JP2013032345A - Composition for external use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring-suppressed, user-friendly and highly stable composition for external use, which contains a compound selected from a group consisting of hydroquinone and derivatives thereof, vitamin As, ascorbic acid and its salt.SOLUTION: The composition for external use contains: (a) at least one compound selected from a group consisting of hydroquinone and derivatives thereof, vitamin As, and ascorbic acid and its salt accounting for 3-40 wt.% of the whole amount of the composition; and (b) crosslinking polyglycerol-modified silicone.

Description

  The present invention relates to a composition for external use that stably contains a generally unstable component such as hydroquinone or a derivative thereof, vitamin A, or ascorbic acid or a salt thereof.

Hydroquinone is widely used as a therapeutic agent for pigmentation due to various causes due to its strong reducing action, but it is known that it is easily oxidized and browned by light or heat. Thus, various methods for stabilizing hydroquinone have been studied. For example, Non-Patent Document 1 teaches a method of adding sodium sulfite and a method of adding sodium sulfite and citric acid. Non-Patent Document 2 teaches a method of adding plastibase and a method of blending ascorbic acid and storing at 4 ° C.
However, these methods cannot sufficiently suppress coloring due to oxidation of hydroquinone.

Patent Document 1 discloses that ascorbic acid or a salt thereof is applied to a skin external preparation containing 65% by weight or more of hydroquinone and one or more selected from the group consisting of glycol, glycol ether, glycerin, and diglycerin. When blended, it teaches that coloring of the external preparation for skin is suppressed.
In the external preparation for skin of Patent Document 1, coloring is sufficiently suppressed, but the addition of these polyols decreases the viscosity of the preparation, and depending on the dosage form of the preparation, it may be difficult to use due to dripping during use There is. In addition, when a large amount of a thickener such as a water-soluble polymer is added to prevent liquid dripping, stickiness is likely to occur or dripping or the like is likely to occur during application, resulting in poor usability.

JP 2006-328064

Pharmaceutical Journal, Vol.20, N.10, 1929-1934, 1984 JJSHP, Vol.24, No.7,8,801-804,1988

  The present invention contains a compound selected from the group consisting of hydroquinone and derivatives thereof, vitamin As, and about 3 to 40% by weight of ascorbic acid and salts thereof, and has an excellent external feeling composition with suppressed coloration. The issue is to provide goods.

  The present inventor has repeatedly studied to solve the above-mentioned problems, and includes at least one compound selected from the group consisting of hydroquinone and derivatives thereof, vitamin As, and about 3 to 40% by weight of ascorbic acid and salts thereof. By blending the cross-linked polyglycerin-modified silicone with the external composition, coloring of the composition is suppressed, a good feeling without stickiness is obtained, and further, component separation over time is suppressed. I found.

This invention is completed based on the said knowledge, and provides the following external compositions.
Item 1. (a) hydroquinone and derivatives thereof, vitamin A, and at least one compound selected from the group consisting of 3 to 40% by weight of ascorbic acid and salts thereof based on the total amount of the composition, and (b) a crosslinked type An external composition comprising polyglycerin-modified silicone.
Item 2. Item 2. The composition for external use according to Item 1, comprising 0.01 to 90% by weight of component (b) based on the total amount of the composition.
Item 3. Item (1) or (2), wherein (a) component contains 0.0005 to 9000 parts by weight of component (b) with respect to 1 part by weight of hydroquinone and / or a derivative thereof when it contains hydroquinone and / or a derivative thereof. .
Item 3-1. Item 4. The external composition according to any one of Items 1 to 3, comprising 0.01 to 20% by weight of hydroquinone and / or a derivative thereof based on the total amount of the composition.
Item 4. Item 3. The composition for external use according to Item 1 or 2, comprising 0.002 to 900,000 parts by weight of component (b) with respect to 1 part by weight of vitamin A when component (a) contains vitamin A.
Claim | item 4-1. Item 5. The topical composition according to Item 1, 2, or 4 containing 0.00001 to 5% by weight of vitamin A based on the total amount of the composition.
Item 5. Item 1 comprising 0.00025 to 30 parts by weight of component (b) with respect to 1 part by weight of ascorbic acid and / or salt thereof when 3 to 40% by weight of ascorbic acid and / or salt thereof is included as component (a). Or the composition for external use of 2.
Item 5-1. Item 6. The topical composition according to Item 1, 2, or 5, comprising 3 to 40% by weight of ascorbic acid and / or a salt thereof based on the total amount of the composition.
Item 6. Furthermore, the external composition in any one of claim | item 1 -3, 3-1, 4, 4-1, 5 and 5-1, containing crosslinked type organopolysiloxane.
Item 7. Item 7. The external composition according to Item 6, comprising 0.1 to 95% by weight of the crosslinked organopolysiloxane based on the total amount of the composition.
Item 8. Item 8. The external composition according to Item 6 or 7, comprising 0.0001 to 900 parts by weight of a crosslinked polyorganosiloxane with respect to 1 part by weight of the component (b).
Item 8-1. The topical composition according to any one of Items 1 to 3, 3-1, 4, 4-1, 5, 5-1, and 6 to 8 containing 20% by weight or less of water based on the total amount of the composition .
Item 9. (a) A composition for external use containing at least one compound selected from the group consisting of hydroquinone and derivatives thereof, vitamins A, and 3 to 40% by weight of ascorbic acid and salts thereof with respect to the total amount of the composition. (B) The coloring suppression method of the composition for external use which adds bridge | crosslinking type polyglycerin modified silicone.

Since compounds selected from the group consisting of hydroquinone and derivatives thereof, vitamin As, and about 3 to 40% by weight of ascorbic acid and salts thereof are unstable, compositions containing these compounds are generally It will be colored or discolored. In this regard, the composition for external use of the present invention is difficult to be colored or discolored by containing a crosslinked polyglycerin-modified silicone in addition to the above unstable compound.
In addition, the external composition of the present invention has an appropriate viscosity and does not easily drip even without using a thickening agent such as a large amount of a water-soluble polymer. A good feeling of use without any problem is obtained.
Furthermore, the composition for external use of the present invention is very stable because component separation over time is suppressed.
Further, the external composition of the present invention can uniformly mix each component by a cold process in which no heat is applied during the preparation, whereby hydroquinone and its derivatives, vitamin A, and about 3 to 40% by weight. The modification or decomposition of the compound selected from the group consisting of ascorbic acid and salts thereof by heating can be avoided.

It is the photograph before and behind heat-treating each composition of Examples 1-5 and Comparative Example 1. It is the photograph before and behind heat-treating each composition of Example 6, 7 and the comparative example 1. FIG. It is the photograph before and after heat-treating each composition of Examples 8-13 and the comparative example 1. FIG. It is the photograph before and behind heat-treating each composition of Examples 14-17 and the comparative example 1. FIG.

Hereinafter, the present invention will be described in detail.
The composition for external use of the present invention comprises (a) hydroquinone and a derivative thereof, vitamin A, and at least one compound selected from the group consisting of about 3 to 40% by weight of ascorbic acid and a salt thereof; It is a composition containing a polyglycerin modified silicone.

Hydroquinone Hydroquinone is commercially available.

Hydroquinone derivatives Hydroquinone derivatives include hydroquinone and sugar condensates, and glycosides such as alkyl hydroquinone and sugar condensates obtained by introducing one alkyl group having 1 to 4 carbon atoms into hydroquinone. .
As sugars of glycosides, D-glucose, D-galactose, D-mannose, D-tagatose, D-fructose, L-sorbose, D-tagatose, And hexoses such as D-psicose; L-arabinose, D-xylose, D-ribose, D-xylose, D-lyxose, D-ribose, etc. Pentoses; amino sugars such as D-glucosamine, D-galactosamine, sialic acid, and muramic acid; and uronic acids (acetyl) such as D-glucuronic acid, D-galacturonic acid, D-mannuronic acid, and L-iduronic acid And the like.
Also, pharmaceutically acceptable salts of hydroquinone glycosides can be used, for example, alkali metal salts such as sodium salt and potassium salt; alkaline earth metals such as calcium salt and magnesium salt; ammonium salt; triethylamine salt Organic amine salts such as triethanolamine salt and monoethanolamine salt; and basic amino acid salts such as lysine salt and alginate.

The hydroquinone glycoside can be induced by adding a glycosidase to a solution composed of hydroquinone and sugar. For example, arbutin can be synthesized by enzymatic reaction using β-glucosidase in a solution composed of hydroquinone and D-glucose. Specifically, for example, it can be produced by the method described in JP-A-5-76785.
The hydroquinone glycoside can be obtained by glycating an acetylated sugar obtained by acetylating a sugar and hydroquinone in the presence of glycosidase, and further removing the acetyl group by alkaline hydrolysis.
Moreover, hydroquinone glycoside can be extracted from various plants, for example, arbutin can be extracted from a walnut and cowberry.

  As a hydroquinone derivative, a component used for food addition as an antioxidant, such as butylhydroxyanisole, can be used. Butyl hydroxyani

As hydroquinone derivatives, glycosides are preferable, hexose sugar glycosides are more preferable, and arbutin is particularly preferable.
Hydroquinone and its derivative can be used individually by 1 type or in combination of 2 or more types.

When the composition for external use of the present invention contains hydroquinone and / or a derivative thereof, the content is preferably about 0.01% by weight or more, more preferably about 0.1% by weight or more, and more preferably about 0.5% by weight relative to the total amount of the composition. The above is even more preferable. If it is the said range, effects, such as a whitening effect which hydroquinone and a hydroquinone derivative have, will fully be acquired.
In addition, the content of hydroquinone and / or derivative thereof in the composition is preferably about 20% by weight or less, more preferably about 10% by weight or less, and still more preferably about 5% by weight or less based on the total amount of the composition. preferable. If it is the said range, the coloring or discoloration of a composition with time will be suppressed and a composition with cost merit can be obtained while obtaining a sufficient physiological activity.

The vitamin A in vitamin A present invention include retinol retinal, retinoic acid, these dehydro body, these esters and pro-vitamin A and the like.
Esters include retinol acetate, retinol propionate, retinol butyrate, retinol octylate, retinol laurate, retinol palmitate, retinol stearate, retinol myristate, retinol oleate, retinol linolenate, retinol linoleate, retinol palmitate, Examples thereof include retinal acetate, retinal propionate, methyl retinoate, ethyl retinoate, retinol retinoate, and tocopherol retinoate (which may be any isomer of α, β, γ, and δ). Examples of provitamin A include α-carotene, β-carotene, γ-carotene, δ-carotene, lycopene, zeaxanthin, β-cryptoxanthin, and echinenone.
Of these, retinol, retinoic acid, and esters thereof (retinol palmitate, retinol acetate, etc.) are preferable.
The vitamin A may be either isolated from natural products such as animal materials or chemically synthesized. Vitamin A can also be used in the form of vitamin A oil. The vitamin A oil may be a natural oil extracted and purified from an animal, or a vitamin A dissolved in a vegetable oil or the like. A typical example of the latter is vitamin A oil described in the Japanese Pharmacopoeia (including 30000 vitamin A units (IU) or more per gram), preferably 1 million IU, 1.5 million IU, or 1.7 million IU per gram. Used for
Vitamin A can be used individually by 1 type or in combination of 2 or more types.

When the composition for external use of the present invention contains vitamins A, the content is preferably 0.00001% by weight or more, more preferably 0.0001% by weight or more, and still more preferably 0.001% by weight or more based on the total amount of the composition. If it is the said range, physiological effects, such as promotion of the collagen production which vitamin A has, the proliferation of a keratinocyte, the turnover acceleration | stimulation by the differentiation suppression of a keratinocyte, and an antioxidant effect | action can be exhibited.
The content when vitamin A is included is preferably 5% by weight or less, more preferably 3% by weight or less, and still more preferably 2% by weight or less based on the total amount of the composition. If it is the said range, a composition with cost merit can be obtained, obtaining sufficient physiological effect.
When the vitamin A is contained in the composition in the form of vitamin A oil, the content and ratio of the vitamin A are the weight of vitamin A oil obtained by dissolving the vitamin A in vegetable oil or the like.

Ascorbic acid and its salt Ascorbic acid may be any of L-form, D-form, and mixtures thereof. Among these, L-ascorbic acid is preferable in terms of high physiological activity effects such as whitening action and collagen production promoting action. Ascorbic acid is commercially available.
Examples of ascorbate include sodium salt, potassium salt, calcium salt, magnesium salt, phosphate, and iron salt.

When the composition for external use of the present invention contains ascorbic acid and / or a salt thereof, the content of ascorbic acid and / or a salt thereof in the composition is about 3% by weight or more based on the total amount of the composition, In this case, coloration with time occurs. The content of ascorbic acid and / or a salt thereof is preferably about 4% by weight or more, more preferably about 5% by weight or more based on the total amount of the composition. If it is the said range, the physiological effect of ascorbic acid or its salt, such as a whitening effect | action, a wrinkle suppression effect, and a talmi suppression effect, is fully acquired.
Further, the content of ascorbic acid and / or a salt thereof in the composition is about 40% by weight or less, preferably about 30% by weight or less based on the total amount of the composition. If it is the said range, a composition with cost merit can be obtained, obtaining sufficient physiological effect.

Hydroquinone and its derivatives, vitamin A, and about 3 to 40% by weight of ascorbic acid and its salt can be used alone or in combination of two or more.
For example, as in the case of containing hydroquinone and / or its derivative and vitamin A, (i) hydroquinone and / or its derivative, (ii) vitamin A, and (iii) ascorbic acid or its salt ( i) When including two or more of (ii) and (iii), the total amount is preferably about 0.00001% by weight or more, more preferably about 0.001% by weight or more, and more preferably about 0.01% by weight or more based on the total amount of the composition Even more preferred. The total amount is preferably about 65% by weight or less, more preferably about 30% by weight or less, and still more preferably about 25% by weight or less based on the total amount of the composition.

Crosslinked polyglycerin-modified silicone Crosslinked polyglycerin-modified silicone is a crosslinked organopolysiloxane polymer having a glycerin group. In the present invention, the crosslinked polyglycerin-modified silicone includes a co-modified silicone such as a crosslinked polyglycerin / alkyl co-modified silicone.
The cross-linked polyglycerin-modified silicone may be used in the form of a composition (for example, a paste) containing a liquid oil. For example, the cross-linked polyglycerin-modified silicone, a low viscosity silicone own weight or more 0.65 mm ² / s (25 ℃) ~100.0mm ² / s (25 ° C.), liquid paraffin, squalane, or hydrocarbons such as isododecane You may make it swell to oil, glyceride oils, such as a trioctanoin, or ester oil.
The crosslinked polyglycerin-modified silicone can be used alone or in combination of two or more.

As the cross-linked polyglycerin-modified silicone of the present invention, for example, those described in Japanese Patent No. 4187198 or Japanese Patent No. 4490817 may be used.
Specific examples include cross-linked polyglycerin-modified silicones represented by the following general formula (1).

R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)

In the formula, R ¹ is the same or different organic group selected from an organic group represented by an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, and a fluorine-substituted alkyl group. Group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like alkyl group; cyclopentyl group, cyclohexyl group such as cyclohexyl group; phenyl group, and An aryl group such as a tolyl group; an aralkyl group such as a benzyl group and a phenethyl group; and a fluorine-substituted alkyl group such as a trifluoropropyl group and a heptadecafluorodecyl group. Further, a is a number satisfying 1.0 ≦ a ≦ 2.5, and b is a number satisfying 0.001 ≦ b ≦ 1.5.

In the formula, R ¹ may be an organic group containing a long-chain alkyl group represented by the following general formula (2).

_{-C m H 2m -O- (C 2} H 4 O) c (C 3 H 6 O) d R 3 (2)

In the formula, R ³ is a monovalent carbon hydrogen group having 5 to 30 carbon atoms or an organic group represented by R ⁴ — (CO) —, R ⁴ is a hydrocarbon group having 1 to 30 carbon atoms, and c And d are each an integer of 0 to 50, and m is an integer of 0 to 15. That is, R ¹ is an alkoxy group, an ester group, an alkenyl ether residue, or an alkenyl ester residue. Here, no matter what c and d are, m may be inferior in hydrolysis resistance when m is 0, and if m is 15 or more, since the oily odor is strong, m may be 3 to 11. preferable.

The R ^1, in the case of m = 0, c = 0, d = 0 , the alkoxy group having 5 to 30 carbon atoms, for example, higher alkoxy groups such as Oreirokishi group, and stearoxy group. Alternatively, ester groups such as oleic acid, stearic acid, and behenylic acid can be mentioned.

When m is 1 or more, and c = 0 and d = 0, it is particularly preferable that m is 3, 5, or 11. In this case, R ¹ is allyl ether, pentenyl ether, or undeceni an ether residue, varies depending R ^3, such as allyl stearyl ether residue, such as allyl behenyl ether residue or undecenyl oleyl ether residue. When c or d is not 0, R ¹ has an alkoxy group or an ester group via polyoxyalkylene.

In particular, it is preferable that 50% or more of the total R ¹ is a methyl group, more preferably 70% or more is a methyl group, and 100% may be a methyl group.
R ² is a hydrophilic group represented by the following general formula (3).

-QOX (3)

In formula (I), Q is a divalent hydrocarbon group with 3 to 20 carbon atoms which may contain an ether bond and an ester bond, for example _{- (CH 2) 2 -,} - (CH 2) 3 -, - _{CH 2 CH (CH 3) CH} 2 -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 -, - (CH 2) 8 - _{, - (CH 2) 2 -CH} (CH 2 CH 2 CH 3) -, - CH 2 -CH (CH 2 CH 3) -, - (CH 2) 3 -O- (CH 2) 2 -, - ( _{CH 2) 3 -O- (CH 2} ) 2 -O- (CH 2) 2 -, - (CH 2) 3 -O-CH 2 CH (CH 3) -, and _-CH 2 CH _(CH 3) - COO (CH ₂ ) ₂ — and the like can be exemplified.

X is glycerin.
Examples of R ² include the following residues.
(In the formula, Q is the same as Q in the formula (3), and s in the formula is an integer of 1 to 20. In addition, a part of the hydroxyl group may be substituted with an alkoxy group or an ester group. Good.)

(In the formula, Q is the same as Q in the formula (3), and t in the formula is an integer of 1 to 20. In addition, a part of the hydroxyl group may be substituted with an alkoxy group or an ester group. Good.)

(In the formula, Q is the same as Q in formula (3). Moreover, a part of the hydroxyl group may be substituted with an alkoxy group or an ester group.)

Specific examples of the crosslinked polyglycerin-modified silicone that can be used in the present invention include organohydrogenpolysiloxanes represented by the following general formula (a1) and / or the following general formula (a2), and the following general formula (b1 ) A glycerin derivative having an alkenyl group represented by formula (b2), an organopolysiloxane having an alkenyl group represented by formula (b2), and a hydrocarbon having an alkenyl group represented by formula (b3) below Among at least one kind of compound, an organopolysiloxane polymer obtained by addition polymerization using a component represented by the following general formula (a1) or (b1) as an essential component can be mentioned.
(A1): R ¹ _a R ² _b H _c SiO _{(4-abc) / 2}
(A2): R ¹ _d H _e SiO _{(4-de) / 2}
(B1):
(B2): R ¹ _p R ³ _q SiO _{(4-pq) / 2}
(B3): R ³ (CH ₂ ) _r R ³

The component (a1) is represented by an average composition formula R ¹ _a R ² _b H _c SiO _{(4-abc) / 2} . In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and having no alkenyl group. These are an alkyl group, an aryl group, an aralkyl group or a halogenated hydrocarbon group. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Groups, decyl groups, stearyl groups, and alkyl groups such as behenyl groups; saturated alicyclic hydrocarbon groups such as cyclopentyl groups and cyclohexyl groups; aryl groups such as phenyl groups and tolyl groups; and aralkyl groups such as phenethyl groups And fluorine-substituted alkyl groups such as a trifluoropropyl group, a nonafluorohexyl group, and a heptadecylfluorodecyl group.

R ² is a monovalent group having a glycerin derivative represented by the following formula.
C _X H _2X in the formula is a divalent hydrocarbon group in which X is 2 to 20, and s is an integer of 1 to 20, preferably 1 to 10. Specific examples of the C _X H _2X group include — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, —CH ₂ CH (CH ₃ ) CH ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ -,-(CH ₂ ) ₆ -,-(CH ₂ ) ₇ -,-(CH ₂ ) ₈ -,-(CH ₂ ) ₂ -CH (CH ₂ CH ₂ CH ₃ )-, and -CH ₂ -CH _(CH 2 _{CH 3)} -, and the like.

If the manufacturing method of the said glycerol derivative is described, it is possible to synthesize | combine the glycerol derivative which has 1 mol of allyl groups, for example by making glycerol and allyl glycidyl ether react. It can be obtained by reacting several moles of glycidol as a starting material. R ² can be introduced by subjecting this allylated polyglycerin to an addition reaction according to a conventional method.

The component (a1) is represented by the general formula R ¹ _a R ² _b H _c SiO _{(4-abc) / 2} . Here, a is 1 to 2.3, preferably 1.2 to 2.1, b is 0.001 to 1, but preferably 0.005 to 0.5, c Is 0.001-1, preferably 0.005-0.5. If a is less than 1, the degree of cross-linking becomes too high to contain liquid oil equal to or more than the weight of its own weight, and if it exceeds 2.3, the degree of cross-linking becomes too low, making it difficult to form a three-dimensional cross-linked structure. Become.

If c is less than 0.001, the degree of cross-linking will be low, making it difficult to form a three-dimensional cross-linked structure, and if it is greater than 1, the degree of cross-linking will be too high to contain liquid oil equal to or more than its own weight. Moreover, although a + b + c is 1.5-2.6, Preferably it is 1.8-2.2. The organopolysiloxane is preferably linear or mainly linear from the viewpoint of smoothly proceeding the polymerization reaction, but has a partially branched unit having R ¹ SiO _3/2 or SiO ₂ as a structural unit. It may be any of linear, branched or cyclic containing.
Specific examples of the component (a1) include compounds represented by the following formula.
(Wherein R ¹ and R ² represent the groups described above, x and y are 0 or 1 and x + y = 1,
0 ≦ l ≦ 100, 0 ≦ m ≦ 100, 0 ≦ n ≦ 100, 0 ≦ w ≦ 100,
0 ≦ l + m + n ≦ 200. )
(Wherein R ¹ and R ² represent the groups described above, x and y are 0 or 1 and x + y = 1, 0 ≦ l ′ ≦ 100, 0 ≦ m ′ ≦ 100, 0 ≦ n ′ ≦ 100, 0 ≦ l ′ + m ′ + n ′ ≦ 200,
Q represents an oxygen atom or a C2-C20 divalent hydrocarbon group. )
(In the formula, R ¹ and R ² represent the groups described above, and 0 ≦ g ≦ 8, 0 ≦ h ≦ 8, 0 ≦ i ≦ 8, 3 ≦ g + h + i ≦ 8)

The component (a2) is represented by the general formula R ¹ _d H _e SiO _{(4-de) / 2} . d is 1 to 2.3, preferably 1.2 to 2.1, and e is 0.001 to 1, but preferably 0.005 to 0.5. If d is less than 1, the degree of cross-linking becomes too high to contain liquid oil equal to or more than its own weight, and if it exceeds 2.3, the degree of cross-linking becomes too low, making it difficult to form a three-dimensional cross-linked structure. Become. If e is less than 0.001, the degree of cross-linking becomes too low, so that it is difficult to form a three-dimensional cross-linked structure. If e is larger than 1, the degree of cross-linking becomes too high, and liquid oil of the same weight or more may be included. Disappear. The organopolysiloxane is preferably linear or mainly linear from the viewpoint of smoothly proceeding the polymerization reaction, but has a partially branched unit having R ¹ SiO _3/2 or SiO ₂ as a structural unit. It may be any of linear, branched or cyclic containing.
Specific examples of the component (a2) include compounds represented by the following formula.
(In the formula, R ¹ represents the group described above, and x, l, n, and w are the same as those in the component (a1) described above.)
(In the formula, R ¹ represents the above-described group, and x, l ′, and n ′ are the same as those in the above-described component (a1).)
(In the formula, R ¹ represents the group described above, and g and i are the same as those in the component (a1) described above, and 3 ≦ g + i ≦ 8.)

The component (b1) is a glycerin derivative having an alkenyl group represented by the following formula.
R ³ is an alkenyl group having 2 to 20 carbon atoms and is an aliphatic unsaturated hydrocarbon or an alicyclic unsaturated hydrocarbon. R ³ is preferably a hydrocarbon group having an alkenyl group represented by the general formula C _Y H _2Y-1- , and Y is an integer of 2 to 20. As the -C _Y H _2Y-1 group, a vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methylallyl group, 2-pentenyl group 4-pentenyl group, 5-hexenyl group, and 10-undecenyl group. Of these, vinyl groups and allyl groups with Y = 2 or 3 are preferred. G is glycerin or polyglycerin, and the alkenyl group (R ³ ) in the glycerin derivative is preferably at the end of the derivative. Further, f is an integer of 2 to 10, preferably 2 or 3. Moreover, s is an integer of 1-20. Such a component (b1) is synthesized by an etherification reaction between a hydroxyl group of glycerin or polyglycerin and an alkenyl alcohol or alkenyl glycidyl ether.

Component (b2) is represented by the general formula ^{_{R 1 p R 3 q SiO (}} 4-p-q) / 2. R ³ is an alkenyl group described in the component (b1). p is 1 to 2.3, preferably 1.2 to 2.1, and q is 0.001 to 1, but preferably 0.005 to 0.5. If p is less than 1, the degree of crosslinking becomes too high to contain liquid oil equal to or more than the weight of its own weight, and if it is more than 2.3, the degree of crosslinking becomes too low, making it difficult to form a three-dimensional crosslinked structure. Become. If q is less than 0.001, the degree of cross-linking becomes too low, so that it is difficult to form a three-dimensional cross-linked structure. If q is larger than 1, the degree of cross-linking becomes too high and liquid oil of the same weight or more can be included. Disappear. The organopolysiloxane is preferably linear or mainly linear from the viewpoint of smoothly proceeding the polymerization reaction, but has a partially branched unit having R ¹ SiO _3/2 or SiO ₂ as a structural unit. It may be any of linear, branched or cyclic containing.

Specific examples of the component (b2) include compounds represented by the following formula.
(In the formula, R ¹ and R ³ represent the groups described above. Z is 0 or 1, 0 ≦ k ≦ 100, 0 ≦ l + k ≦ 200.)
(In the formula, R ¹ and R ³ represent the above-described groups. Z is 0 or 1, 0 ≦ k ′ ≦ 100, 0 ≦ l ′ + k ′ ≦ 200.)
(In the formula, R ¹ and R ³ represent the groups described above. 1 ≦ j ≦ 8, 3 ≦ g + j ≦ 8.)
The component (b3) is represented by the general formula R ³ (CH ₂ ) _r R ³ . R ³ is an alkenyl group described in the component (b1). r is an integer of 0-20. Examples of the component (b3) include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene and other dienes, and hexadiene is particularly preferable.

  The organopolysiloxane polymer that can be used in the present invention is a combination of (a1) and any one or more of (b1) to (b3), (a1 + a2), and any one of (b1) to (b3). A combination of more than seeds, a combination of (a2) and (b1), a combination of (a2) and (b1) and (b2), or (a2), (b1), (b2) and (b3) Composed of a combination.

Specific examples of the crosslinked polyglycerin-modified silicone include (dimethicone / polyglycerin-3) crosspolymer. As a product containing a (dimethicone / polyglycerin-3) cross polymer, KSG-710 and the like are commercially available from Shin-Etsu Chemical Co., Ltd.
Specific examples of the crosslinked polyglycerin / alkyl co-modified silicone include (lauryl dimethicone / polyglycerin-3) crosspolymer. KSG-810, KSG-820, KSG-830, KSG-840 and the like are commercially available from Shin-Etsu Chemical Co., Ltd. as products containing lauryl dimethicone / polyglycerin-3) crosspolymer. In addition, (polyglyceryl-3 / lauryl polydimethylsiloxyethyl dimethicone) crosspolymer and the like can also be mentioned. (Polyglyceryl-3 / lauryl polydimethylsiloxyethyl dimethicone) As products containing cross polymers, KSG-820Z, KSG-850Z and the like are commercially available from Shin-Etsu Chemical Co., Ltd.

  The weight average molecular weight of the crosslinked polyglycerin-modified silicone used in the present invention is preferably about 500 to 200,000, more preferably about 1,000 to 100,000.

The content of the crosslinked polyglycerin-modified silicone is preferably about 0.01% by weight or more, more preferably about 0.5% by weight or more, and still more preferably about 1% by weight or more based on the total amount of the composition. If it is the said range, coloring of a composition will be fully suppressed.
The content of the crosslinked polyglycerin-modified silicone is preferably about 90% by weight or less, more preferably about 50% by weight or less, and still more preferably about 20% by weight or less based on the total amount of the composition. If it is the said range, while obtaining sufficient coloring inhibitory effect, a temporal separation of components will be suppressed and a composition with a good feeling of use will be obtained.

When the composition for external use of the present invention contains hydroquinone and / or its derivative, the content of the crosslinked polyglycerin-modified silicone is preferably about 0.0005 part by weight or more with respect to 1 part by weight of hydroquinone and / or its derivative, About 0.01 parts by weight or more is more preferable, and about 0.5 parts by weight or more is even more preferable. If it is the said range, coloring of a composition will be fully suppressed.
Further, the content of the crosslinked polyglycerin-modified silicone is preferably about 9000 parts by weight or less, more preferably about 900 parts by weight or less, and more preferably about 10 parts by weight or less with respect to 1 part by weight of hydroquinone and / or a derivative thereof. Even more preferred. If it is the said range, while obtaining sufficient coloring inhibitory effect, a temporal separation of components will be suppressed and a composition with a good feeling of use will be obtained.

When the composition for external use of the present invention contains vitamins A, the content of the crosslinked polyglycerin-modified silicone is preferably about 0.002 parts by weight or more, and about 0.01 parts by weight or more with respect to 1 part by weight of vitamins A. More preferred is about 1 part by weight or more. If it is the said range, coloring of a composition will be fully suppressed.
The content of the crosslinked polyglycerin-modified silicone is preferably about 900,000 parts by weight or less, more preferably about 10,000 parts by weight or less, and still more preferably about 1000 parts by weight or less, with respect to 1 part by weight of vitamin A. . If it is the said range, while obtaining sufficient coloring inhibitory effect, a temporal separation of components will be suppressed and a composition with a good feeling of use will be obtained.

When the composition for external use of the present invention contains ascorbic acid and / or a salt thereof, the content of the crosslinked polyglycerin-modified silicone is about 0.00025 parts by weight or more with respect to 1 part by weight of ascorbic acid and / or a salt thereof. Preferably, about 0.05 parts by weight or more is more preferable, and about 0.1 parts by weight or more is even more preferable. If it is the said range, coloring of a composition will be fully suppressed.
The content of the crosslinked polyglycerin-modified silicone is preferably about 30 parts by weight or less, more preferably about 20 parts by weight or less, and more preferably about 5 parts by weight or less with respect to 1 part by weight of ascorbic acid and / or a salt thereof. Is even more preferred. While obtaining a sufficient coloring suppression effect, it is possible to suppress component separation over time and to obtain a composition having a good feeling of use.

Crosslinked Organopolysiloxane The composition for external use of the present invention can further contain a crosslinked organopolysiloxane (excluding the crosslinked polyglycerin-modified silicone), thereby further enhancing the coloration suppression and feeling of use. A better composition. The crosslinked organopolysiloxane may be a modified crosslinked organopolysiloxane (excluding crosslinked polyglycerin-modified silicone) or an unmodified crosslinked organopolysiloxane, but may be an unmodified crosslinked organopolysiloxane. preferable.

A cross-linked organopolysiloxane is obtained by forming a cross-linked structure by the action of a cross-linking agent having two or more vinylic reactive sites in the molecule on hydrogen atoms directly bonded to the silicon atoms of the organopolysiloxane. Those are preferred. Those having two or more vinyl reactive sites in the molecule include organopolysiloxanes having two or more vinyl groups in the molecule, polyoxyalkylenes having two or more allyl groups in the molecule, α, and Examples include ω-alkenyl dienes.
Further, the crosslinked organopolysiloxane is modified by containing in the molecule at least one part selected from the group consisting of a polyoxyalkylene part, an alkyl part, an alkenyl part, an aryl part, and a fluoroalkyl part. May be.
The crosslinked organopolysiloxane is preferably swollen with a low-viscosity silicone having a weight higher than its own weight with respect to a low-viscosity silicone of 0.65 to 10.0 mm ² / s.

  Specific examples of cross-linked organopolysiloxanes include dimethicone crosspolymer (9040 Silicone Elastomer Blend, 9045 Silicone Elastomer Blend, 9041 Silicone Elastomer Blend, 9546 Silicone Blend Blend, 9546 Silicone Blend Blend, 9546 Silicone Blend Blend, 9546 Silicone Elastomer Blend. Toray Dow Corning), (Dimethicone / Vinyl Dimethicone) Crosspolymer (KSG-15, KSG-16, KSG-1610; above, Shin-Etsu Chemical Co., Ltd.), Silicone Elastomer Blend, E-506S, S-508, BY29- 129, PF-2001; Uconing), (dimethicone / phenylvinyldimethicone) crosspolymer (KSG-18A; Shin-Etsu Chemical Co., Ltd.), (vinyldimethicone / lauryldimethicone) crosspolymer (KSG-41, KSG-42, KSG-43, KSG-44) Above, Shin-Etsu Chemical Co., Ltd.), (Dimethicone / PEG-10 / 15)) Crosspolymer (KSG-210, KSG-240: Above, Shin-Etsu Chemical Co., Ltd.), (PEG-15 / Lauryl Dimethicone) Cross Polymer (KSG) -310, KSG-320, KSG-330, KSG-340; above, Shin-Etsu Chemical Co., Ltd.), (PEG-15 / lauryl polydimethylsiloxyethyl dimethicone) crosspolymer (KSG-320Z, KSG-350Z; above, Shin-Etsu Chemical) Industry), and (lauryl polydimethylsiloxy) Chill dimethicone / bis vinyl scan dimethicone) crosspolymer (KSG-042Z, KSG-045Z; above, Shin-Etsu Chemical Co., Ltd.).

The content of the crosslinked organopolysiloxane is preferably about 0.1% by weight or more, more preferably about 0.5% by weight or more, and still more preferably about 1% by weight or more based on the total amount of the composition. If it is the said range, coloring of a composition will be suppressed more effectively.
The content of the cross-linked organopolysiloxane is preferably about 95% by weight or less, more preferably about 70% by weight or less, and still more preferably about 60% by weight or less based on the total amount of the composition. If it is the said range, the composition which is excellent in the use feeling in which the feeling of stickiness was suppressed and which suppresses component separation with time is obtained.

Further, the content of the cross-linked organopolysiloxane is preferably about 0.0001 parts by weight or more, more preferably about 0.01 parts by weight or more, and more preferably about 0.5 parts by weight or more with respect to 1 part by weight of the cross-linked polyglycerin-modified silicone. More preferred. If it is the said range, the composition by which the sticky feeling was suppressed will be obtained.
Further, the content of the crosslinked polyglycerin-modified silicone is preferably about 900 parts by weight or less, more preferably about 100 parts by weight or less, and more preferably about 30 parts by weight or less with respect to 1 part by weight of the crosslinked polyglycerin-modified silicone. Even more preferred. If it is the said range, a composition with a sufficient feeling of use in which component separation with time is suppressed and stickiness is suppressed can be obtained.

Composition for external use of the water present invention may contain water, but may not include preferably contains water. The water content in the case of containing water should just exceed 0 weight% with respect to the whole quantity of a composition, 0.5 weight% or more is preferable and 1 weight% or more is more preferable. If it is the said range, precipitation of a component with time will be suppressed and it will become a stable composition.
The water content is preferably 20% by weight or less, more preferably 15% by weight or less, and still more preferably 10% by weight or less, based on the total amount of the composition. If it is the said range, while obtaining sufficient coloring suppression effect, a time-dependent component separation will be suppressed and it will become a composition with a sufficient usability | use_condition.

pH
The pH of the external composition of the present invention is preferably about 1 to 10, more preferably about 2 to 8, and still more preferably about 2 to 7 acidic region. If it is this range, sufficient effect will be acquired.

Hardness The hardness of the external composition of the present invention is not particularly limited, but is preferably about 1 to 200 g, more preferably about 10 to 180 g, and still more preferably about 30 to 140 g. If it is this range, there will be no dripping and a favorable feeling of use will be obtained.
The hardness in the present invention is a value measured using a rheometer (trade name “NRM-2002J”, manufactured by Fudo Kogyo Co., Ltd.). Specifically, the sample was put in a plastic 50 g jar, and the maximum value until a cylindrical elastic compression adapter with a diameter of 30 mm was entered by 1 cm at a speed of 2 cm / min with the above rheometer. Hardness.

Formulation Form The composition for external use of the present invention comprises hydroquinone and derivatives thereof, vitamin A, and at least one compound selected from the group consisting of about 3 to 40% by weight of ascorbic acid and salts thereof, crosslinked polyglycerin-modified silicone Further, if necessary, the cross-linked organopolysiloxane is mixed with a base or carrier usually used in cosmetics or quasi-drugs and, if necessary, additives, cosmetics or quasi-drugs. It can be set as the composition for external use.

The form of the composition for external use is not particularly limited. For example, liquids, suspensions, emulsions, creams, ointments, gels, liniments, lotions, aerosols, sticks, and non-woven fabrics are impregnated with chemicals. Sheet agent and the like. Of these, emulsions, creams, ointments, gels, and lotions are preferred, and creams and gels are more preferred.
When an oily base and an aqueous base are included as in creams and emulsions, they may be W / O type or O / W type, but W / O type is preferred.
Specific applications of the composition for external use of the present invention include, for example, lotions, emulsions, gels, creams, cosmetics, sunscreen cosmetics, packs, masks, hand creams, body lotions, and body creams. Basic cosmetics; and cleansing cosmetics such as facial cleansers, makeup removers, body shampoos, shampoos, rinses, and treatments.

As a base or carrier base or carrier, for example, liquid paraffin, squalane, vaseline, hydrocarbon gel (such as Plastibase), ozokerite, alpha-olefin oligomers, and hydrocarbons such as light liquid paraffin; methylpolysiloxane, Highly polymerized methylpolysiloxane, cyclic silicone, alkyl-modified silicone, amino-modified silicone, polyether-modified silicone, polyglycerin-modified silicone, silicone-alkyl chain co-modified polyether-modified silicone, silicone-alkyl chain co-modified polyglycerin-modified silicone, poly Silicone oils such as ether-modified branched silicones, polyglycerin-modified branched silicones, acrylic silicones, phenyl-modified silicones, and silicone resins; cetanol, cetostearyl alcohol Higher alcohols such as ethyl, stearyl alcohol, and behenyl alcohol; cellulose derivatives such as ethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose; polyvinylpyrrolidone; carrageenan; polyvinyl butyrate; polyethylene glycol; dioxane; butylene glycol adipic acid polyester; Esters such as isopropyl acid, octyldodecyl myristate, isopropyl palmitate, cetyl palmitate, isononyl isononanoate, pentaerythritol tetra-2-ethylhexanoate, and jojoba oil; polysaccharides such as dextrin and maltodextrin; Lower alcohols such as ethanol and isopropanol; ethylene glycol monomethyl ether Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monoethyl ether And glycol ethers such as dipropylene glycol monopropyl ether; polyhydric alcohols such as polyethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin, isoprene glycol, diglycerin, and dipropylene glycol; and aqueous systems such as water Examples include bases.
Since hydroquinone and derivatives thereof, vitamin As, and ascorbic acid and salts thereof are unstable in water, the composition for external use of the present invention is suitable for a composition containing water as a base or carrier. Although effective even with a composition that does not contain water.
Among these, polyhydric alcohols, higher alcohols, hydrocarbons, esters, and silicone oils are preferable, and polyhydric alcohols are more preferable. Among the polyhydric alcohols, 1,3-butylene glycol, propylene glycol, isoprene glycol, glycerin, diglycerin, dipropylene glycol, and 1,2-pentanediol are preferable, and 1,3-butylene glycol, propylene glycol, glycerin Diglycerin and 1,2-pentanediol are more preferred. Preferable examples of the composition of the present invention include creams, gels and emulsions containing a polyhydric alcohol as a base.
A base or a support | carrier can be used individually by 1 type or in combination of 2 or more types.

Additives In the composition for external use of the present invention, known additives that are added to cosmetics or quasi-drugs, for example, antioxidants, surfactants, thickeners, as long as the effects of the present invention are not impaired. , Preservatives, pH adjusters, stabilizers, irritation reducers, preservatives, colorants, fragrances, pearlescent agents, and the like can be added.
Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, sorbic acid, sodium sulfite, ascorbic acid, ascorbic acid derivative, tocopherol, tocopherol derivative, erythorbic acid, and L-cysteine hydrochloride.

  Examples of the surfactant include sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, diglycerol sorbitan penta-2-ethylhexylate, and diglycerol sorbitan tetra-2-ethylhexylate. Sorbitan fatty acid esters such as propylene glycol fatty acid esters such as propylene glycol monostearate; polyoxyethylene hydrogenated castor oil 40 (HCO-40), polyoxyethylene hydrogenated castor oil 50 (HCO-50), polyoxyethylene Hardened castor oil 60 (HCO-60) and hardened castor oil derivatives such as polyoxyethylene hardened castor oil 80; polyoxyethylene (20) sorbitan monolaurate (polysorbate 20), Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene stearate (20) sorbitan (polysorbate 60), polyoxyethylene monooleate (20) sorbitan (polysorbate 80), and polyoxyethylene (20) sorbitan isostearate; Polyoxyethylene monococonut oil fatty acid glyceryl; glycerin alkyl ether; alkyl glucoside; polyoxyalkylene alkyl ether such as polyoxyethylene cetyl ether; amines such as stearylamine and oleylamine; and polyoxyethylene methylpolysiloxane Silicone systems such as polymers, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and PEG-9 polydimethylsiloxyethyl dimethicone Surface active agents, and the like.

  When a thickener is included in addition to the cellulosic thickener, for example, guar gum, locust bean gum, carrageenan, xanthan gum, polyvinyl alcohol, polyvinyl pyrrolidone, carboxyvinyl polymer, alkyl methacrylate copolymer, polyethylene glycol, bentonite , Alginic acid, macrogol, sodium chondroitin sulfate and the like.

  Examples of the preservatives or preservatives include benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, butyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, Examples include benzyl paraoxybenzoate, methyl paraoxybenzoate, phenoxyethanol, benzyl alcohol, chlorobutanol, sorbic acid and its salts, chlorhexidine gluconate, and alkanediol.

  Examples of pH adjusters include inorganic acids (such as hydrochloric acid and sulfuric acid), organic acids (such as lactic acid, sodium lactate, citric acid, sodium citrate, succinic acid, and sodium succinate), inorganic bases (potassium hydroxide, And sodium hydroxide), and organic bases (such as triethanolamine, diisopropanolamine, and triisopropanolamine).

Examples of the stabilizer include sodium polyacrylate, dibutylhydroxytoluene, and bitylhydroxyanisole.
Examples of the irritation reducing agent include licorice extract and sodium alginate.

  An additive can be used individually by 1 type or in combination of 2 or more types.

Other active ingredients The composition for external use of this invention can contain another active ingredient in the range which does not impair the effect of this invention. Specific examples of active ingredients include, for example, moisturizing ingredients, anti-inflammatory ingredients, antibacterial ingredients, vitamins, peptides or derivatives thereof, amino acids or derivatives thereof, cell activation ingredients, anti-aging ingredients, blood circulation promoting ingredients, keratin softening ingredients, Examples include whitening ingredients and astringent ingredients.

  Examples of moisturizing ingredients include polyhydric alcohols such as glycerin, 1,3-butylene glycol, propylene glycol, polyethylene glycol, and diglycerin trehalose; sodium hyaluronate, heparin analog, chondroitin sulfate sodium, collagen, elastin, keratin , Chitin, and polymeric compounds such as chitosan; amino acids such as glycine, aspartic acid, and arginine; natural moisturizing factors such as sodium lactate, urea, and sodium pyrrolidonecarboxylate; such as ceramide, cholesterol, and phospholipids And lipids; plant extract extracts such as chamomile extract, chamelle extract, tea extract, and perilla extract.

  Examples of the anti-inflammatory component include a component derived from a plant (for example, Comfrey), allantoin, glycyrrhizic acid or a derivative thereof, zinc oxide, pyridoxine hydrochloride, tocopherol acetate, salicylic acid or a derivative thereof, and ε-aminocaproic acid. It is done.

  Antibacterial or bactericidal components include, for example, chlorhexidine, salicylic acid, benzalkonium chloride, acrinol, sulfur, resorcin, ethanol, benzethonium chloride, adapalene, benzoyl peroxide, clindamycin, cresol, gluconic acid and its derivatives, popidone iodine, iodine Potassium iodide, iodine, isopropylmethylphenol, triclocarban, triclosan, photosensitizer 101, photosensitizer 201, paraben, phenoxyethanol, 1,2-pentanediol, alkyldiaminoglycine hydrochloride, chlorhexidine gluconate, and zinc paraphenolsulfonate Etc.

  Examples of vitamins include vitamin E such as dl-α-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol succinate, and dl-α-tocopherol calcium succinate; riboflavin, flavin mononucleotide, flavin Vitamin B2s such as adenine dinucleotide, riboflavin butyrate, riboflavin tetrabutyrate, sodium riboflavin 5′-phosphate, and riboflavin tetranicotinate; dl-α-tocopherol nicotinate, benzyl nicotinate, methyl nicotinate, Nicotinic acids such as β-butoxyethyl nicotinate and 1- (4-methylphenyl) ethyl nicotinate; Vitamin Ds such as methyl hesperidin, ergocalciferol, and cholecalciferol Vitamin Ks such as phylloquinone and farnoquinone; γ-oryzanol, dibenzoylthiamine, dibenzoylthiamine hydrochloride, thiamine hydrochloride, thiaminecetyl hydrochloride, thiamine thiocyanate, thiamine lauryl hydrochloride, thiamine nitrate, thiamine monophosphate , Thiamine lysine salt, thiamine triphosphate, thiamine monophosphate phosphate, thiamine monophosphate, thiamine diphosphate, thiamine diphosphate hydrochloride, thiamine triphosphate, and thiamine triphosphate monophosphate Vitamin B1; vitamin B6 such as pyridoxine hydrochloride, pyridoxine acetate, pyridoxal hydrochloride, 5'-pyridoxal phosphate, and pyridoxamine hydrochloride; cyanocobalamin, hydroxocobalamin, and de Vitamin B12s such as oxyadenosylcobalamin; folic acids such as folic acid and pteroylglutamic acid; nicotinic acids such as nicotinic acid and nicotinamide; pantothenic acid, calcium pantothenate, pantothenyl alcohol (panthenol), D- Pantothenic acids such as panthesign, D-panthetin, coenzyme A and pantothenyl ethyl ether; biotins such as biotin and bioticin; and vitamin-like agents such as carnitine, ferulic acid, α-lipoic acid and orotic acid Etc.

  Peptides or derivatives thereof include, for example, keratin-degrading peptide, hydrolyzed keratin, collagen, fish-derived collagen, atelocollagen, gelatin, elastin, elastin-degrading peptide, collagen-degrading peptide, hydrolyzed collagen, hydroxypropylammonium chloride hydrolyzed collagen, elastin Degraded peptide, conchiolin degrading peptide, hydrolyzed conchiolin, silk proteolytic peptide, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soy proteolytic peptide, hydrolyzed soy protein, wheat protein, wheat proteolytic peptide, hydrolyzed wheat protein, casein Degraded peptides, acylated peptides (palmitoyl oligopeptides, palmitoyl pentapeptides, palmitoyl tetrapeptides, etc.) and the like can be mentioned.

  Examples of amino acids or derivatives thereof include betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, β-alanine, threonine, glutamic acid, glutamine, asparagine, aspartic acid, cysteine, cystine. Methionine, leucine, isoleucine, valine, histidine, taurine, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid, carnitine, carnosine, creatine and the like.

Cell activation components include, for example, amino acids such as γ-aminobutyric acid and ε-aminoproic acid; vitamins such as retinol, thiamine, riboflavin, pyridoxine hydrochloride, and pantothenic acids; α- such as glycolic acid and lactic acid Hydroxy acids; Tannins; Flavonoids; Saponins; Allantoins;
Examples of anti-aging components include pangamic acid, kinetin, ursolic acid, turmeric extract, sphingosine derivatives, silicon, silicic acid, N-methyl-L-serine, and mevalonolactone.

  Examples of the blood circulation promoting component include plants (e.g., ginseng, ashitaba, arnica, ginkgo, fennel, enmelio, Dutch oak, chamomile, roman chamomile, carrot, gentian, burdock, rice, hawthorn, shiitake, hawthorn, papaver, Senkyu, assembly, thyme, clove, chimpi, spruce, spruce, spruce, carrot, garlic, butcher bloom, grapes, buttons, maronier, melissa, yuzu, yokuinin, rosemary, rosehip, chimpi, spruce, spruce, peach, apricot , Walnuts, and corn); and glucosyl hesperidin.

Examples of the keratin softening component include urea, salicylic acid, glycolic acid, fruit acid, phytic acid, and sulfur.
Examples of the whitening component include tocopherol.
Examples of the astringent component include zinc paraphenol sulfonate, zinc oxide, menthol, and ethanol.

  Other active ingredients can be used alone or in combination of two or more.

Method of Use The method of using the composition for external use of the present invention varies depending on the skin condition, age, sex and the like of the subject of use, but may be the following method, for example.
That is, an appropriate amount (for example, about 0.05 to 5 g) may be applied to the skin several times a day (for example, about 1 to 5 times, preferably 1 to 3 times). Further, the composition may be applied so that the daily use amount of hydroquinone and / or a derivative thereof is, for example, about 0.005 to 5000 mg, and the daily use amount of vitamin A is, for example, about 0.00005 to 5000 mg. What is necessary is just to apply | coat a composition so that the daily usage-amount of about 3-40 weight% ascorbic acid and / or its salt may be set to about 1-100,000 mg, for example. The application period may be, for example, about 3 to 365 days, preferably about 7 to 180 days.

Others The present invention relates to a composition comprising at least one compound selected from the group consisting of hydroquinone and derivatives thereof, vitamin As, and about 3 to 40% by weight of ascorbic acid and salts thereof, in a crosslinked polyglycerin-modified silicone. The method of suppressing coloring or discoloration of a composition over time is included by suppressing the stickiness or component separation. The kind and amount of each component, the properties of the composition, and the like are as described for the external composition of the present invention.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
(1) Preparation of composition At room temperature, the A component shown in Tables 1 to 3 below was mixed with the B component, and this mixture was mixed with the cross-linked organopolysiloxane to prepare a composition for external use.

(2) Acceleration test Each composition described above was placed in a glass screw cap bottle and allowed to stand in a thermostatic bath at 25 ° C or 60 ° C for 2 days.
The appearance was visually observed before and after heating at 60 ° C. for 2 days. In addition, two male and female panels in their 20s to 30s applied to the arm or face and evaluated the feeling of use.
A result is combined with Tables 1-3 and shown. Moreover, the photograph of the composition before and behind a heating is shown to FIGS.

The components of the products in Tables 1 to 3 are shown below.
KSG-710: (Dimethicone / polyglycerin-3) mixture of cross polymer and dimethicone
KSG-810: (Lauryl dimethicone / polyglycerin-3) mixture of cross polymer and mineral oil
KSG-210: (Dimethicone / (PEG-10 / 15)) Mixture of cross polymer and dimethicone
KF-6104: Polyglyceryl-3 polydimethylsiloxyethyl dimethicone
KSG-15: (Dimethicone / Vinyl Dimethicone) Mixture of cross polymer and cyclopentasiloxane
KSG-045Z: (Lauryl polydimethylsiloxyethyl dimethicone / bisvinyl dimethicone) mixture of cross polymer and cyclopentasiloxane
KSG-16: (Dimethicone / Vinyl Dimethicone) Mixture of cross polymer and dimethicone
KSG-19: (Dimethicone / Vinyl Dimethicone) Mixture of cross polymer and dimethicone
KSG-016F: (Dimethicone / Vinyl Dimethicone) Mixture of cross polymer and dimethicone
KSG-43: (Vinyl Dimethicone / Lauryl Dimethicone) Mixture of Cross Polymer and Triethylhexanoin

  As is apparent from Tables 1 to 3, the compositions of the examples of the present invention were suppressed in coloring, had good formulation stability, and had a good feeling in use. On the other hand, the composition of Comparative Example 1 using a cross-linked polyether-modified silicone instead of the cross-linked polyglycerin-modified silicone had a strong yellow coloring. In addition, the composition of Comparative Example 2 using the linear polyglycerin-modified silicone gave a sticky feel. Similarly, the composition of Comparative Example 3 using a linear polyglycerin-modified silicone and a crosslinked organopolysiloxane was separated.

Formulation examples are shown below. The unit is% by weight.
Formulation Example 1 Cream Crosslinked polyglycerin modified silicone (KSG-820) 15.00
Propylene glycol 15.00
Concentrated glycerin 13.00
Water 5.00
Hydroquinone 1.00
Camellia extract 0.05
Sodium pyrosulfite 0.05
Fragrance 0.1
Cross-linked organopolysiloxane 50.8
100

Formulation Example 2 Cream Cross-linked polyglycerin modified silicone (KSG-830) 18.00
Propylene glycol 65.00
Ascorbic acid 3.00
Fragrance 0.1
Tocopherol 0.5
Cross-linked organopolysiloxane 13.4
100

Formulation Example 3 Cream Crosslinked polyglycerin modified silicone (KSG-820Z) 18.00
Propylene glycol 5.00
Butylene glycol 2.00
Concentrated glycerin 1.00
Water 20.00
Retinol palmitate (1 million IU / g) 0.075
Cross-linked organopolysiloxane 53.925
100

  The composition for external use of the present invention is suppressed in coloring while containing a compound selected from the group consisting of hydroquinone and its derivatives, vitamin A, and about 3 to 40% by weight of ascorbic acid and its salt, which are generally unstable. ing. Moreover, since it is stable and has a good feeling of use, it is useful as a cosmetic or quasi-drug.

Claims (9)

  (a) hydroquinone and derivatives thereof, vitamin A, and at least one compound selected from the group consisting of 3 to 40% by weight of ascorbic acid and salts thereof based on the total amount of the composition, and (b) a crosslinked type An external composition comprising polyglycerin-modified silicone.   The external composition of Claim 1 which contains 0.01 to 90 weight% of (b) component with respect to the whole quantity of a composition.   The composition for external use according to claim 1 or 2, comprising 0.0005 to 9000 parts by weight of component (b) with respect to 1 part by weight of hydroquinone and / or a derivative thereof when hydroquinone and / or a derivative thereof are included as component (a). object.   The composition for external use according to claim 1 or 2, comprising 0.002 to 900,000 parts by weight of component (b) with respect to 1 part by weight of vitamin A when component (a) contains vitamin A.   In the case where 3 to 40% by weight of ascorbic acid and / or a salt thereof is included as component (a), 0.00025 to 30 parts by weight of component (b) is included with respect to 1 part by weight of ascorbic acid and / or salt thereof. The external composition as described in 1 or 2.   Furthermore, the composition for external use in any one of Claims 1-5 containing bridge | crosslinking-type organopolysiloxane.   The composition for external use according to claim 6, comprising 0.1 to 95% by weight of the crosslinked organopolysiloxane based on the total amount of the composition.   The external composition according to claim 6 or 7, comprising 0.0001 to 900 parts by weight of a crosslinked polyorganosiloxane with respect to 1 part by weight of the component (b).   (a) A composition for external use containing at least one compound selected from the group consisting of hydroquinone and derivatives thereof, vitamins A, and 3 to 40% by weight of ascorbic acid and salts thereof with respect to the total amount of the composition. (B) The coloring suppression method of the composition for external use which adds bridge | crosslinking type polyglycerin modified silicone.