HK1175701B - Topical composition - Google Patents

Description

Topical compositions

Technical Field

The present invention relates to a composition for external use which stably contains generally unstable ingredients such as hydroquinone or its derivatives, vitamin A, or ascorbic acid or its salts.

Background Art

Hydroquinone is widely used as a treatment for pigmentation caused by various reasons due to its strong reducing effect. However, it is easily oxidized by light and heat, causing browning. Therefore, 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. Furthermore, Non-Patent Document 2 teaches a method of adding a composite ointment base (plastic base) of liquid paraffin and polyethylene, and a method of adding ascorbic acid and storing at 4°C.

However, these methods cannot sufficiently suppress coloration caused by oxidation of hydroquinone.

Furthermore, Patent Document 1 teaches that when ascorbic acid or a salt thereof is added to a skin external preparation containing hydroquinone and 65% by weight or more of one or more of two or more selected from the group consisting of ethylene glycol, glycol ether, glycerol, and diglycerol, coloring of the skin external preparation can be suppressed.

While the skin external preparation of Patent Document 1 can sufficiently suppress coloration, the addition of these polyols reduces the viscosity of the preparation. Depending on the dosage form, this can cause dripping during use, making it difficult to use. Furthermore, if a large amount of a thickener such as a water-soluble polymer is added to prevent dripping, the preparation becomes sticky and wrinkles may form during application, resulting in a poor feel during use.

Patent Document 1: Japanese Patent Application Laid-Open No. 2006-328064

Non-patent document 1: Medical Medical Research Institute, Vol. 20, N. 10, 1929-1934, 1984

Non-patent document 2: JJSHP, Vol. 24, No. 7, 8, 801-804, 1988

Summary of the Invention

An object of the present invention is to provide an external-use composition comprising 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 salts, which suppresses coloration and provides a good feel during use.

As a result of continuous research to solve the above-mentioned problems, the present inventors have discovered that by adding a cross-linked polyglycerol-modified silicone to an external composition containing a compound selected from the group consisting of hydroquinone and its derivatives, vitamins A, and approximately 3 to 40% by weight of ascorbic acid and its salts, coloring of the composition is suppressed while providing a good, non-sticky feel during use and suppressing separation of the components over time.

The present invention has been completed based on the above findings, and provides the following external use compositions.

Item 1. A composition for external use comprising (a) at least one compound selected from the group consisting of hydroquinone and its derivatives, vitamin A, and 3 to 40% by weight of ascorbic acid and its salts relative to the total weight of the composition, and (b) a cross-linked polyglycerol-modified silicone.

Item 2. The external use composition according to Item 1, comprising 0.01 to 90% by weight of the component (b) based on the total weight of the composition.

Item 3. The external use composition according to Item 1 or Item 2, wherein the component (a) contains hydroquinone and/or its derivative, and the component (b) contains 0.0005 to 9000 parts by weight per 1 part by weight of the hydroquinone and/or its derivative.

Item 3-1. The external use composition according to any one of Items 1 to 3, comprising 0.01 to 20% by weight of hydroquinone and/or its derivatives based on the total weight of the composition.

Item 4. The external use composition according to Item 1 or Item 2, wherein the component (a) contains vitamin A, and the component (b) contains 0.002 to 900,000 parts by weight per part by weight of the vitamin A.

Item 4-1. The external use composition according to Item 1, Item 2 or Item 4, comprising 0.00001 to 5% by weight of vitamin A relative to the total weight of the composition.

Item 5. The external use composition according to Item 1 or Item 2, wherein the component (a) contains 3 to 40% by weight of ascorbic acid and/or its salt, and the component (b) contains 0.00025 to 30 parts by weight per part by weight of ascorbic acid and/or its salt.

Item 5-1. The external use composition according to Item 1, Item 2, or Item 5, comprising 3 to 40% by weight of ascorbic acid and/or a salt thereof relative to the total weight of the composition.

Item 6. The external use composition according to any one of Items 1 to 3, Item 3-1, Item 4, Item 4-1, Item 5, and Item 5-1, further comprising a crosslinked organopolysiloxane.

Item 7. The external use composition according to Item 6, comprising 0.1 to 95% by weight of a cross-linked organopolysiloxane based on the total weight of the composition.

Item 8. The external use composition according to Item 6 or 7, comprising 0.0001 to 900 parts by weight of the crosslinked organopolysiloxane per 1 part by weight of the component (b).

Item 8-1. The external use composition according to any one of Items 1 to 3, Item 3-1, Item 4, Item 4-1, Item 5, Item 5-1, and Items 6 to 8, which contains 20% by weight or less of water relative to the total amount of the composition.

Item 9. A method for inhibiting coloration of an external-use composition, comprising adding (b) a cross-linked polyglycerol-modified silicone to an external-use composition containing (a) at least one compound selected from the group consisting of hydroquinone and its derivatives, vitamins A, and 3 to 40% by weight of ascorbic acid and its salts relative to the total weight of the composition.

Because compounds selected from the group consisting of hydroquinone and its derivatives, vitamins A, and approximately 3 to 40% by weight of ascorbic acid and its salts are unstable, compositions containing these compounds often discolor or change color over time. To address this issue, the external-use composition of the present invention contains a cross-linked polyglycerol-modified silicone in addition to these unstable compounds, making it less susceptible to discoloration or color change.

Furthermore, the external-use composition of the present invention has a moderate viscosity and is not prone to dripping, even without using a large amount of an extra thickener such as a water-soluble polymer, and provides a good feel during use without stickiness or wrinkles.

Furthermore, the composition for external use of the present invention is very stable because separation of components over time is suppressed.

Furthermore, the external use composition of the present invention can be prepared by a cold process without heating to uniformly mix the ingredients, thereby avoiding the modification or decomposition of the 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 salts caused by heating.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a photograph of each composition of Examples 1 to 5 and Comparative Example 1 before and after heat treatment.

FIG2 is a photograph of each composition of Examples 6, 7 and Comparative Example 1 before and after heat treatment.

FIG3 is a photograph of each composition of Examples 8 to 13 and Comparative Example 1 before and after heat treatment.

FIG. 4 is a photograph of each composition of Examples 14 to 17 and Comparative Example 1 before and after heat treatment.

DETAILED DESCRIPTION

The present invention will be described in detail below.

The external use composition of the present invention comprises (a) at least one 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 salts, and (b) a crosslinked polyglycerol-modified silicone.

Hydroquinone

Hydroquinone is commercially available.

Derivatives of hydroquinone

Preferred examples of hydroquinone derivatives include glycosides such as condensates of hydroquinone and sugars and condensates of alkylhydroquinones obtained by introducing an alkyl group having 1 to 4 carbon atoms into hydroquinone and sugars.

Examples of sugars of glycosides include hexoses such as D-glucose, D-galactose, D-mannose, D-tagatose, D-fructose, L-sorbose, D-tagatose, and D-psicose; pentoses such as L-arabinose, D-xylose, D-ribose, D-xylulose, D-lyxose, and D-ribulose; amino sugars such as D-glucosamine, D-galactosamine, sialic acid, and muramic acid; and uronic acids (acetylated, etc.) such as D-glucuronic acid, D-galacturonic acid, D-mannuronic acid, and L-iduronic acid.

In addition, pharmaceutically acceptable salts of hydroquinone glycosides can also be used, including alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; ammonium salts; organic amine salts such as triethylamine salts, triethanolamine salts and monoethanolamine salts; and basic amino acid salts such as lysine salts and alginate salts.

Hydroquinone glycosides can be derived by adding a glycosidase to a solution of hydroquinone and sugar and allowing it to react. For example, arbutin can be synthesized by an enzymatic reaction using β-glucosidase in a solution of hydroquinone and D-glucose. Specifically, it can be prepared, for example, by the method described in Japanese Patent Application Laid-Open No. 5-176785.

Furthermore, hydroquinone glycoside can be obtained by forming a glycosidic bond between an acetylated sugar obtained by acetylation of a sugar and hydroquinone in the presence of a glycosidase, and then removing the acetyl group by alkaline hydrolysis.

Furthermore, hydroquinone glycosides can be extracted from various plants, for example, arbutin can be extracted from bearberry or bilberry.

As the hydroquinone derivative, there may be used ingredients such as butylated hydroxyanisole, which are added to foods as antioxidants.

The hydroquinone derivative is preferably a glycoside, more preferably a hexose glycoside, and among these, arbutin is preferred.

Hydroquinone and its derivatives may be used alone or in combination of two or more.

When the external composition of the present invention contains hydroquinone and/or its derivatives, the content thereof is preferably at least about 0.01% by weight, more preferably at least about 0.1% by weight, and even more preferably at least about 0.5% by weight, relative to the total amount of the composition. Within this range, the whitening effects and other effects of hydroquinone and hydroquinone derivatives can be fully achieved.

Furthermore, the content of hydroquinone and/or its derivatives in the composition is preferably about 20% by weight or less, more preferably about 10% by weight or less, and even more preferably about 5% by weight or less, relative to the total weight of the composition. Within this range, coloration or discoloration of the composition over time is suppressed, sufficient physiological activity is achieved, and a cost-effective composition can be obtained.

Vitamin A

The vitamin A of the present invention includes retinol, retinal, retinoic acid, their dehydrogenates, their esters, provitamin A and the like.

Examples of esters include retinyl acetate, retinyl propionate, retinyl butyrate, retinyl octanoate, retinyl laurate, retinyl palmitate, retinyl stearate, retinyl myristate, retinyl oleate, retinyl linolenate, retinyl linoleate, retinaldehyde palmitate, retinaldehyde acetate, retinaldehyde propionate, methyl retinoate, ethyl retinoate, retinol retinoate, and tocopheryl retinoate (which may be any of the α, β, γ, and δ isomers). Examples of provitamin A include α-carotene, β-carotene, γ-carotene, δ-carotene, lycopene, zeaxanthin, β-cryptoxanthin, and echinone.

Among them, retinol, retinoic acid, and esters thereof (retinol palmitate, retinol acetate, etc.) are preferred.

Vitamin A can be vitamin A isolated from natural products such as animal materials, or can be chemically synthesized vitamin A. In addition, vitamin A can also be used in the form of vitamin A oil. Vitamin A oil can be a natural oil extracted and refined from animals, or can be a vitamin A oil obtained by dissolving vitamin A in vegetable oil or the like. As a representative example of the latter, the vitamin A oil described in the Japanese Pharmacopoeia (containing more than 30,000 vitamin A units (IU) per 1g) can be cited, preferably containing 1,000,000 IU, 1,500,000 IU or 1,700,000 IU per 1g.

Vitamin A can be used alone or in combination of two or more.

When the external composition of the present invention contains vitamin A, the content thereof is preferably 0.00001% by weight or greater, more preferably 0.0001% by weight or greater, and even more preferably 0.001% by weight or greater, relative to the total weight of the composition. Within this range, the physiological effects of vitamin A, such as its effects on promoting collagen production, keratinocyte proliferation, metabolic stimulation due to inhibition of keratinocyte differentiation, and antioxidant effects, can be exerted.

Furthermore, when vitamin A is included, the content is preferably 5% by weight or less, more preferably 3% by weight or less, and even more preferably 2% by weight or less, relative to the total weight of the composition. Within this range, a composition having a sufficient physiological effect can be obtained while being cost-effective.

When vitamin A is contained in the composition in the form of vitamin A oil, the above-mentioned content and ratio of vitamin A are the weight of vitamin A oil obtained by dissolving vitamin A in vegetable oil or the like.

Ascorbic acid and its salts

Ascorbic acid may be in the form of L-, D-, or a mixture thereof. L-ascorbic acid is preferred because of its excellent physiological effects, such as whitening and collagen production promotion. Commercially available ascorbic acid is available.

Examples of ascorbic acid salts include sodium salts, potassium salts, calcium salts, magnesium salts, phosphates, and iron salts.

When the external-use composition of the present invention contains ascorbic acid and/or its salt, the content of ascorbic acid and/or its salt in the composition is about 3% by weight or more relative to the total weight of the composition. In this case, coloration occurs over time. The content of ascorbic acid and/or its salt is preferably about 4% by weight or more, more preferably about 5% by weight or more, relative to the total weight of the composition. Within this range, the physiological effects of ascorbic acid or its salt, such as whitening, wrinkle suppression, and sagging suppression, can be fully achieved.

Furthermore, the content of ascorbic acid and/or its salts in the composition is about 40% by weight or less, preferably about 30% by weight or less, relative to the total weight of the composition. Within this range, a composition having a sufficient physiological effect can be obtained while being cost-effective.

Hydroquinone and its derivatives, vitamin A, and about 3 to 40% by weight of ascorbic acid and its salts can be used alone or in combination of two or more.

For example, in the case of containing hydroquinone and/or its derivatives and vitamin A, when two or more of (i) hydroquinone and/or its derivatives, (ii) vitamin A, and (iii) ascorbic acid or its salts are contained, the total amount thereof is preferably at least about 0.00001% by weight, more preferably at least about 0.001% by weight, and even more preferably at least about 0.01% by weight, relative to the total amount of the composition. Furthermore, the total amount thereof is preferably at most about 65% by weight, more preferably at most about 30% by weight, and even more preferably at most about 25% by weight, relative to the total amount of the composition.

Cross-linked polyglycerol-modified silicone

Cross-linked polyglycerol-modified silicone is a cross-linked organopolysiloxane polymer having a glycerol group. In the present invention, cross-linked polyglycerol-modified silicone also includes co-modified silicones such as cross-linked polyglycerol-alkyl co-modified silicone.

Cross-linked polyglycerol-modified silicone can also be used in the form of a composition (e.g., a paste) containing a liquid oil. For example, the cross-linked polyglycerol-modified silicone can be swollen in a low-viscosity silicone (0.65 mm ² /s (25°C) to 100.0 ^{mm 2} /s (25°C)) with a viscosity greater than its own weight, a hydrocarbon oil such as liquid paraffin, squalane, or isododecane, or a glyceride oil or ester oil such as tricaprylin.

The cross-linked polyglycerin-modified silicones may be used alone or in combination of two or more.

As the cross-linked polyglycerin-modified silicone of the present invention, for example, the cross-linked polyglycerin-modified silicone described in Japanese Patent No. 4187198 or Japanese Patent No. 4490817 can be used.

Specifically, cross-linked polyglycerin-modified silicone represented by the following general formula (1) can be mentioned.

R ¹ _a R ² _b SiO _(4-ab)/2 (1)

In the formula, ^R1 is an organic group of the same or different types selected from an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, and a fluorine-substituted alkyl group. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenethyl; and fluorine-substituted alkyl groups such as trifluoropropyl and heptafluorodecyl. Furthermore, a is a number 1.0 ≤ a ≤ 2.5, and b is a number 0.001 ≤ b ≤ 1.5.

In the formula, R ¹ may further 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, ^R3 is a monovalent hydrocarbon group having 5 to 30 carbon atoms or an organic group represented by ^R4 -(CO)-, ^R4 is a hydrocarbon group having 1 to 30 carbon atoms, c and d are each integers of 0 to 50, and m is an integer of 0 to 15. In other words, ^R1 is an alkoxy group, an ester group, an alkenyl ether residue, or an alkenyl ester residue. Regardless of the values of c and d, if m is 0, hydrolysis resistance may be poor, while if m is 15 or greater, the oily odor may be too strong. Therefore, m is preferably 3 to 11.

When m=0, c=0, and d=0, R ¹ may include alkoxy groups having 5 to 30 carbon atoms, such as higher alkoxy groups such as octadecyloxy and stearyloxy, or ester groups of oleic acid, stearic acid, and behenic acid.

When m is 1 or greater, c = 0, and d = 0, m is particularly preferably 3, 5, or 11. In this case, ^R1 is an allyl ether, pentenyl ether, or undecenyl ether residue. Although it varies depending on ^R3 , examples thereof include allyl stearyl ether residue, allyl behenyl ether residue, and undecenyl oleyl ether residue. When c or d is not 0, ^R1 is a group having an alkoxy group or ester group via a polyoxyalkylene group.

It is particularly preferred that 50% or more of all R ^1s are methyl groups, further preferably 70% or more, and 100% may be methyl groups.

^R2 is a hydrophilic group represented by the following general formula (3).

-Q-O-X (3)

In the formula, Q represents a divalent hydrocarbon group having 3 to 20 carbon atoms which may contain an ether bond and an ester bond, and examples thereof 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 )-, -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 -, and - ₍ CH ₂ ) ₃ -O-CH ₂ CH(CH ₃ )- and -CH ₂ CH(CH ₃ )-COO(CH ₂ ) ₂ -, etc.

X is glycerol.

Examples of R ² include the following residues.

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

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

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

Specific examples of the cross-linked polyglycerol-modified silicone that can be used in the present invention include organopolysiloxane polymers obtained by addition polymerization of an organohydrogenpolysiloxane represented by the following general formula (a1) and/or the following general formula (a2), a glycerol derivative having an alkenyl group represented by the following general formula (b1), an organopolysiloxane having an alkenyl group represented by the following general formula (b2), and at least one compound selected from hydrocarbons having an alkenyl group represented by the following general formula (b3), with the component represented by the following general formula (a1) or (b1) as an essential component.

(a1):R ¹ _a R ² _b H _c SiO _(4-abc)/2

(a2):R ¹ _{d He} 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 the 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 not having an alkenyl group. These are alkyl groups, aryl groups, aralkyl groups, or halogenated hydrocarbon groups. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, stearyl, and behenyl; saturated alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; aralkyl groups such as phenethyl; and fluorine-substituted alkyl groups such as trifluoropropyl, nonafluorohexyl, and heptafluorodecyl.

^R2 is a monovalent group having a glycerol derivative represented by the following formula.

In the formula, C _X H _2X , X is a divalent hydrocarbon group of 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 )-.

Regarding the production method of the glycerol derivatives, for example, a glycerol derivative having one mole of allyl groups can be synthesized by reacting glycerol with allyl glycidyl ether. Polyglycerol derivatives can be obtained by reacting several moles of glycidol with glycerol monoallyl ether as a starting material. ^R2 is introduced into the allylated polyglycerol by an addition reaction according to conventional methods.

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, preferably 0.005 to 0.5, and c is 0.001 to 1, preferably 0.005 to 0.5. If a is less than 1, the degree of crosslinking becomes too high, preventing the inclusion of liquid oil equal to or greater than the weight of the component itself. If a is greater than 2.3, the degree of crosslinking becomes too low, making it difficult to form a three-dimensional crosslinked structure.

When c is less than 0.001, the crosslinking degree becomes too low, making it difficult to form a three-dimensional crosslinked structure. When it is greater than 1, the crosslinking degree becomes too high, preventing the inclusion of liquid oil equal to or greater than its own weight. Furthermore, a+b+c is 1.5 to 2.6, preferably 1.8 to 2.2. To facilitate the polymerization reaction, the organopolysiloxane is preferably linear or predominantly linear. However, it may be linear, branched, or _cyclic , containing partial branching units, such as ^R1SiO3 _/2 or SiO2, as its constituent units.

Specific examples of the component (a1) include compounds represented by the following formulas.

(In the formula, R ¹ and R ² represent the above-mentioned groups, x and y are 0 or 1, and x+y=1, 0≤l≤100, 0≤m≤100, 0≤n≤100, 0≤w≤100, and 0≤l+m+n≤200.)

(In the formula, R ¹ and R ² represent the aforementioned groups, 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, and Q represents an oxygen atom or a divalent hydrocarbon group having 2 to 20 carbon atoms.)

(In the formula, R ¹ and R ² represent the above-mentioned groups, 0≤g≤8, 0≤h≤8, 0≤i≤8, 3≤g+h+i≤8.)

Component (a2) is represented by the general formula R ¹ _{d He} SiO _(4-de)/2 . d is 1 to 2.3, preferably 1.2 to 2.1, and e is 0.001 to 1, preferably 0.005 to 0.5. If d is less than 1, the degree of crosslinking becomes too high, preventing the incorporation of liquid oil equal to or greater than the weight of the organopolysiloxane. If d is greater than 2.3, the degree of crosslinking becomes too low, making it difficult to form a three-dimensional crosslinked structure. If e is less than 0.001, the degree of crosslinking becomes too low, preventing the incorporation of liquid oil equal to or greater than the weight of the organopolysiloxane. If e is greater than 1, the degree of crosslinking becomes too high, preventing the incorporation of liquid oil equal to or greater than the weight of the organopolysiloxane. To facilitate the polymerization reaction, the organopolysiloxane is preferably linear or predominantly linear, but may also be linear, branched, or cyclic, containing partial branching units, such as R ¹ SiO _3/2 or SiO ₂ , as its constituent units.

Specific examples of the component (a2) include compounds represented by the following formulas.

(In the formula, ^R1 represents the above-mentioned group, and x, l, n, and w are the same as those in the case of the above-mentioned component (a1).)

(In the formula, ^R1 represents the above-mentioned group, and x, l', and n' are the same as those in the case of the above-mentioned component (a1).)

(In the formula, ^R1 represents the above-mentioned group, g and i are the same as in the case of the above-mentioned component (a1), and 3≤g+i≤8.)

The component (b1) is a glycerol derivative having an alkenyl group represented by the following formula.

^R3 is an alkenyl group having 2 to 20 carbon atoms, and is an aliphatic unsaturated hydrocarbon or an alicyclic unsaturated hydrocarbon. ^R3 is preferably a hydrocarbon group having an alkenyl group represented by the general formula C _Y H _2Y-1 -, where Y is an integer of 2 to 20. Examples of the -C _Y H _2Y-1 group include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylallyl, 2-pentenyl, 4-pentenyl, 5-hexenyl, and 10-undecenyl. Among them, vinyl and allyl groups with Y=2 or 3 are preferred. G is glycerol or polyglycerol, and the alkenyl group ( ^R3 ) in the glycerol derivative is preferably at the end of the derivative. Furthermore, f is an integer of 2 to 10, preferably 2 or 3. Furthermore, s is an integer of 1 to 20. Such a component (b1) is synthesized by an etherification reaction of a hydroxyl group of glycerol or polyglycerol with an alkenyl alcohol or alkenyl glycidyl ether.

Component (b2) is represented by the general formula R ¹ _p R ³ _q SiO _(4-pq)/2 . ^{R 3} is the alkenyl group described in component (b1). p is 1 to 2.3, preferably 1.2 to 2.1, and q is 0.001 to 1, preferably 0.005 to 0.5. When p is less than 1, the degree of crosslinking becomes too high, preventing the incorporation of liquid oil equal to or greater than the weight of the organic polysiloxane. When p is greater than 2.3, the degree of crosslinking becomes too low, making it difficult to form a three-dimensional crosslinked structure. When q is less than 0.001, the degree of crosslinking becomes too low, preventing the incorporation of liquid oil equal to or greater than the weight of the organic polysiloxane. When q is greater than 1, the degree of crosslinking becomes too high, preventing the incorporation of liquid oil equal to or greater than the weight of the organic polysiloxane. From the perspective of a smooth polymerization reaction, the organopolysiloxane is preferably linear or predominantly linear, but may also be linear, branched, or cyclic, containing partial branching units, such as R ¹ SiO _3/2 or SiO ₂ .

Specific examples of the component (b2) include compounds represented by the following formulas.

(In the formula, R ¹ and R ³ represent the above-mentioned groups. z is 0 or 1, 0≤k≤100, and 0≤1+k≤200.)

(In the formula, R ¹ and R ³ represent the above-mentioned groups. z is 0 or 1, 0≤k′≤100, 0≤l′+k′≤200.)

(In the formula, R ¹ and R ³ represent the above-mentioned groups. 1≤j≤8, 3≤g+j≤8.)

Component (b3) is represented by the general formula R ³ (CH ₂ ) _r R ^3. R ³ is the alkenyl group described in component (b1). r is an integer from 0 to 20. Component (b3) includes dienes such as butadiene, pentadiene, hexadiene, heptadiene, octadiene, and nonadiene, with hexadiene being particularly preferred.

The organopolysiloxane polymers that can be used in the present invention include a combination of (a1) and any one or more of (b1) to (b3), a combination of (a1+a2) and any one or more of (b1) to (b3), a combination of (a2) and (b1), a combination of (a2) and (b1) and (b2), or a combination of (a2) and (b1) and (b2) and (b3).

Specific examples of cross-linked polyglycerin-modified silicones include (dimethicone/polyglycerin-3) cross-linked polymers, etc. Commercial products containing (dimethicone/polyglycerin-3) cross-linked polymers include KSG-710, etc., which is commercially available from Shin-Etsu Chemical Co., Ltd.

Specific examples of crosslinked polyglyceryl-alkyl co-modified silicones include (lauryl dimethicone/polyglyceryl-3) crosspolymers. Commercial products containing (lauryl dimethicone/polyglyceryl-3) crosspolymers include KSG-810, KSG-820, KSG-830, and KSG-840, commercially available from Shin-Etsu Chemical Co., Ltd. Also included are (polyglyceryl-3/lauryl dimethylsiloxyethyl dimethicone) crosspolymers. Commercial products containing (polyglyceryl-3/lauryl dimethylsiloxyethyl dimethicone) crosspolymers include KSG-820Z and KSG-850Z, commercially available from Shin-Etsu Chemical Co., Ltd.

The weight average molecular weight of the cross-linked polyglycerol-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 polyglycerol-modified silicone is preferably about 0.01% by weight or more, more preferably about 0.5% by weight or more, and even more preferably about 1% by weight or more relative to the total weight of the composition. Within this range, coloring of the composition can be sufficiently suppressed.

Furthermore, the content of the cross-linked polyglycerol-modified silicone is preferably about 90% by weight or less, more preferably about 50% by weight or less, and even more preferably about 20% by weight or less, relative to the total weight of the composition. Within this range, a sufficient coloration-inhibiting effect is achieved, and separation of components over time is suppressed, resulting in a composition with a good feel during use.

When the external-use composition of the present invention contains hydroquinone and/or its derivatives, the content of the cross-linked polyglycerol-modified silicone is preferably about 0.0005 parts by weight or more, more preferably about 0.01 parts by weight or more, and even more preferably about 0.5 parts by weight or more, per 1 part by weight of the hydroquinone and/or its derivatives. Within this range, coloration of the composition can be sufficiently suppressed.

Furthermore, the content of the cross-linked polyglycerol-modified silicone is preferably about 9000 parts by weight or less, more preferably about 900 parts by weight or less, and even more preferably about 10 parts by weight or less, per 1 part by weight of hydroquinone and/or its derivatives. Within this range, a sufficient coloration-inhibiting effect is achieved, and separation of components over time is suppressed, resulting in a composition with a good feel during use.

When the external use composition of the present invention contains vitamin A, the content of the cross-linked polyglycerol-modified silicone is preferably at least about 0.002 parts by weight, more preferably at least about 0.01 parts by weight, and even more preferably at least about 1 part by weight, per 1 part by weight of vitamin A. Within this range, coloration of the composition can be sufficiently suppressed.

Furthermore, the content of the cross-linked polyglyceryl-modified silicone is preferably about 900,000 parts by weight or less, more preferably about 10,000 parts by weight or less, and even more preferably about 1,000 parts by weight or less, per 1 part by weight of the vitamin A. Within this range, a sufficient coloration-inhibiting effect is achieved, and separation of components over time is suppressed, resulting in a composition with a good feel during use.

When the external composition of the present invention contains ascorbic acid and/or its salt, the content of the cross-linked polyglycerol-modified silicone is preferably at least about 0.00025 parts by weight, more preferably at least about 0.05 parts by weight, and even more preferably at least about 0.1 parts by weight, per 1 part by weight of ascorbic acid and/or its salt. Within this range, coloration of the composition can be sufficiently suppressed.

Furthermore, the content of the cross-linked polyglyceryl-modified silicone is preferably about 30 parts by weight or less, more preferably about 20 parts by weight or less, and even more preferably about 5 parts by weight or less, relative to 1 part by weight of ascorbic acid and/or its salt. Within this range, a sufficient coloration-inhibiting effect is achieved, and separation of components over time is suppressed, resulting in a composition with a good feel during use.

Cross-linked organopolysiloxane

The external-use composition of the present invention may further contain a crosslinked organopolysiloxane (other than the crosslinked polyglycerol-modified silicone), thereby further enhancing coloration suppression and providing a composition with a better feel during use. The crosslinked organopolysiloxane may be a modified crosslinked organopolysiloxane (other than the crosslinked polyglycerol-modified silicone) or an unmodified crosslinked organopolysiloxane, but an unmodified crosslinked organopolysiloxane is preferred.

The crosslinked organopolysiloxane is preferably obtained by allowing a crosslinking agent having two or more ethylenically reactive sites in the molecule to act on hydrogen atoms directly bonded to silicon atoms of the organopolysiloxane, thereby forming a crosslinked structure. Examples of substances having two or more ethylenically 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, and α- and ω-alkenyl dienes.

Furthermore, the crosslinked organopolysiloxane may be modified so as to contain at least one moiety selected from the group consisting of a polyoxyalkylene moiety, an alkyl moiety, an alkenyl moiety, an aryl moiety, and a fluoroalkyl moiety in the molecule.

Furthermore, the crosslinking organopolysiloxane preferably contains low-viscosity siloxane in an amount equal to or greater than its own weight relative to the low-viscosity siloxane of 0.65 to 10.0 mm ² /s and is swollen.

Specific examples of the crosslinked organopolysiloxane include dimethicone crosspolymer (9040 Silicone Elastomer Blend, 9045 Silicone Elastomer Blend, 9041 Silicone Elastomer Blend, 9546 Silicone Elastomer Blend, 9027 Silicone Elastomer Blend, EL-8040ID Silicone Organic Blend; all manufactured by Toray Daikoning Co., Ltd.), (dimethicone/vinyl dimethicone) crosspolymer (KSG-15, KSG-16, KSG-1610; all manufactured by Shin-Etsu Chemical Co., Ltd.), Silicone Elastomer Blend, E-506S, S-508, BY29-129, PF-2001; all manufactured by Toray Daikoning Co., Ltd.), (Dimethicone/Phenyl Vinyl Dimethicone) Crosspolymer (KSG-18A; manufactured by Shin-Etsu Chemical Co., Ltd.), (Vinyl Dimethicone/Lauryl Dimethicone) Crosspolymer (KSG-41, KSG-42, KSG-43, KSG-44; all manufactured by Shin-Etsu Chemical Co., Ltd.), (Dimethicone·PEG-10/15) Crosspolymer (KSG-210, KSG-240; all manufactured by Shin-Etsu Chemical Co., Ltd. (PEG-15/Lauryl Dimethicone) Crosspolymer (KSG-310, KSG-320, KSG-330, KSG-340; all manufactured by Shin-Etsu Chemical Co., Ltd.), (PEG-15/Lauryl Dimethicone Siloxyethyl Dimethicone) Crosspolymer (KSG-320Z, KSG-350Z; all manufactured by Shin-Etsu Chemical Co., Ltd.), and (Lauryl Dimethicone Siloxyethyl Dimethicone/Bisvinyl Dimethicone) Crosspolymer (KSG-042Z, KSG-045Z; all manufactured by Shin-Etsu Chemical Co., Ltd.).

The content of the crosslinked organopolysiloxane is preferably at least about 0.1% by weight, more preferably at least about 0.5% by weight, and even more preferably at least about 1% by weight relative to the total weight of the composition. Within this range, coloration of the composition can be more effectively suppressed.

Furthermore, the content of the crosslinked organopolysiloxane is preferably about 95% by weight or less, more preferably about 70% by weight or less, and even more preferably about 60% by weight or less, relative to the total weight of the composition. Within these ranges, a composition can be obtained that has a suppressed stickiness, a good feel during use, and suppressed separation of components over time.

Furthermore, the content of the crosslinked organopolysiloxane is preferably at least about 0.0001 parts by weight, more preferably at least about 0.01 parts by weight, and even more preferably at least about 0.5 parts by weight per part by weight of the crosslinked polyglycerin-modified silicone. Within this range, a composition with a suppressed sticky feel can be obtained.

Furthermore, the content of the cross-linked polyglycerol-modified silicone is preferably about 900 parts by weight or less, more preferably about 100 parts by weight or less, and even more preferably about 30 parts by weight or less, relative to 1 part by weight of the cross-linked polyglycerol-modified silicone. Within this range, a composition having suppressed separation of components over time and a suppressed sticky feel, and having a good feel during use, can be obtained.

water

The topical composition of the present invention may or may not contain water, but preferably contains water. When containing water, the water content relative to the total amount of the composition may be greater than 0% by weight, preferably 0.5% by weight or more, and more preferably 1% by weight or more. If within the above range, the precipitation of components over time can be suppressed, resulting in a stable composition.

Furthermore, the water content is preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less, relative to the total weight of the composition. Within this range, a sufficient coloration-inhibiting effect can be achieved, and component separation over time is suppressed, resulting in a composition with a good feel during use.

pH

The pH of the external composition of the present invention is preferably about 1 to 10, more preferably about 2 to 8, and even more preferably in the acidic region of about 2 to 7. Within this range, sufficient effects can be obtained.

hardness

The hardness of the external use 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 even more preferably about 30 to 140 g. Within this range, there is no dripping phenomenon and a good feeling during use can be obtained.

The hardness of the present invention is a value measured using a rheometer (trade name "NRM-2002J", manufactured by Fudo Industry Co., Ltd.). Specifically, the preparation is placed in a 50g plastic jar as a sample. The hardness is measured by inserting a cylindrical, 30mm diameter, compressible elastic tube into the rheometer at a speed of 2cm/min to a depth of 1cm.

Preparation form

The external composition of the present invention can be prepared by mixing at least one 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 salts, a cross-linked polyglycerol-modified silicone, and optionally a cross-linked organopolysiloxane, with a base or carrier commonly used in cosmetics or quasi-drugs, and optionally additives, to form a cosmetic or quasi-drug external composition.

The form of the external composition is not particularly limited, and examples thereof include liquids, suspensions, emulsions, creams, ointments, gels, liniments, lotions, aerosols, sticks, and sheet preparations obtained by impregnating a nonwoven fabric with a drug solution. Among these, emulsions, creams, ointments, gels, and lotions are preferred, and creams and gels are more preferred.

When containing an oily base and an aqueous base like a cream or an emulsion, it may be a W/O type or an O/W type, but a W/O type is preferred.

Specific uses of the external-use composition of the present invention include, for example, basic cosmetics such as lotions, emulsions, gels, creams, serums, sunscreen cosmetics, facial masks, skin care masks, hand creams, body lotions, and moisturizers; and cleansing cosmetics such as facial cleansers, makeup removers, body washes, shampoos, conditioners, and treatments.

Base or carrier

Examples of bases or carriers include hydrocarbons such as liquid paraffin, squalane, petrolatum, colloidal hydrocarbons (composite ointment bases of liquid paraffin and polyethylene, etc.), ozokerite, α-olefin oligomers, and light liquid paraffin; silicone oils such as methyl polysiloxane, high-polymer methyl polysiloxane, cyclic silicone, alkyl-modified silicone, amino-modified silicone, polyether-modified silicone, polyglycerol-modified silicone, silicone-alkyl chain co-modified polyether-modified silicone, silicone-alkyl chain co-modified polyglycerol-modified silicone, polyether-modified branched silicone, polyglycerol-modified branched silicone, acrylic silicone, phenyl-modified silicone, and silicone resin; higher alcohols such as cetyl alcohol, cetostearyl alcohol, stearyl alcohol, and behenyl alcohol; and cellulose such as ethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methylcellulose. Derivatives of vitamin C; Polyvinyl pyrrolidone, carrageenan, polyvinyl butyrate, polyethylene glycol, dioxane, butylene glycol adipate polyester, isopropyl myristate, 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 isopropyl alcohol, ethylene glycol adipate polyester, isopropyl myristate, 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 isopropyl alcohol, Glycol ethers such as alcohol 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 dipropylene glycol monopropyl ether; polyols such as polyethylene glycol, propylene glycol, 1,3-butylene glycol, glycerol, isoprene glycol, diglycerol and dipropylene glycol; and water-based agents such as water.

Hydroquinone and its derivatives, vitamin A, and ascorbic acid and its salts are particularly unstable in water. Therefore, the external composition of the present invention is suitable for compositions containing water as a base or carrier, but the effects can be obtained even in compositions not containing water.

Among these, polyols, higher alcohols, hydrocarbons, esters, and silicone oils are preferred, with polyols being more preferred. Among the polyols, 1,3-butylene glycol, propylene glycol, isoprene glycol, glycerol, diglycerol, dipropylene glycol, and 1,2-pentanediol are preferred, with 1,3-butylene glycol, propylene glycol, glycerol, diglycerol, and 1,2-pentanediol being more preferred. Preferred examples of the compositions of the present invention include creams, gels, and emulsions containing a polyol base.

The base or carrier may be used alone or in combination of two or more.

additive

The external use composition of the present invention may contain known additives that can be added to cosmetics and quasi-drugs, such as antioxidants, surfactants, thickeners, preservatives, pH adjusters, stabilizers, anti-irritants, preservatives, colorants, fragrances, and pearlescent agents, within a range that does not impair the effects of the present invention.

Examples of the antioxidant include butylated hydroxytoluene, butylated hydroxyanisole, sorbic acid, sodium sulfite, ascorbic acid, ascorbic acid derivatives, tocopherol, tocopherol derivatives, isoascorbic acid, and L-cysteine hydrochloride.

Examples of the surfactant include sorbitan fatty acid esters such as sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan penta(2-ethylhexanoic acid) diglyceride and sorbitan tetra(2-ethylhexanoic acid) diglyceride, propylene glycol fatty acid esters such as propylene glycol monostearate, hydrogenated castor oil derivatives such as polyoxyethylene hydrogenated castor oil 40 (HCO-40), polyoxyethylene hydrogenated castor oil 50 (HCO-50), polyoxyethylene hydrogenated castor oil 60 (HCO-60) and polyoxyethylene hydrogenated castor oil 80, and polyoxyethylene (20) sorbitan monolaurate. Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene (20) sorbitan monostearate (polysorbate 20), polyoxyethylene (20) sorbitan monostearate (polysorbate 60), polyoxyethylene (20) sorbitan monooleate (polysorbate 80) and polyoxyethylene (20) sorbitan isostearate, polyoxyethylene monococonut fatty acid glyceride, glycerol alkyl ether, alkyl glucoside, polyoxyethylene cetyl ether and other polyoxyalkylene alkyl ethers, stearylamine and oleylamine, and silicone surfactants such as polyoxyethylene methyl polysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl polydimethicone and PEG-9 polydimethylsiloxyethyl polydimethicone.

When a thickener is contained in addition to the cellulose-based thickener, examples thereof include guar gum, locust bean gum, carrageenan, xanthan gum, polyvinyl alcohol, polyvinyl pyrrolidone, carboxyvinyl polymer, acrylic acid alkyl methacrylate copolymer, polyethylene glycol, bentonite, alginic acid, polyethylene glycol, and sodium chondroitin sulfate.

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

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

Examples of the stabilizer include sodium polyacrylate, dibutylhydroxytoluene, and butylhydroxyanisole.

Examples of the anti-irritant include licorice extract and sodium alginate.

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

Other active ingredients

The external use composition of the present invention may contain other active ingredients within the scope that does not hinder the effects of the present invention. Specific examples of active ingredients include moisturizing ingredients, anti-inflammatory ingredients, antibacterial ingredients, vitamins, peptides or their derivatives, amino acids or their derivatives, cell-activating ingredients, anti-aging ingredients, blood circulation promoting ingredients, keratin softening ingredients, whitening ingredients, and astringent ingredients.

Examples of moisturizing ingredients include polyols such as glycerin, 1,3-butylene glycol, propylene glycol, polyethylene glycol, and diglycerol trehalose; polymer compounds such as sodium hyaluronate, heparin analogs, sodium chondroitin sulfate, collagen, elastin, keratin, chitin, and chitosan; amino acids such as glycine, aspartic acid, and arginine; natural moisturizing factors such as sodium lactate, urea, and sodium pyrrolidonecarboxylate; lipids such as ceramide, cholesterol, and phospholipids; and plant extracts such as chamomile extract, witch hazel extract, tea extract, and perilla extract.

Examples of the anti-inflammatory ingredient include ingredients derived from plants (eg, comfrey), allantoin, glycyrrhizic acid or its derivatives, zinc oxide, pyridoxine hydrochloride, tocopheryl acetate, salicylic acid or its derivatives, and ε-aminocaproic acid.

Examples of the antibacterial or bactericidal ingredients include chlorhexidine, salicylic acid, benzalkonium chloride, rivanol, sulfur, resorcinol, ethanol, benzethonium chloride, adapalene, benzoyl peroxide, clindamycin, cresol, gluconic acid and its derivatives, povidone iodine, potassium iodide, iodine, isopropyl methylphenol, triclocarban, triclosan, photosensitive element No. 101, photosensitive element No. 201, parabens, phenoxyethanol, 1,2-pentanediol, alkyldiaminoglycine hydrochloride, chlorhexidine gluconate, and zinc p-hydroxybenzenesulfonate.

Examples of vitamins include vitamin E such as dl-α-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol succinate, and calcium dl-α-tocopherol succinate; vitamin B2 such as riboflavin, flavin mononucleotide, flavin adenine dinucleotide, riboflavin butyrate, riboflavin tetrabutyrate, riboflavin 5'-sodium phosphate, and riboflavin tetranicotinate; nicotinic acids such as dl-α-tocopherol nicotinate, nicotinate benzyl nicotinate, nicotinate methyl ester, nicotinate β-butoxyethyl nicotinate, and nicotinate 1-(4-methylphenyl)ethyl ester; vitamin D such as methyl hesperidin, ergocalciferol, and cholecalciferol; vitamin K such as phylloquinone and farnesquinone; γ-oryzanol, dibenzoylthiamine, dibenzoylthiamine hydrochloride, thiamine hydrochloride, thiamine cetyl hydrochloride, thiamine thiocyanate, and thiamine lauryl hydrochloride. , thiamine nitrate, thiamine monophosphate, thiamine lysinate, thiamine triphosphate, thiamine monophosphate phosphate, thiamine monophosphate, thiamine diphosphate, thiamine diphosphate hydrochloride, thiamine triphosphate and thiamine triphosphate monophosphate, etc. Vitamin B1; pyridoxine hydrochloride, pyridoxine acetate, pyridoxal hydrochloride, pyridoxal 5'-phosphate and pyridoxamine hydrochloride, etc. Vitamin B6; cyanocobalamin, hydroxycobalamin and deoxyadenosylcobalamin, etc. Vitamin B12; folic acid such as folic acid and pteroylglutamic acid; niacin such as niacin and niacinamide; pantothenic acid such as pantothenic acid, calcium pantothenate, panthenol, D-panthenylthiothionine, D-pantethine, coenzyme A and panthenol ethyl ether; biotin such as biotin and biocytin; and vitamin-like action factors such as carnitine, ferulic acid, α-lipoic acid and orotic acid.

Examples of peptides or their derivatives include keratin decomposition peptides, hydrolyzed keratin, collagen, fish collagen, atelocollagen, gelatin, elastin, elastin decomposition peptides, collagen decomposition peptides, hydrolyzed collagen, hydroxypropylammonium chloride hydrolyzed collagen, elastin decomposition peptides, conchiolin decomposition peptides, hydrolyzed conchiolin, silk protein decomposition peptides, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soy protein decomposition peptides, hydrolyzed soy protein, wheat protein, wheat protein decomposition peptides, hydrolyzed wheat protein, casein decomposition peptides, and acylated peptides (palmitoyl oligopeptides, palmitoyl pentapeptides, palmitoyl tetrapeptides, etc.).

Examples of amino acids or their derivatives 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, and creatine.

Examples of cell-activating ingredients include amino acids such as γ-aminobutyric acid and ε-aminocaproic acid; vitamins such as retinol, thiamine, riboflavin, pyridoxine hydrochloride, and pantothenic acid; α-hydroxy acids such as glycolic acid and lactic acid; tannins; flavonoids; saponins; allantoin, and photosensitizer 301.

Examples of the anti-aging ingredients include pannic acid, kinetin, ursolic acid, turmeric extract, sphingosine derivatives, silicon, silicic acid, N-methyl-L-serine, and mevalonolactone.

Examples of ingredients that promote blood circulation include ingredients derived from plants (e.g., ginseng, ashitaba, arnica, ginkgo, fennel, Enmeisou, orandakashi, chamomile, Roman chamomile, carrot, gentian, burdock, rice, hawthorn, shiitake mushroom, hawthorn, European juniper, Chuanxiong, Japanese swertia, thyme, clove, tangerine peel, angelica, peach kernel, tangerine peel, carrot, garlic, butcher's clover, grape, peony, horse chestnut, lemon balm, grapefruit, coix seed, rosemary, rose hip, tangerine peel, angelica, tangerine peel, peach, apricot, walnut, or corn); and glucosylhesperidin.

Examples of the keratin softening component include urea, salicylic acid, glycolic acid, fruit acid, phytic acid, and sulfur.

Examples of the whitening ingredient include tocopherol.

Examples of astringent ingredients include zinc p-hydroxybenzenesulfonate, zinc oxide, menthol, and ethanol.

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

How to use

The method of using the external composition of the present invention varies depending on the skin condition, age, sex, etc. of the user, but the following method may be used, for example.

Specifically, an appropriate amount (e.g., about 0.05 to 5 g) can be applied to the skin several times a day (e.g., 1 to 5 times, preferably 1 to 3 times). Furthermore, a daily dosage of hydroquinone and/or its derivatives, for example, about 0.005 to 5000 mg can be applied to the composition, a daily dosage of vitamin A, for example, about 0.00005 to 5000 mg can be applied to the composition, and a daily dosage of about 3 to 40% by weight ascorbic acid and/or its salts, for example, about 1 to 100,000 mg can be applied to the composition. The application period can be, for example, about 3 to 365 days, preferably about 7 to 180 days.

other

The present invention includes a method for suppressing stickiness or component separation, and suppressing coloration or discoloration of the composition over time, by adding a cross-linked polyglycerol-modified silicone to a composition containing at least one compound selected from the group consisting of hydroquinone and its derivatives, vitamin A class Z, and approximately 3 to 40% by weight of ascorbic acid and its salts. The method comprises: the addition of a cross-linked polyglycerol-modified silicone to a composition containing at least one compound selected from the group consisting of hydroquinone and its derivatives, vitamin A class Z, and approximately 3 to 40% by weight of ascorbic acid and its salts. The method comprises: the addition of a cross-linked polyglycerol-modified silicone to a composition containing at least one compound selected from the group consisting of hydroquinone and its derivatives, vitamin A class Z, and approximately 3 to 40% by weight of ascorbic acid and its salts. The method further ... ascorbic acid and its salts, thereby suppressing stickiness or component separation, and suppressing coloration or discoloration of the composition over time. The types and amounts of the components used, and the properties of the composition are as described above for the external use composition of the present invention.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(1) Preparation of composition

Component A and component B shown in Tables 1 to 3 described later were mixed at room temperature, and the mixture was mixed with a crosslinked organopolysiloxane to prepare a composition for external use.

(2) Accelerated test

Each of the above compositions was placed in a glass screw 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 subjects in their 20s and 30s applied the product to their wrists or faces and evaluated the feel of the product.

The results are shown in Tables 1 to 3. In addition, photographs of the compositions before and after heating are shown in Figures 1 to 4.

[Table 1]

(Unit:w/w%)

[Table 2]

(Unit:w/w%)

[Table 3]

(Unit:w/w%)

The ingredients of the commercial products in Tables 1 to 3 are shown below.

KSG-710: A mixture of (dimethicone/polyglyceryl-3) crosspolymer and dimethicone

KSG-810: A mixture of (Lauryl Dimethicone/Polyglycerin-3) Crosspolymer and Mineral Oil

KSG-210: A mixture of (dimethicone/(PEG-10/15)) crosspolymer and dimethicone

KF-6104: Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone

KSG-15: A blend of (dimethicone/vinyl dimethicone) crosspolymer and cyclopentasiloxane

KSG-045Z: A blend of (lauryl dimethylsiloxyethyl dimethicone/bisvinyl dimethicone) crosspolymer and cyclopentasiloxane

KSG-16: A blend of (dimethicone/vinyl dimethicone) crosspolymer and dimethicone

KSG-19: A blend of (dimethicone/vinyl dimethicone) crosspolymer and dimethicone

KSG-016F: A mixture of (dimethicone/vinyl dimethicone) crosspolymer and dimethicone

KSG-43: A mixture of (vinyl dimethicone/lauryl dimethicone) crosspolymer and triethylhexanoin

As shown in Tables 1-3, the compositions of the examples of the present invention exhibit suppressed coloration, good formulation stability, and a pleasant feel during use. On the other hand, the composition of Comparative Example 1, which uses a cross-linked polyether-modified siloxane instead of a cross-linked polyglycerin-modified siloxane, exhibits a strong yellow tint. Furthermore, the composition of Comparative Example 2, which uses a linear polyglycerin-modified siloxane, exhibits a sticky feel during use. Similarly, the composition of Comparative Example 3, which uses a linear polyglycerin-modified siloxane and a cross-linked organopolysiloxane, exhibits component separation.

The following are examples of preparations. The unit is weight %.

Preparation Example 1 Cream

Preparation Example 2 Cream

Preparation Example 3 Cream

Industrial applicability

The external-use composition of the present invention contains a compound selected from the group consisting of hydroquinone and its derivatives, vitamin A, and approximately 3 to 40% by weight of ascorbic acid and its salts, which is generally unstable. This composition can suppress coloration. Furthermore, it is stable and has a good feel during use, making it useful as a cosmetic or quasi-drug.

Claims (6)

1. A topical composition comprising (a) at least one compound selected from the group consisting of hydroquinone, retinol, and ascorbic acid in a total amount of 3 to 40% by weight relative to the composition, and (b) at least one cross-linked polyglycerol-modified siloxane selected from the group consisting of (polydimethylsiloxane/polyglycerol-3) cross-linked polymer, (lauryl polydimethylsiloxane/polyglycerol-3) cross-linked polymer, and (polyglycerol-3/lauryl polydimethylsiloxyethyl polydimethylsiloxane) cross-linked polymer, wherein the water content is 8% by weight or less. When hydroquinone is present as component (a), it contains 0.5 to 900 parts by weight of component (b) relative to 1 part by weight of hydroquinone. When retinol is present as component (a), component (b) is present in a proportion of 1 part by weight to 1000 parts by weight of retinol. When component (a) contains 3 to 40% by weight of ascorbic acid, it contains 0.1 to 20 parts by weight of component (b) relative to 1 part by weight of ascorbic acid. 2. The topical composition according to claim 1, wherein the composition contains 0.01 to 90% by weight of component (b) relative to the total amount of the composition. 3. The topical composition according to claim 1, wherein when hydroquinone is contained as component (a), 0.5 to 10 parts by weight of component (b) are contained relative to 1 part by weight of hydroquinone. 4. The topical composition according to claim 1, wherein as component (a) contains 3 to 40% by weight of ascorbic acid, it contains 0.1 to 5 parts by weight of component (b) relative to 1 part by weight of ascorbic acid. 5. The topical composition according to any one of claims 1 to 4, further comprising at least one cross-linked organopolysiloxane selected from the group consisting of (polydimethylsiloxane/vinyl polydimethylsiloxane) cross-linked polymer, (vinyl polydimethylsiloxane/lauryl polydimethylsiloxane) cross-linked polymer and (lauryl polydimethylsiloxyethyl polydimethylsiloxane/bisvinyl polydimethylsiloxane) cross-linked polymer. The composition contains 1 to 60% by weight of cross-linked organopolysiloxane relative to its total weight. It contains 0.5 to 30 parts by weight of cross-linked organopolysiloxane relative to 1 part by weight of component (b). 6. A method for inhibiting color staining in a topical composition, comprising adding (b) at least one cross-linked polyglycerol-modified siloxane selected from the group consisting of (a) a compound selected from hydroquinone, retinol, and ascorbic acid in a total amount of 3 to 40 wt% relative to the composition, to a topical composition containing at least one compound selected from the group consisting of (polydimethylsiloxane/polyglycerol-3) cross-linked polymer, (lauryl polydimethylsiloxane/polyglycerol-3) cross-linked polymer, and (polyglycerol-3/lauryl polydimethylsiloxyethyl polydimethylsiloxane) cross-linked polymer, wherein the water content of the topical composition is 8 wt% or less. When hydroquinone is present as component (a), it contains 0.5 to 900 parts by weight of component (b) relative to 1 part by weight of hydroquinone. When retinol is present as component (a), component (b) is present in a proportion of 1 part by weight to 1000 parts by weight of retinol. When component (a) contains 3 to 40% by weight of ascorbic acid, it contains 0.1 to 20 parts by weight of component (b) relative to 1 part by weight of ascorbic acid.