO, tetramethylxylylene diisocyanate, and the like. Of these, hexamethylene diisocyanate is preferably used.

  Examples of the aromatic diisocyanate include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4- Examples include naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate.

  Examples of the alicyclic diisocyanate include hydrogenated xylylene diisocyanate and isophorone diisocyanate.

  Examples of the biphenyl diisocyanate include biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, and 3,3′-dimethoxybiphenyl diisocyanate.

  Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ′. , 5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis (4-isothiontphenyl) methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane 3,3′-diisocyanate, 4,4′-diethoxydiphenylmethane-3,3′-diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenylmethane-4,4′-diisocyanate, 3,3′- Dichlorodiphenyldimethyl Tan-4,4'-diisocyanate, benzophenone-3,3'-diisocyanate, and the like.

  Examples of the triisocyanate of phenylmethane include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, and 1,3,7-naphthalenetriisocyanate. Isocyanate, biphenyl-2,4,4′-triisocyanate, diphenylmethane-2,4,4′-triisocyanate, 3-methyldiphenylmethane-4,6,4′-triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenyl) Such as thiophosphate It is below.

  As the polyisocyanate, dimer or trimer (isocyanurate bond) of the above polyisocyanate may be used, or biuret obtained by reacting the above polyisocyanate with an amine may be used.

Furthermore, you may use the polyisocyanate which has the urethane bond which reacted these polyisocyanate and polyol. The polyol used here is preferably a divalent to octavalent one, and the aforementioned polyol is preferable.
In addition, when using polyisocyanate more than trivalence as "R _< ¹³ _> -(NCO) _{h1 + 1} ", the polyisocyanate which has said urethane bond is preferable.

The polyether monoalcohol represented by “HO— (R ¹⁴ —O) _n1 —R ¹⁵ ” is not particularly limited as long as it is a monohydric alcohol polyether.
Such a compound can be obtained by addition polymerization of a monohydric alcohol with an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, or the like.
Therefore, the hydrocarbon group represented by R ¹⁵ is determined by the monovalent alcohol used for the synthesis of the compound (A-1). The hydrocarbon group represented by R ¹⁴ is determined by an alkylene oxide or the like that undergoes addition polymerization to a monovalent alcohol.

The monovalent alcohol here is an alcohol represented by the following general formula (2), (3), or (4).
Therefore, R ¹⁵ corresponds to a group excluding the hydroxyl group in the following general formulas (2) to (4).

Formula ^(2): R a -OH
Formula ^{(3): R b -CH (} R c) -R d -OH
General formula (4): R < ^e > -CH (R < ^f >)-OH

In the general formulas (2) to (4), R ^a , R ^b , R ^c , R ^e , and R ^f each independently represent a hydrocarbon group, specifically, for example, an alkyl group, an alkenyl group, Examples thereof include hydrocarbon groups such as an alkylaryl group, a cycloalkyl group, and a cycloalkenyl group.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl. , Tridecyl, isotridecyl, myristyl, palmityl, stearyl, isostearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl branched-isostearyl and the like.

  Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

  Examples of alkylaryl groups include toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, and nonylphenyl groups. Can be mentioned.

  Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, and the like. Examples of the cycloalkenyl group include cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl. And methylcycloheptenyl group.

In the general formula (3), R ^c represents a divalent hydrocarbon group, and specific examples include an alkylene group, an alkenylene group, an alkylarylene group, a cycloalkylene group, and a cycloalkenylene group.
Examples of these hydrocarbon groups include alkylene groups and alkenylenes in which one hydrogen atom is removed from the preferred examples of the alkyl group, alkenyl group, alkylaryl group, cycloalkyl group, and cycloalkenyl group listed above. Groups, alkylarylene groups, cycloalkylene groups, and cycloalkenylene groups.

  Alkylene oxide, etc., which is addition-polymerized to the above-mentioned monohydric alcohol, is particularly easily available, and in order to exert excellent effects, alkylene oxides having 2 to 4 carbon atoms are preferred, and ethylene oxide is particularly preferred. .

Homopolymerization may be sufficient as the form of addition polymerization, such as alkylene oxide, and the copolymerization using 2 or more types may be sufficient as it. The copolymerization may be random polymerization or block polymerization. The addition polymerization method may be a normal method.
N1 which shows a polymerization degree should just be the range of 0-1000, the range of 1-200 is preferable, and the range of 10-200 is more preferable.
Ratio of ethylene groups in the total ^{R 14} is the range of 50 to 100 mass% of the total ^{R 14,} more preferably in the range of 65 to 100 mass%.

  Compound (A-1): As a method for producing the compound represented by the general formula (1-1), for example, at a temperature of 80 to 90 ° C., 1 to 3 in the same manner as the reaction of an ordinary polyether and isocyanate. It can be obtained by heating for hours and reacting.

A polyether polyol represented by ^- _{'[(O-R 12) k1} -OH] m1 R 11 "(a), - the" ^R 13 _{(NCO) h1 + 1} "represented by a polyisocyanate (b)," When the polyether monoalcohol (c) represented by “HO— (R ¹⁴ —O) _n1 —R ¹⁵ ” is reacted, other than the compound (copolymer) represented by the general formula (1-1) Things can also be a by-product.
For example, when a diisocyanate is used, the main product is a c-b-a-b-c type copolymer represented by the general formula (1-1). , Cb- (ab) _x -abc type copolymers may be by-produced.
In this case, the c-b-a-b-c type copolymer represented by the general formula (1-1) is used in the skin external preparation of the present invention in the form of a mixture containing the copolymer without separation. May be.

As the compound (A-1) used in the present invention, compounds described in JP-A-9-71766 are preferably used.
In the present invention, PEG-240 / decyltetradeceth-20 / hexamethylene diisocyanate (HDI) copolymer is particularly suitable as compound (A-1).
Such a copolymer is commercially available from ADEKA Corporation under the trade name “Adecanol GT-700”.

[Compound represented by formula (1-2)]
In the present invention, the compound represented by the general formula (1) is preferably a compound represented by the following general formula (1-2) (hereinafter sometimes referred to as the compound (A-2)).

In the general formula (1-2), R ²¹ represents a m2-valent saturated hydrocarbon group having 6 to 36 carbon atoms, and R ²² represents a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, 3-methyl. −3,5,5-trimethylcyclohexylene group, dimethylphenylene group, or tolylene group, and R ²³ represents a hydrogen atom or a methyl group. n2 represents an integer of 90 to 900, and m2 represents an integer of 1 to 5.
Here, as R < ²¹ >, it is a C6-C36 saturated hydrocarbon group, Especially, a C6-C36 linear alkyl group or a branched alkyl group is preferable.

Compound (A-2) includes a polyalkylene oxide compound represented by “H— (O—CHR ²³ CH ₂ ) _n2 —OH (wherein R ²³ and n2 are as defined above)”, and “HO -R ²¹ (where R ²¹ is as defined above) "and" R ²² <(NCO) ₂ (where R ²² is as defined above) " It can be obtained by reacting these compounds with a diisocyanate compound represented by

Specific examples of the polyalkylene oxide compound represented by “H— (O—CHR ²³ CH ₂ ) _n2 —OH” include polyethylene oxide, polypropylene oxide, polyethylene oxide / polypropylene oxide (preferably ethylene oxide and propylene). Oxide copolymer) and the like.
Among these polyalkylene oxide compounds, polyalkylene oxide compounds containing 70% by mass or more of ethylene oxide groups are preferable, and polyalkylene oxide compounds having 95% by mass or more of ethylene oxide groups are more preferable.

The monovalent hydrophobic alcohol represented by “HO—R ²¹ ” is preferably an alcohol having a solubility in water in the range of 0.4% by mass or less. Specifically, for example, hexyl alcohol, heptyl Alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, aralkyl alcohol, 2- Examples thereof include octyldodecanol and behenyl alcohol, preferably cetyl alcohol and behenyl alcohol.
These monovalent hydrophobic alcohols may be used alone or in combination of two or more.

  The monovalent hydrophobic alcohol is preferably used in a proportion of 0.2 mol to 1.0 mol, and used in a proportion of 0.25 mol to 0.70 mol, relative to 1 mol of the polyalkylene oxide compound. It is more preferable.

Specific examples of the diisocyanate compound represented by “R ²² <(NCO) ₂ ” include 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), and dicyclohexylmethane-4,4 ′. -Diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzole-2,4-diisocyanate, 2,4-tolylene diisocyanate (TDI), etc. It is done.
Among these diisocyanate compounds, dicyclohexylmethane-4,4′-diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI) are preferable.
These diisocyanate compounds may be used alone or in combination of two or more.

  The diisocyanate compound is composed of the number of moles of isocyanate groups of the isocyanate compound ([—NCO] relative to the total number of moles of terminal hydroxyl groups of the polyalkylene oxide compound and the monovalent hydrophobic alcohol compound (number of moles of [—OH]). ] Is preferably used at a ratio of 0.67 mol to 0.91 mol, and more preferably at a ratio of 0.70 mol to 0.90 mol.

Examples of the method for reacting the polyalkylene oxide compound, the monovalent hydrophobic alcohol, and the diisocyanate compound described above include, for example, a method of reacting by dissolving or dispersing in a reaction solvent such as toluene, xylene, dimethylformamide, or the like; For example, there may be mentioned a method of pulverizing (powder) or melting into a liquid and mixing them uniformly and then heating them to a predetermined temperature for reaction.
As a method for synthesizing compound (A-2), methods described in paragraphs [0049] to [0051] of JP2013-116941A are preferably used.

  In the present invention, as compound (A-2), bisstearyl PEG / PPG-8 / 6 (methylenediphenyl diisocyanate / PEG-400) copolymer, that is, commercially available from Sumitomo Seika Co., Ltd. under the trade name “Apeck HU type C”. The compounds described are preferred.

The content of the compound (A) in the external preparation for skin of the present invention is preferably 0.4% by mass or more, more preferably 0.8% by mass or more, and 1.2% by mass or more with respect to the total amount of the external preparation for skin. Is more preferable.
When used at 0.4% by mass or more, a skin external preparation with sufficient viscosity and reduced odor can be obtained.
In addition, the upper limit of the content of the compound (A) is preferably 5.0% by mass or less, more preferably 4.0% by mass or less from the viewpoint of usability. The preferred range of the content of the compound (A) is the above Can be determined based on the upper and lower limits.

[Specific stabilizer (B)]
The external preparation for skin of the present invention is abbreviated as magnesium ascorbate phosphate magnesium (sometimes abbreviated as magnesium ascorbyl phosphate, “APM”) and sodium ascorbyl phosphate ester (sodium ascorbyl phosphate as “APS”). At least one compound selected from the group (specific stabilizer (B)).
The specific stabilizer (B) is a compound that itself hardly undergoes crystal precipitation over time, and is a compound that can prevent oxidative degradation of the carotenoid (C) that coexists and improve the stability of the carotenoid (C). .
The external preparation for skin of the present invention using the specific stabilizer (B) is improved in the stability of carotenoid (C), does not show crystal precipitation over time, and is excellent in stability over time. Become.

  As the specific stabilizer (B), magnesium ascorbate phosphate is preferable from the viewpoint of carotenoid stability.

As the specific stabilizer (B), a commercially available product may be used.
Specifically, for example, ascorbic acid magnesium phosphate, trade name: ascorbic acid PM (Showa Denko), trade name: NIKKOL (registered trademark) VC-PMG (Nikko Chemicals), trade name: Seamate (Takeda Pharmaceutical) Industrial) and the like.
Ascorbic acid sodium phosphate ester includes: Ascorbic acid PS (Showa Denko) and the like.

The content of the specific stabilizer (B) in the external preparation for skin of the present invention is determined from the viewpoint of carotenoid stability and odor reduction.
Specifically, the content of the specific stabilizer (B) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 0.3% by mass with respect to the total mass of the external preparation for skin. The above is more preferable. As an upper limit of content of a specific stabilizer (B), 10 mass% is preferable, 5 mass% is more preferable, and 3 mass% is still more preferable.
The preferable range of content of a specific stabilizer (B) can be determined based on said upper limit and lower limit.

(Other ascorbic acid or ascorbic acid derivatives)
In the present invention, in addition to the specific stabilizer (B), other ascorbic acid or ascorbic acid derivatives other than the specific stabilizer (B) may be used in combination.

Other ascorbic acid or ascorbic acid derivatives include ascorbic acid, sodium ascorbate, potassium ascorbate, calcium ascorbate, ascorbyl sulfate, ascorbyl sulfate disodium salt, ascorbyl-2-glucoside, trisodium ascorbyl phosphate palmitate, etc. Can be mentioned.
Among these, those suitable for use in combination with the specific stabilizer (B) are ascorbic acid, sodium ascorbate, ascorbyl-2-glucoside, trisodium ascorbyl palmitate, which is difficult to crystallize. .

  These ascorbic acid or its derivative can use what is generally marketed suitably. For example, L-ascorbic acid (Takeda Pharmaceutical, Fuso Chemical, BASF Japan, Daiichi Pharmaceutical, etc.), L-Ascorbic acid Na (Takeda Pharmaceutical, Fuso Chemical, BASF Japan, Daiichi Pharmaceutical, etc.), Ascorbyl-2-glucoside (Trade name AA-2G: Hayashibara Biochemical Research Institute) and the like.

[Carotenoid (C)]
The skin external preparation of the present invention contains a carotenoid (C).
Carotenoid (C) is a pigment of yellow to red terpenoids, and examples thereof include those derived from plants, algae, and bacteria.
The carotenoid (C) used in the present invention includes those derived from natural products and those obtained in accordance with ordinary methods, and those derived from natural products are preferred from the viewpoint of the odor reduction effect of the present invention.

Specific examples of the carotenoid (C) include lycopene, α-carotene, β-carotene, γ-carotene, δ-carotene, actinioerythrol, bixin, canthaxanthin, capsorubin, β-8′-apo-carotenal ( Apocarotenal), β-12′-apo-carotenal, xanthophylls (for example, astaxanthin, fucoxanthin, lutein, zeaxanthin, capsanthin, β-cryptoxanthin, violaxanthin, and the like) and hydroxyl or carboxyl derivatives thereof.
The carotenoid (C) is preferably at least one selected from the group consisting of astaxanthin, lycopene, β-carotene, fucoxanthin, and lutein from the standpoint of singlet oxygen scavenging ability, so-called antioxidant effect, and astaxanthin. , Lycopene, and β-carotene are more preferable, and at least one selected from the group consisting of astaxanthin and lycopene is most preferable.
These carotenoids may be used alone or in combination of two or more.

  The carotenoid (C) in the present invention is a crystalline carotenoid. Here, the “crystalline carotenoid” does not represent a specific carotenoid, and when it is in the form of oil or paste containing carotenoid, due to various factors such as its production method, treatment, storage, etc. It means a carotenoid that can exist as a crystal at any temperature in the temperature range of 5 ° C to 35 ° C. In particular, lycopene and astaxanthin, which will be described later, β-carotene, δ-carotene, zeaxanthin, lutein and the like are carotenoids in which crystals are likely to exist.

(Astaxanthin)
Astaxanthin mentioned as a preferable thing in this invention includes at least one of derivatives, such as an ester of astaxanthin and an astaxanthin. In the present invention, unless otherwise specified, these are collectively referred to as “astaxanthin”.

Astaxanthin used in the present invention can be any natural product such as plants, algae, crustaceans and bacteria, as long as it can be obtained according to a conventional method.
Examples of natural astaxanthin include red yeast Phaffia, green algae hematococcus, marine bacteria (paracoccus), krill, and adonis. Moreover, the extract from the culture etc. can be mentioned.
Astaxanthin may be contained in the skin external preparation of the present invention as an astaxanthin-containing oil obtained as a separate or extract from a natural product containing astaxanthin. Astaxanthin may be a product obtained by appropriately purifying a product separated or extracted from this natural product as necessary, or may be a synthetic product.
As astaxanthin, those extracted from Haematococcus algae (also referred to as Haematococcus alga extract) and pigments derived from krill are particularly preferred from the viewpoint of quality or productivity.

  Specific examples of astaxanthin derived from an extract of Haematococcus alga that can be used in the present invention include Haematococcus pluviaris, Haematococcus lacustris, Examples include, but are not limited to, astaxanthin derived from extracts from Haematococcus droebakensis, Haematococcus zimbabiensis, and the like.

The Haematococcus alga extract that can be used in the present invention is prepared by using the above-mentioned raw materials, if necessary, by crushing the cell wall by a method disclosed in, for example, JP-A-5-68585, etc., and adding acetone, ether, chloroform, and alcohol. You may obtain by adding organic solvents, such as (ethanol, methanol, etc.), and extraction solvents, such as a supercritical carbon dioxide.
In the present invention, as the astaxanthin, a widely marketed Haematococcus alga extract can be used. Commercially available products include, for example, ASTOTS-S, -2.5 O, -5 O, -10 O, etc. manufactured by Takeda Paper Instruments Co., Ltd., Asteryl Oil 50F manufactured by Fuji Chemical Industry Co., Ltd. 5F and the like, BioAstin SCE7 manufactured by Toyo Enzyme Chemical Co., Ltd. and the like.

The content of pure astaxanthin in the Haematococcus alga extract that can be used in the present invention is preferably 0.001% by mass to 50% by mass, more preferably from the viewpoint of handling during composition production. It is 0.01 mass%-25 mass%.
In addition, the Haematococcus alga extract that can be used in the present invention may contain astaxanthin or an ester thereof as a pure pigment, as in the dye described in JP-A-2-49091. In this case, those containing 50 mol% or more, preferably 75 mol% or more, more preferably 90 mol% or more can be preferably used.

(Lycopene)
Lycopene, which is mentioned as preferable in the present invention, is a carotenoid represented by the chemical formula C ₄₀ H ₅₆ , belongs to a carotenoid of carotenoids, and is a red pigment having an absorption maximum at 474 nm (acetone).

  In lycopene, there are also cis- and trans- isomers of a conjugated double bond at the center of the molecule, and examples include all-trans-, 9-cis and 13-cis isomers. In the present invention, Any of these may be used.

  Lycopene may be contained in the skin external preparation of the present invention as a lycopene-containing oil or lycopene-containing paste separated or extracted from a natural product containing it.

Lycopene is naturally contained in tomatoes, strawberries, watermelons, and pink grapefruits, and the above-mentioned lycopene-containing oil may be separated or extracted from these natural products. There are four known product types: oil type, emulsion type, paste type, and powder type.
The lycopene used in the present invention may be an extract, a product obtained by appropriately purifying the extract as necessary, or a synthetic product.

One particularly preferred form of lycopene in the present invention is a fat-soluble extract extracted from tomato pulp. The fat-soluble extract extracted from tomato pulp is particularly preferable from the viewpoint of stability, quality or productivity in the composition containing the fat-soluble extract.
Here, the fat-soluble extract extracted from tomato pulp is extracted from a pulp-like solid obtained by further centrifuging a pulverized product obtained by pulverizing tomato using an oily solvent. It means an extract.
As lycopene which is a fat-soluble extract, a tomato extract widely marketed as lycopene-containing oil or paste can be used. Examples of commercially available products include Lyc-O-Mato 15%, Lyc-O-Mato 6% sold by Sunbright Co., Ltd., and lycopene 18 sold by Kyowa Hakko Kogyo Co., Ltd. .

The content of carotenoid (C) in the external preparation for skin of the present invention can be determined from the types of carotenoid, the expression of singlet oxygen scavenging ability (antioxidant effect), and the color of the external preparation for skin.
Specifically, the content of carotenoid (C) is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and further more preferably 0.002% by mass or more based on the total mass of the external preparation for skin. preferable. As an upper limit of content of carotenoid (C), 10 mass% is preferable, 5 mass% is more preferable, and 2 mass% is still more preferable.

  In the skin external preparation of the present invention, the carotenoid (C) is preferably contained as emulsified particles containing the carotenoid (C). By making it into the form of emulsified particles, carotenoid (C) can be stably contained in the system of the external preparation for skin.

The skin external preparation of the present invention may be an emulsion. The emulsion may be an oil-in-water emulsion (O / W emulsion) or a water-in-oil emulsion (W / O emulsion). Can be selected.
The external skin preparation of the present invention is more preferably an oil-in-water emulsion having emulsified particles containing carotenoid (C) as one of the oil phase components from the viewpoint of stabilization in the system of carotenoid (C). preferable.

〔water〕
The skin external preparation of the present invention may further contain water.
In particular, the external preparation for skin of the present invention is preferably an emulsion containing emulsion particles containing water and containing carotenoids.
The water used here is not particularly limited as long as it can be applied to an external preparation for skin.
When the skin external preparation of the present invention is used as an emulsion, water is one of the components constituting the aqueous phase.

[Other ingredients]
The external preparation for skin of the present invention can contain other components as necessary in addition to the above components within the range not impairing the effects of the present invention.
That is, the other components shown below are components that do not correspond to the compound (A), the specific stabilizer (B), and the carotenoid (C) in the present invention.

(Phospholipids and their derivatives)
The external preparation for skin of the present invention may contain phospholipids and derivatives thereof.
Phospholipids and derivatives thereof contribute to the emulsion stability when the external preparation for skin of the present invention is an emulsion having emulsion particles containing carotenoids.

The phospholipid in the present invention is an ester composed of fatty acid, alcohol, phosphoric acid and nitrogen compound among complex lipids, and is a group having a phosphate ester and a fatty acid ester, a glycerophospholipid not containing glycerin, and a sphingo containing sphingosine. It refers to phospholipids.
Specific examples of the phospholipid used in the present invention include phosphatidic acid, bisphosphatidic acid, lecithin (phosphatidylcholine), phosphatidylethanolamine, phosphatidylmethylethanolamine, phosphatidylserine, phosphatidylinositol, phosphatidylglycerol, diphosphatidylglycerol, sphingo Examples include myelin and the like, and those derived from plants such as soybeans, corn, peanuts, rapeseed, and wheat, those derived from animals such as egg yolk and cows, and various lecithins derived from microorganisms such as E. coli. Can be mentioned. A mixture of these, lecithin and hydrogenated lecithin can also be used.
The origin of these phospholipids is not particularly limited. For example, vegetable oils such as soybean oil, those derived from animals such as egg yolk, etc. are used, and particularly purified ones are suitable.

In the present invention, as a glycerophospholipid, glycerophospholipid having one fatty acid residue in one molecule as a result of enzymatic degradation, that is, lysolecithin is also included.
Such lysolecithin can be obtained by hydrolysis of lecithin with an acid or alkali catalyst, but can also be obtained by hydrolysis of lecithin with phospholipase A ₁ or A ₂ .
Examples of such lysolecithin include lysophosphatidic acid, lysophosphatidylglycerin, lysophosphatidylinositol, lysophosphatidylethanolamine, lysophosphatidylmethylethanolamine, lysophosphatidylcholine (lysolecithin), lysophosphatidylserine and the like.

As the glycerophospholipid represented by the above lecithin, hydrogenated or hydroxylated one can also be used in the present invention. Specifically, for example, hydrogenated lecithin, enzymatically decomposed lecithin, enzymatically decomposed hydrogenated lecithin, Hydroxylecithin or the like can be used.
The hydrogenation is performed, for example, by reacting lecithin with hydrogen in the presence of a catalyst, and the unsaturated bond of the fatty acid moiety is hydrogenated. Hydrogenation improves the stability of lecithin.
Moreover, the said hydroxylation heats a lecithin with organic acids, such as high concentration hydrogen peroxide and an acetic acid, tartaric acid, butyric acid, and the unsaturated bond of a fatty-acid part is hydroxylated. Hydroxylation improves the hydrophilicity of lecithin.

In the present invention, lecithin is particularly preferable from the viewpoint of emulsion stability.
Examples of commercially available lecithins include the Riken series manufactured by Riken Vitamin Co., Ltd. and Recimar EL.

Although lecithin having a purity of 60% by mass or more is industrially used as lecithin, the lecithin used in the present invention preferably has a lecithin purity of 80% by mass or more generally called “high purity lecithin” More preferably, it is 90 mass% or more.
This lecithin purity (mass%) is obtained by subtracting the mass of the toluene insoluble matter and the acetone soluble matter by utilizing the property that lecithin is easily dissolved in toluene and not dissolved in acetone. High-purity lecithin is preferred because it has higher lipophilicity than lysolecithin, and therefore, the compatibility between lecithin and the oil component is increased, and the emulsion stability can be improved.
The phospholipids and derivatives thereof used in the present invention can be used alone or in the form of a mixture of plural kinds.

  When using phospholipid and its derivative for the skin external preparation of this invention, content of phospholipid and its derivative is 0.001 mass%-5 with respect to the total mass of skin external preparation from viewpoints of emulsification stability etc. It is preferable that it is mass%, More preferably, it is 0.002 mass%-3 mass%.

(emulsifier)
The skin external preparation of the present invention may contain an emulsifier.
The emulsifier is suitably used when the external preparation for skin of the present invention is an emulsion having emulsified particles containing carotenoids.

The emulsifier used in the present invention is not particularly limited as long as it is an emulsifier that dissolves in an aqueous medium, that is, a water-soluble emulsifier. For example, a nonionic emulsifier having an HLB of 10 or more, preferably an HLB of 12 or more is preferable.
If the HLB is less than 10, the emulsifying power may be insufficient. Moreover, it is preferable that HLB is 16 or less from a viewpoint of emulsion stability.

Here, HLB is a hydrophilic-hydrophobic balance that is usually used in the field of surfactants, and a commonly used calculation formula such as the Kawakami formula can be used. In the present invention, the Kawakami equation is adopted.
HLB = 7 + 11.7log (Mw / Mo)
Here, Mw is the molecular weight of the hydrophilic group, and Mo is the molecular weight of the hydrophobic group.
Moreover, you may use the numerical value of HLB described in the catalog etc.
Further, as can be seen from the above formula, an emulsifier having an arbitrary HLB value can be obtained by utilizing the additivity of HLB.

The emulsifier used in the present invention is not particularly limited, but the above-described nonionic emulsifier is preferable.
Examples of the nonionic emulsifier include glycerin fatty acid ester, organic acid monoglyceride, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyglycerin condensed ricinoleic acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester. More preferred are polyglycerin fatty acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters.
The emulsifier is not necessarily highly purified by distillation or the like, and may be a reaction mixture.

Examples of the polyglycerol fatty acid ester used in the present invention include an average degree of polymerization of 2 or more, preferably 6 to 15, more preferably 8 to 10 and a fatty acid having 8 to 18 carbon atoms such as caprylic acid. , Esters with capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid.
Preferred examples of polyglycerol fatty acid esters include hexaglycerol monooleate, hexaglycerol monostearate, hexaglycerol monopalmitate, hexaglycerol monomyristate, hexaglycerol monolaurate, decaglycerol monooleate , Decaglycerin monostearic acid ester, decaglycerin monopalmitic acid ester, decaglycerin monomyristic acid ester, decaglycerin monolauric acid ester and the like. These polyglycerin fatty acid esters can be used alone or in combination.

  Examples of commercially available polyglycerin fatty acid esters include Nikko Chemicals Co., Ltd., NIKKOL DGMS, NIKKOL DGMO-CV, NIKKOL DGMO-90V, NIKKOL DGDO, NIKKOL DGKI, NIKKOL DGGIS, NIKKOL TGIS 1-O, NIKKOL Tettaglyn 3-S, NIKKOL Tettaglyn 5-S, NIKKOL Tetlagyn 5-O, NIKKOL Hexagly 1-M S, NIKKOL Hexaglyn 4-B, NIKKOL Hexaglyn 5-S, NIKKOL Hexaglyn 5-O, NIKKOL Hexaglyn PR-15, NIKKOL Decaglyn 1-L, NIKKOL Decaglyn 1-M, NIKKOL Decaglyn 1-SV, NIKKOL Decaglyn 1-50SV, NIKKOL Decaglyn 1- ISV, NIKKOL Decaglyn 1-O, NIKKOL Decaglyn 1-OV, NIKKOL Decaglyn 1-LN, NIKKOL Decaglyn 2-SV, NIKKOL Decaglyn 2-ISV, NIKKOL Decaglyn 3-SV, NIKKOL Decaglyn 3-OV, NIKKOL Decaglyn 5-SV, NIKK OL Decaglyn 5-HS, NIKKOL Decaglyn 5-IS, NIKKOL Decaglyn 5-OV, NIKKOL Decaglyn 5-O-R, NIKKOL Decaglyn 7-S, NIKKOL Decaglyn 7-O, NIKKOL Decaglyn 10-SV, NIKKOL Decaglyn 10-IS, NIKKOL Decaglyn 10-OV, NIKKOL Decaglyn 10-MAC, NIKKOL Decaglyn PR-20, etc. ("NIKKOL" is a registered trademark); Ryoto-polyglyceride LD-10, manufactured by Mitsubishi Chemical Foods Co., Ltd. 10D, M-7D, P-8D, S-28D, S-24D, SWA-20D, SWA-15D, SWA-10D, O- 50D, O-15D, B-100D, B-70D, ER-60D, Taiyo Chemical Co., Ltd. Sunsoft Q-17UL, Sunsoft Q-14S, Sunsoft A-141C, etc. ("Sunsoft" is all Registered trademark); Poem DO-100 manufactured by Riken Vitamin Co., Ltd., Poem J-0021, etc. (all "Poem" are registered trademarks);

  The sorbitan fatty acid ester used in the present invention preferably has 8 or more carbon atoms, more preferably 12 or more. Preferred examples of sorbitan fatty acid esters include sorbitan monocaprylate, sorbitan monolaurate, sorbitan monostearate, sorbitan sesquistearate, sorbitan tristearate, sorbitan isostearate, sorbitan sesquiisostearate, sorbitan oleate, sorbitan sesquioleate And sorbitan trioleate. These sorbitan fatty acid esters can be used alone or in combination.

  As a commercial item of sorbitan fatty acid ester, Nikko Chemicals Co., Ltd. make, NIKKOL SL-10, SP-10V, SS-10V, SS-10MV, SS-15V, SS-30V, SI-10RV, SI-10 15RV, SO-10V, SO-15MV, SO-15V, SO-30V, SO-10R, SO-15R, SO-30R, SO-15EX, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Sorgen 30V, 40V, 50V, 90, 110 etc. are mentioned.

The sucrose fatty acid ester used in the present invention preferably has a fatty acid having 12 or more carbon atoms, more preferably 12-20.
Preferred examples of sucrose fatty acid esters include sucrose dioleate, sucrose distearate, sucrose dipalmitate, sucrose dimyristic ester, sucrose dilaurate, sucrose monooleate, sucrose Examples thereof include sugar monostearate, sucrose monopalmitate, sucrose monomyristate, and sucrose monolaurate. In the present invention, these sucrose fatty acid esters can be used alone or in combination.

  Examples of commercially available sucrose fatty acid esters include Ryoto Sugar Esters S-070, S-170, S-270, S-370, S-370F, S-570, and S- manufactured by Mitsubishi Chemical Foods Corporation. 770, S-970, S-1170, S-1170F, S-1570, S-1670, P-070, P-170, P-1570, P-1670, M-1695, O-170, O-1570, OWA-1570, L-195, L-595, L-1695, LWA-1570, B-370, B-370F, ER-190, ER-290, POS-135, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , DK ester SS, F160, F140, F110, F90, F70, F50, F-A50, F-20W, F-10, F-A10E, Cosmelike B-30, S-10 S-50, S-70, S-110, S-160, S-190, SA-10, SA-50, P-10, P-160, M-160, L-10, L-50, L- 160, L-150A, L-160A, R-10, R-20, O-10, O-150 and the like.

  When an emulsifier is used in the external preparation for skin of the present invention, the content of the emulsifier is obtained from the viewpoint of obtaining fine emulsified particles, obtaining the stability of the emulsion, and suppressing foaming of the emulsion. The total mass is preferably 0.001% by mass to 10% by mass, and more preferably 0.002% by mass to 5% by mass.

(Tocopherol)
The external preparation for skin of the present invention may contain tocopherol as one of oily components from the viewpoint of preventing carotenoid oxidation.
Usable tocopherols are not particularly limited and are selected from the group of compounds consisting of tocopherols or derivatives thereof.
Specific examples of the compound group consisting of tocopherol or derivatives thereof include dl-α-tocopherol, dl-β-tocopherol, dl-γ-tocopherol, dl-δ-tocopherol, dl-α-tocopherol acetate, nicotinic acid- Examples include tocopherols and derivatives thereof such as dl-α-tocopherol, linoleic acid-dl-α-tocopherol, and dl-α-tocopherol succinate, α-tocotrienol, β-tocotrienol, γ-tocotrienol, and δ-tocotrienol.
These are often used in the form of a mixture, and can be used in a state called extracted tocopherol, mixed tocopherol or the like.

  When tocopherol is used in the external preparation for skin of the present invention, the content of tocopherol is 0.1 to 5 times based on the mass of carotenoid in terms of mass, from the point of being effective in preventing carotenoid oxidation. Is preferable, more preferably 0.2 times to 3 times, and still more preferably 0.5 times to 2 times.

(Other oil components)
The external preparation for skin of the present invention may contain various oils applicable to the external preparation for skin as other oil components.
Specific examples of various oils include lauroyl sarcosine isopropyl, caprylic / capric triglycerides (also known as tri (caprylic / capric) glyceryl), isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate Butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, di-2 -Ethylene glycol ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, Diisostearyl golate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, tri-2-ethylhexanoic acid Glycerin, glyceryl trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid Methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl Esters, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, sebacic acid Ester oils such as diethyl, 2-ethylhexyl succinate, triethyl citrate;
Hydrocarbon oils such as squalane and liquid paraffin;
Silicone oils such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher alcohol-modified organopolysiloxane;
Fluorine oils such as fluoropolyether and perfluoroalkyl ether silicone;
Vegetable oils such as olive oil and jojoba oil;
Examples thereof include animal oils such as liquid lanolin.

  When other oily components are used in the skin external preparation of the present invention, the content of other oily components is preferably 0.001% by mass to 20% by mass, more preferably 0.002% by mass to 15% by mass. %.

(Polyhydric alcohol)
The skin external preparation of the present invention can contain a polyhydric alcohol from the viewpoint of obtaining fine emulsified particles, obtaining stability of the emulsion, and improving the feeling of use (moisturizing properties).
Examples of the polyhydric alcohol include glycerin, 1,3-butanediol, ethylene glycol, or polysaccharides such as reduced starch syrup, sucrose, erythritol, xylitol, glucose, galactose, sorbitol, maltotriose, trehalose, and the like. Can be mentioned. A polyhydric alcohol can be used individually by 1 type or in combination of 2 or more types.

  When polyhydric alcohol is used for the skin external preparation of the present invention, the content of the polyhydric alcohol is preferably 0.01% by mass to 20% by mass of the total mass of the skin external preparation, and 0.05% by mass to It is more preferably 10% by mass, and further preferably 0.1% by mass to 10% by mass.

(Water-soluble polymer compound)
The external preparation for skin of the present invention may contain a water-soluble polymer compound for stabilizing the emulsion.
As the water-soluble polymer compound, a wide range of synthetic polymers, natural polymers, and semi-synthetic polymers can be used. Among them, in particular, carotenoid (C) and the like can be favorably stabilized. Protein is preferred.

Any kind of protein can be used as long as it is a polymer or oligomer in which amino acids are polymerized by peptide bonds, but it is preferably derived from a natural product and water-soluble.
Proteins include simple proteins composed of amino acids and complex proteins containing components other than amino acids, and both can be used.
Examples of simple proteins include gelatin, collagen, casein, fibroin, sericin, keratin, protamine and the like.
Complex proteins include glycoproteins that bind to carbohydrates, lipoproteins that bind to lipids, metal proteins that bind to metal ions, nucleoproteins that bind to ribonucleic acid, phosphate groups There are phosphoproteins that are proteins bound to

Proteins are often often referred to as protein raw materials, and examples include animal muscle protein, milk protein, egg protein, rice protein, wheat protein (wheat gluten), soy protein, yeast protein, and bacterial protein.
The protein may also be used as a mixture.
Among these proteins, water-soluble collagen, hydrolyzed collagen, and a mixture thereof are particularly preferable from the viewpoint of stabilization of the emulsion.

  When a water-soluble polymer compound is used in the external preparation for skin of the present invention, the water-soluble polymer compound can be added at an arbitrary ratio with respect to the entire oil component, but for stabilizing the emulsion, 0.1 times or more and 100 times or less are preferable with respect to the oil component, and 0.5 times or more and 50 times or less are more preferable.

(Other additive ingredients)
The external preparation for skin of the present invention can contain an additive component usually used for cosmetics or pharmaceuticals based on the intended use within a range not impairing the effects of the present invention.
Examples of the additive component include water-soluble organic solvents such as ethanol, chelating agents, whitening agents, emollients such as triisodecyl isononanoate, moisturizers, antioxidants, agar, and hydrophilic thickeners such as xanthan gum and colorants. , Preservatives, pH adjusters, buffers, UV absorbers, fragrances, colorants, and the like.

[Form and application of external preparation for skin]
The form of the external preparation for skin of the present invention is not particularly limited as long as it contains the compound (A), the specific stabilizer (B), and the carotenoid (C) described above, and is appropriately selected depending on the application. Just do it.
As a form which the external preparation for skin of this invention can take, a liquid or solid is mentioned.
The form of the external preparation for skin of the present invention may be an emulsion composition (emulsion), an oily composition, a water-soluble composition, or the like.
In particular, the external preparation for skin of the present invention is preferably in the form of an emulsion having emulsified particles containing carotenoids in order to stably contain carotenoid (C) in the system of external preparation for skin.

The external preparation for skin of the present invention can be applied to uses such as cosmetics or pharmaceuticals.
Examples of the external preparation for skin of the present invention include skin care cosmetics (skin lotions, cosmetic liquids, emulsions, creams, etc.), UV care cosmetics such as lipsticks and sunscreen cosmetics, and makeup cosmetics. However, it is not limited to these.
The skin external preparation of the present invention is particularly preferably used as a skin care cosmetic from the viewpoint of scavenging ability (antioxidant effect) of singlet oxygen possessed by carotenoid (C).
When using the skin external preparation of this invention as cosmetics or a pharmaceutical, normally, the various components which can be mix | blended as cosmetics and a pharmaceutical can be used according to the objective.

〔Production method〕
The method for producing the external preparation for skin of the present invention is selected according to the intended form.
For example, when the external preparation for skin of the present invention is an emulsion having emulsified particles containing carotenoid (C), it is preferably produced by the following method.

The emulsion having the emulsified particles containing carotenoid (C) in the present invention is prepared by a production method including mixing an oil phase composition containing carotenoid (C) and an aqueous phase composition and emulsifying by a conventional method. Manufactured.
In the present invention, the oil phase composition preferably contains phospholipid or a derivative thereof, tocopherol, and other oily components together with the carotenoid (C).
On the other hand, the aqueous phase composition preferably contains the compound (A), the specific stabilizer (B), an emulsifier, a polyhydric alcohol, and water.
In addition, using the aqueous composition which does not contain a compound (A) and a specific stabilizer (B), and the said oil composition, first, the emulsion liquid (compound (A) and specific which contains the emulsion particle | grains containing a carotenoid (C)) Stabilizer (B) is not contained, and the emulsion is prepared by mixing an aqueous mixed solution containing at least the compound (A) and the specific stabilizer (B) with the emulsion. It may be prepared.

Hereinafter, a method for producing an emulsion having emulsified particles containing a carotenoid (C) in the present invention using an aqueous composition not containing the compound (A) and the specific stabilizer (B) and the oily composition. This will be described in detail.
For example, a) A water-soluble emulsifier is dissolved in an aqueous medium containing water to obtain an aqueous phase composition. B) A phospholipid or derivative thereof, tocopherol, and other oily components are mixed and dissolved to obtain an oil phase. A composition is obtained, and c) An emulsion containing emulsion particles containing carotenoid (C) is obtained by mixing the aqueous phase composition and the oil phase composition under stirring and carrying out emulsification dispersion.

  When emulsifying and dispersing, for example, after emulsification using a normal emulsifying device using a shearing action such as a stirrer, impeller stirring, homomixer, continuous flow type shearing device, etc., two or more types are passed by a method such as passing through a high-pressure homogenizer. It is particularly preferable to use the above emulsifying apparatus together. By using a high-pressure homogenizer, the emulsified particles can be made more uniform in particle size. For the purpose of further homogenizing the particle size, emulsification and dispersion may be performed a plurality of times.

The high-pressure homogenizer includes a chamber-type high-pressure homogenizer having a chamber in which a flow path for processing liquid is fixed, and a homogeneous valve-type high-pressure homogenizer having a homogeneous valve.
The homogeneous valve type high-pressure homogenizer can easily adjust the width of the flow path of the treatment liquid, so that the pressure and flow rate during operation can be arbitrarily set, and the operation range is wide. Can be used.
Although the degree of freedom in operation is low, a chamber type high pressure homogenizer can be suitably used for applications that require ultra-high pressure because a mechanism for increasing pressure is easy to make.

Examples of the chamber type high-pressure homogenizer include a microfluidizer (manufactured by Microfluidics), a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), an optimizer (manufactured by Sugino Machine Co., Ltd.), and the like.
As the homogeneous valve type high-pressure homogenizer, Gorin type homogenizer (manufactured by APV), Lanier type homogenizer (manufactured by Lanier), high-pressure homogenizer (manufactured by Niro Soabi), homogenizer (manufactured by Sanwa Machinery Co., Ltd.), high-pressure homogenizer ( Izumi Food Machinery Co., Ltd.), ultra-high pressure homogenizer (manufactured by Ika), and the like.

In the present invention, the pressure of the high-pressure homogenizer is preferably 50 MPa or more, more preferably 50 to 250 MPa, still more preferably 100 to 250 MPa.
It is preferable from the viewpoint of maintaining the particle size of the emulsified particles that the emulsified liquid, which is an emulsified and dispersed composition, is cooled through some cooler within 30 seconds immediately after passing through the chamber, preferably within 3 seconds.

  In the emulsion containing the emulsified particles containing carotenoid (C) obtained as described above, the content of carotenoid (C) is preferably 0.1% by mass to 30% by mass, and 1% by mass to 20% by mass. Is more preferable, and 5 mass%-15 mass% is still more preferable.

Subsequently, the emulsion particles containing the carotenoid (C) are mixed with the emulsion liquid containing the emulsion particles containing the carotenoid (C) and the aqueous mixed solution containing the compound (A) and the specific stabilizer (B). Is produced.
In addition to these, the aqueous mixed solution containing the compound (A) and the specific stabilizer (B) preferably contains a polyhydric alcohol, a water-soluble polymer compound, an additive component, and the like.

The mixing of the above-described emulsion and aqueous mixed solution is not particularly limited, and a small amount of the emulsion may be added to a large amount of the aqueous mixed solution so that the emulsion becomes a part of the aqueous mixed solution.
The amount of the emulsion added to the aqueous mixed solution can be appropriately changed according to the use of the emulsion to be produced, but is generally 0.01% by mass to 10% by mass with respect to the mass of the entire emulsion. From the viewpoint of coloring density, an amount of 0.05% by mass to 5% by mass is more preferable, and an amount of 0.1% by mass to 1% by mass is still more preferable.

5-7.5 is preferable and, as for pH of the skin external preparation of this invention, it is more preferable that it is 6.5-7.5.
By setting it as this pH range, when the skin external preparation of this invention is an emulsion, the storage stability of an emulsion, especially the storage stability at room temperature can be made favorable.
Here, the room temperature in the present invention means 25 ° C.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to them.

(Preparation of emulsion)
Each component constituting the aqueous phase composition described in the following Table 1 to Table 4 is used in the content (% by mass) described in the following Table 1 to Table 4 and dissolved for 1 hour while heating at 70 ° C. An aqueous composition was obtained.
Each component constituting the oil phase composition described in Tables 1 to 4 below is used in the content (% by mass) described in Tables 1 to 4 below, and mixed and dissolved for 1 hour while heating at 70 ° C. Each oil phase composition was obtained.
Details of each component described in Tables 1 to 4 will be described later.

According to the description in Tables 1 to 4, the aqueous phase composition and the oil phase composition were combined, and emulsions 1 to 4 containing carotenoid (C) were obtained as follows.
That is, with the aqueous phase composition kept at 70 ° C., the mixture was stirred with a homogenizer (vacuum emulsifier PVQ-1D type manufactured by Mizuho Kogyo Co., Ltd.) (10000 rpm), and the oil phase composition was added thereto to give an emulsion. Obtained.
The obtained emulsified liquid was subjected to high-pressure emulsification at 40 ° C. using an optimizer HJP-25005 (manufactured by Sugino Machine Co., Ltd.) at a pressure of 200 MPa.
Then, it filtered with the micro filter with an average hole diameter of 1 micrometer, and prepared the emulsion 1-the emulsion 4.

(Preparation of aqueous mixed solution)
All components other than the “emulsion” listed in Table 5 below were mixed at 80 ° C. and cooled to 35 ° C. or lower to obtain aqueous mixed solutions used in each Example and Comparative Example.

[Example 1]
(Preparation of emulsion)
As shown in Table 5 below, the emulsion 1 and the aqueous mixed solution were mixed at 35 ° C. or less to obtain a red transparent emulsion.
The total amount of the emulsion 1 and the aqueous mixed solution is 100% by mass.

[Example 2 to Example 10, Comparative Example 1 to Comparative Example 7]
(Preparation of emulsion)
In the preparation of the emulsion of Example 1, a red transparent emulsion was obtained in the same manner as in Example 1 except that the emulsion described in Table 5 below and the aqueous mixed solution were used.
In addition, the total amount of the emulsion 1 or the emulsion 4 and the aqueous mixed solution is 100% by mass.

[Evaluation]
The following evaluations were performed using the emulsions of Examples 1 to 10 and Comparative Examples 1 to 7 obtained above and the test samples taken from the emulsions.
The evaluation results are shown in Table 5.

(1) Measurement of viscosity Viscosity of the emulsions of Examples 1 to 10 and Comparative Examples 1 to 7 was measured by the method described above.

(2) Odor Evaluation After storing the test sample at 4 ° C. and 40 ° C. for 1 month, sensory evaluation was performed on the odor of the test sample.
Five evaluators were asked to evaluate odor in the following four stages.
The evaluator
If you feel that the skin preparation for external use after storage at 4 ° C. and 40 ° C. has no odor at all, or both odors are almost unchanged, score “4”.
If you feel that “in the external preparation for skin after storage at 4 ° C. and 40 ° C., the person stored at 40 ° C. has almost no odor, or both have almost no odor.” Scoring,
If you feel that the external preparation for skin after storage at 4 ° C and 40 ° C has a slight odor in both, score "2".
When the skin external preparation after storage at 4 ° C. and 40 ° C. had a strong odor in both, it was scored as “1”.
This scoring result was averaged, and the numerical value rounded off to the nearest decimal point was taken as the odor evaluation result.
It shows that there are few odors of a skin external preparation, so that this figure is large.

(3) Evaluation of carotenoid stability The carotenoid content in the test sample before storage and the test sample stored at 40 ° C for one month was compared to determine the carotenoid residual rate, It was evaluated.
The amount of carotenoid was measured by measuring the absorption of carotenoid using a UV spectrophotometer (transmission measurement, using 1 cm cell). Absorbance between 400 nm and 500 nm was measured, and the amount of carotenoid was determined using the wavelength of the peak top of the test sample before storage of each carotenoid. When the carotenoid content of the test sample before storage was set to 100%, the carotenoid content of the test sample after storage was defined as the carotenoid residual rate and evaluated based on the following indices.
-Evaluation criteria-
G1: Carotenoid survival rate is 95% or more G2: Carotenoid survival rate is 90% or more and less than 95% G3: Carotenoid survival rate is less than 90%

(4) Evaluation of crystal precipitation After storing the test sample at 40 ° C. for 2 months, the crystal precipitation in the test sample was visually observed.
G1: Precipitation from carotenoid stabilizer is observed NG: Precipitation from carotenoid stabilizer is not observed

  In the emulsions of Examples 1 to 10, the odor was reduced, the carotenoid stability was high, and crystal precipitation of the carotenoid stabilizer was not observed.

In Comparative Example 1 in which APM was not used, carotenoid stability was insufficient.
The comparative example 2 which does not use GT-700 and the comparative example 3 with few amounts of GT-700 had a low viscosity, and could not suppress an odor.
In Comparative Example 4 using APPS: trisodium ascorbyl palmitate (palmitoyl ester of ascorbyl phosphate) instead of APM or APS, esterified palmitic acid was precipitated as crystals.
Since Comparative Example 5 using a carboxyvinyl polymer that is generally used as a thickener has insufficient salt resistance, the viscosity is low and the odor cannot be suppressed.
In Comparative Examples 6 and 7 thickened using polysaccharides, although the viscosity exceeded 1 Pa · s, the suppression of odor was insufficient.

[Example 11, Example 12]
An emulsion was obtained in the same manner as in Example 1 except that the emulsion 1 used in Example 1 was replaced with an emulsion 2 containing krill-derived astaxanthin and an emulsion 3 containing Adnisparestina-derived astaxanthin, respectively. . The emulsion of Example 11 uses the emulsion 2 and the emulsion of Example 12 uses the emulsion 4.
When the above evaluation was performed on the obtained emulsions of Example 11 and Example 12, the same effect as in Example 1 was obtained.

[About each component]
[Emulsions]
(Carotenoid (C))
-Astaxanthin-containing oil (derived from Haematococcus algae, containing 20% by mass of astaxanthin): ASTOTS-S, Takeda Paper Co., Ltd.
・ Astaxanthin-containing oil (derived from krill, containing 5% by mass of astaxanthin): Astax ST, Marine Daio / Astaxanthin-containing oil (derived from Adonis Palestine, containing 5% by mass of astaxanthin): Astarose, Takeda Paper Instruments
・ Tomato extract oil (containing 6% by mass of lycopene): Lyc-O-Mato 6%, Sunbright Co., Ltd.
(Other ingredients)
Decaglycerin oleate: NIKKOL (registered trademark) Decaglyn 1-O (HLB = 12), Nikko Chemicals, sucrose stearate: Ryoto sugar ester S-1670, Mitsubishi Chemical Foods Co., Ltd.
・ Mix tocopherol: Riken E Oil 800, Riken Vitamin Co., Ltd.
・ Lecithin: Lesion P (derived from soybean), RIKEN VITAMIN Co., Ltd.

[Components of aqueous mixed solution]
(Compound (A) and comparative polymer compound)
PEG-240 / decyltetradeceth-20 / HDI (hexamethylene diisocyanate) Copolymer: Adecanol GT-700, ADEKA, Inc. Hydroxyethyl cellulose (polymer compound for comparison): HEC Daicel SE900, Daicel Xanthan Gum (comparison) Polymer compound): San Ace C, Saneigen / Carboxyvinyl polymer (Comparative polymer compound): Carbopol 980, Lubrizol

(Specific stabilizer (B) and APPS)
APM: magnesium ascorbate phosphate, Nikko Chemicals APS: sodium ascorbate phosphate, Showa Denko APPS: trisodium ascorbyl phosphate palmitate, Showa Denko

(Other ingredients)
・ Glycerin: Kao ・ BG (1,3-butanediol): 1.3 butanediol, Daicel Co., Ltd. ・ Water-soluble collagen: Nitta gelatin ・ Hydrolyzed collagen: Nitta gelatin ・ Methylparaben: Platinth M, Ueno

Claims (7)

A compound represented by the following general formula (1), at least one compound selected from magnesium ascorbate phosphate sodium and sodium ascorbate phosphate, and a carotenoid, containing a B-type viscometer at 25 ° C., 12 rpm The external preparation for skin, wherein the viscosity of the external preparation for skin when measured under a measurement condition of 30 s is 1 Pa · s or more.

In the general formula (1), R ¹ represents an m-valent hydrocarbon group having ² to 36 carbon atoms, R ² and R ⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms, R ³ may have a urethane bond, represents a linear, branched, or h + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, R ⁵ represents a divalent hydrocarbon group, R ⁶ represents Represents a hydrogen atom or a hydroxy group. m is an integer greater than or equal to 2, h is an integer greater than or equal to 1, k and n represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k and n Will never be zero.   The skin external preparation according to claim 1, wherein the content of one compound selected from magnesium ascorbate phosphate sodium and sodium ascorbate phosphate is 0.1% by mass or more based on the total mass of the skin external preparation. . The compound represented by the general formula (1) is at least one selected from the group consisting of a compound represented by the following general formula (1-1) and a compound represented by the following general formula (1-2). The skin external preparation according to claim 1 or 2, which is a compound.

In general formula (1-1), R ¹¹ represents a m1-valent hydrocarbon group having 2 to 12 carbon atoms, and R ¹² and R ¹⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms. , R ¹³ may have a urethane bond, and represents a linear, branched, or h1 + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, and R ¹⁵ represents a monovalent hydrocarbon group. m1 is an integer greater than or equal to 2, h1 is an integer greater than or equal to 1, k1 and n1 represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k1 and n1 Will never be zero.

In the general formula (1-2), R ²¹ represents a m2-valent saturated hydrocarbon group having 6 to 36 carbon atoms, and R ²² represents a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, 3-methyl. −3,5,5-trimethylcyclohexylene group, dimethylphenylene group, or tolylene group, and R ²³ represents a hydrogen atom or a methyl group. n2 represents an integer of 90 to 900, and m2 represents an integer of 1 to 5.   PEG-240 / decyltetradeceth-20 / hexamethylene diisocyanate copolymer in which the compound represented by the general formula (1) is a compound represented by the general formula (1-1), and the general formula (1-2) The skin external preparation according to claim 3, which is at least one copolymer selected from the group consisting of bisstearyl PEG / PPG-8 / 6 (methylenediphenyl diisocyanate / PEG-400) copolymer, which is a compound represented by the formula:   The skin external preparation according to any one of claims 1 to 4, wherein the carotenoid is astaxanthin.   Content of the compound represented by General formula (1) is 0.4 mass% or more with respect to the total mass of skin external preparation, The skin external preparation of any one of Claims 1-5. . The external preparation for skin according to any one of claims 1 to 6, which is an emulsion having emulsified particles containing carotenoids.