JP2003226635A - Water-in-oil emulsified cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a water-in-oil type emulsified cosmetic which is stably formulated with vitamin A and/or its fatty acid ester, has excellent storage stability with time, wrinkle ameliorating effect and a improved feeling of use. <P>SOLUTION: This oil-in-water emulsified cosmetic comprises a crosslinked silicone, vitamin A and/or its fatty acid ester and an oil-soluble antioxidant. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-in-oil type emulsion cosmetic which is excellent in storage stability over time and has a wrinkle improving effect and a good feeling during use.

[0002]

2. Description of the Related Art Vitamin A and / or its fatty acid esters are known to be effective ingredients for the prevention and treatment of cutaneous keratoses and the prevention and recovery of skin aging. Used in cosmetics. However,
Vitamin A and / or its fatty acid ester is structurally extremely unstable, and easily undergoes various isomerizations, decompositions, polymerizations, etc. by light, air, heat, metal ions, etc., so it is stably incorporated in cosmetics. It was difficult to do. Therefore, cosmetics containing vitamin A and / or its fatty acid ester have been mixed with various stabilizers such as antioxidants and sequestering agents in order to ensure storage stability over time (for example, See Patent Documents 1 and 2.).

[0003]

[Patent Document 1] Japanese Unexamined Patent Publication No. 4-210902

[Patent Document 2] JP-A-6-32713

[0004]

However, even if various stabilizers are added, when the composition is an aqueous type or an oil-in-water type, the stabilization of vitamin A and / or its fatty acid ester may not be sufficient. However, even if the amount of the stabilizer is increased, the feeling of use as a cosmetic may be adversely affected. In the case of oily type, vitamin A
The storage stability of the fatty acid ester and / or its fatty acid ester is excellent, but the feeling of use such as slimy or sticky feeling of oil is poor,
On the other hand, the water-in-oil type also has excellent storage stability of vitamin A and / or its fatty acid ester, but in order to ensure stability as a formulation, there are restrictions on the type and blending amount of the oil agent. As a result, it was difficult to obtain a sufficiently satisfactory feeling of use because the feeling of stickiness and the weight of elongation occurred. Therefore, it has been desired to develop a cosmetic composition containing vitamin A and / or a fatty acid ester thereof in a stable manner, which has an excellent effect of improving wrinkles and a feeling of use and has good storage stability over time.

[0005]

Means for Solving the Problems The present inventor has conducted extensive studies in the above-mentioned circumstances and, as a result, used a combination of a crosslinkable silicone, vitamin A and / or a fatty acid ester thereof and an oil-soluble antioxidant, and The present invention has been completed by finding that a water-in-oil emulsion cosmetic having excellent wrinkle improving effect and feeling of use and good storage stability over time can be obtained by using a water-in-water emulsion composition. .

That is, the present invention provides components (a) to (c); (a) crosslinked silicone (b) vitamin A and / or its fatty acid ester (c) water-in-oil emulsion containing an oil-soluble antioxidant. Cosmetics. Further, it is a water-in-oil type emulsion cosmetic containing silicone oil as the component (d). Furthermore, it is a water-in-oil type emulsion cosmetic containing a silicone-based surfactant as the component (e).

[0007]

DETAILED DESCRIPTION OF THE INVENTION The structure of the present invention will be described below. The crosslinkable silicone of the component (a) used in the present invention improves the storage stability of a water-in-oil type emulsion cosmetic over time, and has good spreadability, non-greasiness of the back skin, and a moist body. It is contained for the purpose of imparting a good feel such as a certain feeling of use. The crosslinkable silicone of the component (a) used in the present invention is not particularly limited as long as it is commonly used in cosmetics. Specifically, crosslinkable methyl such as (dimethicone / vinyl dimethicone) crosspolymer is used. Polysiloxane, crosslinked methylphenylpolysiloxane such as (dimethicone / phenyldimethicone) crosspolymer, crosslinked polyether modified silicone such as dimethicone copolyol crosspolymer, crosslinked alkyl modified silicone, (lauryl dimethicone / PEG) crosspolymer, etc. Cross-linked alkyl
Examples thereof include polyether modified silicone. These can be used alone or in combination of two or more as appropriate. As commercially available products, KSG-6, KSG-15, KSG-16 as a mixture of crosslinked methylpolysiloxane and dimethylpolysiloxane, KSG-8 as a mixture of crosslinked methylphenylpolysiloxane and phenyltrimethicone, KSG-18, a mixture of crosslinkable polyether modified silicone and dimethylpolysiloxane, KSG-21, a mixture of crosslinkable alkyl polyether modified silicone and oil, KSG-
31, KSG-32, KSG-33, KSG-34, K as a mixture of a cross-linking alkyl-modified silicone and an oil agent,
SG-41, KSG-42, KSG-43, KSG-4
4 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be preferably used.

The content of the crosslinkable silicone as the component (a) in the water-in-oil type emulsion cosmetic of the present invention is not particularly limited, but is 0.01 to 30% by mass (hereinafter , Simply referred to as “%”) is preferable, and in order to obtain a particularly excellent stability improving effect and usability, 0.1 to 20 is preferable.
% Is more preferable.

The component (b) Vitamin A and / or its fatty acid ester used in the present invention is a component effective for the prevention and treatment of cutaneous keratoses, prevention of skin aging and recovery, and a wrinkle improving effect. It is contained for the purpose. Examples of vitamin A and / or its fatty acid ester used in the present invention include vitamin A, vitamin A acetate ester, vitamin A palmitate ester, and the like.
It is preferably 11-trans type or 13-cis type, and may be a mixture thereof. They are,
One kind or two or more kinds can be appropriately selected and used in combination.

The content of vitamin A and / or its fatty acid ester as component (b) in the water-in-oil type emulsion cosmetic of the present invention is not particularly limited, but is 0.00
1 to 10% is preferable, and 0.01 to 1% is more preferable for obtaining a particularly excellent wrinkle improving effect.

The oil-soluble antioxidant of the component (c) used in the present invention prevents deterioration of the component A (b) of vitamin A and / or its fatty acid ester over time, and has storage stability such as odor and discoloration. It is contained for the purpose of improving The oil-soluble antioxidant of component (c) used in the present invention is not particularly limited as long as it is generally used in cosmetics, and specifically, dibutylhydroxytoluene (hereinafter referred to as BHT), Butyl hydroxyanisole (hereinafter referred to as BHA), α, β, γ, σ-tocopherols, propyl gallate, L-ascorbic acid fatty acid ester, and the like. These can be used alone or in combination of two or more as appropriate.

The content of the oil-soluble antioxidant of the component (c) in the water-in-oil type emulsion cosmetic of the present invention is not particularly limited, but is preferably 0.001 to 10%, and particularly excellent. In order to obtain the effect of improving storage stability of vitamin A and / or its fatty acid ester, 0.01 to 1% is more preferable.

In the water-in-oil type emulsion cosmetic of the present invention, it is possible to add a silicone oil as the component (d) for the purpose of improving the usability. The silicone oil as the component (d) can synergistically improve the feeling of use such as good spreadability during use and non-stickiness of the back skin. The silicone oil of component (d) is not particularly limited as long as it is usually used in cosmetics, but includes dimethylpolysiloxane, cyclic silicone, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher fatty acid-modified organopolysiloxane, Higher alcohol-modified organopolysiloxane, alkyl-modified polysiloxane,
Examples thereof include fluorine-modified polysiloxane and trimethylsiloxysilicate. These can be used alone or in combination of two or more as appropriate. Among these, cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and methylphenylpolysiloxane are particularly preferable from the viewpoints of good spreadability and non-stickiness of the back skin.

The content of the silicone oil as the component (d) in the water-in-oil type emulsion cosmetic of the present invention is not particularly limited, but is preferably 0.01 to 90%, and particularly excellent usability is improved. In order to obtain the effect, 0.1 to 50% is more preferable.

The water-in-oil type milk cosmetic of the present invention may contain a silicone-based surfactant as the component (e) for the purpose of improving the feeling of use and the storage stability. The silicone-based surfactant of component (e) is
It is possible to further synergistically improve the feeling of use such as spread and spread during use and non-stickiness, and to significantly improve the storage stability over time. The silicone surfactant as the component (e) is not particularly limited as long as it is usually used in a water-in-oil type emulsion cosmetic, and it is a polyoxyalkylene-modified organopolysiloxane, a long-chain alkyl-containing polyoxyalkylene-modified organo. Polysiloxane and the like are preferable because they are excellent in the feeling of use and the effect of improving storage stability. These can be used alone or in combination of two or more as appropriate. More specifically, examples of the polyoxyalkylene-modified organopolysiloxane include those having a structure represented by the following general formula (1), and commercially available products include ABIL EM97 (manufactured by Gold Schmidt), SH-3772C, SH3775C ( Toray Dow Corning), KF-6012, KF-6015,
KF-6016, KF-6017 (made by Shin-Etsu Chemical Co., Ltd.)
Etc. can be used suitably.

[0016]

[Chemical 1]

[Wherein R¹Is alkyl having 1 to 5 carbon atoms
Group or phenyl group. R^TwoIs -Q¹-O- (C_Two
H_FourO)_h-(C_ThreeH₆O)_i-R^Three(However, Q¹Is
Represents a divalent hydrocarbon group having 1 to 5 carbon atoms, R^ThreeIs hydrogen
Represents an atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group
You h is an integer of 1 to 50, i is an integer of 0 to 50
It ) G¹And G^TwoCan be the same or different,
Each R¹Or R^TwoIndicates. j is an integer from 0 to 150, k
Represents an integer of 0 to 50. However, when k = 0, G ¹,
G^TwoAt least one of R^TwoIs. ]

The long-chain alkyl-containing polyoxyalkylene-modified organopolysiloxane has the following general formula (2):
The structure shown in FIG.
BIL EM90 (Gold Schmitt), KF-
6026 (produced by Shin-Etsu Chemical Co., Ltd.) and the like are preferably used.

[0019]

[Chemical 2]

[Wherein R^FiveIs an alkyl group having 1 to 5 carbon atoms
Alternatively, it represents a phenyl group. R⁷Is -Q ^Two-O- (C_TwoH
_FourO)_c-(C_ThreeH₆O)_d-R⁹Indicated by Q^TwoIs charcoal
Represents a divalent hydrocarbon group having a prime number of 1 to 5, R⁹Is hydrogen
Represents an alkyl group having 1 to 5 carbon atoms or an acetyl group.
c is an integer of 1 to 50 and d is an integer of 0 to 50. R⁶
Is-(C_ThreeH₆O)_e-R¹⁰, E is 0-5
Integer, R¹⁰Is an alkyl or alkenyl group of 6 to 18
Is. l is an integer of 5 to 150, m is an integer of 5 to 40,
n is an integer of 2-40. ]

Furthermore, a polyoxyalkylene group-containing silicone compound having a structure represented by the following general formula (3) can be mentioned, and as a commercial product, KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are preferably used. R ¹¹ _p R ¹² _q R ¹³ _r SiO _{(4-p-q-r) / 2} (3) (wherein R ^{11 in} the formula is an alkyl group having 1 to 30 carbon atoms,
Aryl group, aralkyl group, fluorine-substituted alkyl group or the following general formula _{(4) -C y H 2y -O-} (C 2 H 4 O) s (C 3 H 6 O) t -R 14 ... (4), R ¹² is the same or different organic group selected from the organic groups represented, and R ¹² is the following general formula (5) —C _y H _{2 y} —O— (C ₂ H ₄ O) _u (C ₃ H ₆ O). _v -R ¹⁵ ... polyoxyalkylene group represented by ^{(5), R 13} is represented by the following general formula _{^{(6) -C z H 2z -}} (SiR 11 R 11 O) tables in ^{w -SiR} ₁₁ 3 ... (6) R ¹⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ¹⁶ — (CO) —, and R ¹⁵ is a hydrogen atom or 1 to 30 carbon atoms.
Is a hydrocarbon group or an organic group represented by R ¹⁶ — (CO) —, and R ¹⁶ is a hydrocarbon group having 1 to 30 carbon atoms. p,
q and r are 1.0 ≦ p ≦ 2.5 and 0.001 ≦ q, respectively.
≦ 1.5, 0.001 ≦ r ≦ 1.5, s and t are integers of 0 ≦ s ≦ 50 and 0 ≦ t ≦ 50, respectively, and u,
v is 2 ≦ u ≦ 200, 0 ≦ v ≦ 198, and u
+ V is an integer of 3 to 200. Also, y is 0 ≦ y ≦ 1
5 is an integer, w is an integer of 0 ≦ w ≦ 500, and z is 1 ≦
It is a positive number of z ≦ 5. )

The content of the component (e) of the silicone-based surfactant in the water-in-oil type emulsion cosmetic of the present invention is not particularly limited, but is preferably 0.01 to 20%,
In order to obtain a more excellent usability and storage stability improving effect, 0.1 to 10% is more preferable.

In the water-in-oil type emulsion cosmetic of the present invention, in addition to the above-mentioned components, as components usually used in cosmetics, for example, oil agents such as hydrocarbons, esters, fats and oils, fluorine-based oils, anionic agents, etc. Surfactants, amphoteric surfactants, cationic surfactants, nonionic surfactants, lower alcohols, aqueous components such as polyols, water-soluble polymers, water-soluble antioxidants, ultraviolet absorbers, fragrances, preservatives Agent, colorant,
A cosmetic agent, an inorganic powder, an organic powder, etc. can be added within a range that does not impair the effects of the present invention.

The water-in-oil type emulsion cosmetics of the present invention include those having various properties such as low viscosity, liquid at room temperature, creamy, and solid. The use of the water-in-oil type emulsion cosmetic of the present invention is not particularly limited, and examples thereof include beauty essence, milky lotion, cream, pack, cleansing,
Examples include skin care cosmetics such as massage charges, foundation foundations, makeup cosmetics such as eyeliners, sunscreen cosmetics such as sun protect.

[0025]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited thereto.

Examples 1 to 10 and Comparative Examples 1 to 3: Water-in-oil type emulsion cosmetics Water-in-oil type emulsion cosmetics having the compositions shown in Table 1 below were prepared by the following production method, and (1) feeling of use (elongation) Good spread, no stickiness), (2) Feeling (feeling when using), (3)
Wrinkle improvement effect, (4) Storage stability (separation, odor, discoloration)
The evaluation items were evaluated by the following methods, and the results are also shown in Table 1.

[0027]

[Table 1]

(Production Method) A: Components (1) to (11) are uniformly mixed at room temperature. B: Components (12) to (14) are uniformly mixed at room temperature. C: B was added to A and emulsified to obtain a water-in-oil emulsion cosmetic.

[Evaluation Items 1 and 2 and Evaluation Method] 20 women with a makeup history of 10 years or more were used as a panel, and (1) feeling of use (good spreadability, non-stickiness), (2) feeling of use (use) (A feeling of sensation at the time) was evaluated according to the following (A) five-step evaluation standard, and the average value of the scores of each sample was determined using the (B) four-step evaluation standard.

(A) Five-step evaluation standard (Score): (Evaluation) 5 points: Very good 4 points: Good 3 points: Normal 2 points: defective 1 point: Very bad (B) 4-step judgment standard (Average score): (Judgment) Average score of 4.5 or more: ◎ Average score of 3.5 or more and less than 4.5: ○ Average score of 2.5 or more and less than 3.5: △ Average point less than 2.5: ×

[Evaluation item 3 and its evaluation method] (3) Regarding the wrinkle improving effect, 20 women with a makeup history of 10 years or more were used as a panel, and the wrinkle improving effect was applied to the skin twice a day for 1 month. Was evaluated according to the following (C) four-stage evaluation criteria, and the average value of the scores of each sample was determined using the (D) four-stage evaluation criteria.

(C) 4-step evaluation criteria (Score): (Evaluation) 4 points: Very effective in improving wrinkles 3 points: Wrinkle-reducing effect 2 points: Slightly improved wrinkles 1 point: Wrinkle improvement effect is not seen (D) 4-step judgment criteria (Average score): (Judgment) Average score of 3.5 or more: ◎ Average score of 2.5 or more and less than 3.5: ○ Average score of 1.5 or more and less than 2.5: △ Average point less than 1.5: ×

[Evaluation Item 4 and Evaluation Method Thereof] (4) Regarding storage stability (separation, discoloration, discoloration), each sample was stored in a constant temperature bath at 40 ° C. and 5 ° C. for 1 month, and immediately after preparation. Based on the state, judgment was made using the following (E) four-step judgment criteria.

(E) 4-step judgment standard (Evaluation): (Judgment) No change: ◎ Minor changes: ○ Slight change: △ Significant change: ×

As is clear from the results shown in Table 1, the water-in-oil type emulsion cosmetics of Examples 1 to 10 of the present invention were compared with the water-in-oil type emulsion cosmetics of Comparative Examples 1 to 3. , Good spreadability, non-greasy feeling on use, excellent wrinkle-relieving effect, and separation of the preparation over time and vitamin A
There was no odor or discoloration due to deterioration of the product, and it was very excellent in storage stability.

[0036] Example 11: Serum     (Component) (%) 1. Vitamin A propionate 0.2 2. Tocopherol 0.3 3. Ascorbyl tetra-2-hexyldecanoate 0.2 4. BHT 0.1 5. Octamethylcyclotetrasiloxane 10.0 6. Dimethylpolysiloxane (6 mPa · s) 6.0 7. Cross-linked methyl polysiloxane (Note 1) 4.0 8. Polyoxyalkylene-modified organopolysiloxane     (Note 5) 1.0 9. Sodium chloride 1.0 10. Glycerin 10.0 11. Polyethylene glycol 2.0 12.1,3-butylene glycol 10.0 13. Purified water Remaining amount Note 5. ABIL EM97 (made by Gold Schmidt)

(Manufacturing method) A: Components (1) to (8) are uniformly mixed at room temperature. B: Components (9) to (13) are uniformly mixed at room temperature. C: B was added to A and emulsified to obtain a beauty essence.

The serum of Example 11 was excellent in the feeling of use and the effect of improving wrinkles, and the separation of the preparation with time and vitamin A
There was no odor or discoloration due to deterioration of the product, and it was very excellent in storage stability.

[0039] Example 12: Pack cosmetic     (Component) (%) 1. Vitamin A succinate 0.5 2. Tocopherol acetate 0.3 3. Ascorbyl tetra-2-hexyldecanoate 0.2 4. Decamethylcyclotetrasiloxane 10.0 5. Methylphenyl polysiloxane 10.0 6.2 Glyceryl 2-ethylhexanoate 20.0 7. Cross-linked alkyl-modified silicone (Note 6) 5.0 8. Cetyl polyoxyalkylene modified organopoly     Loxanes (Note 7) 2.0 9. Sodium chloride 1.0 10. Dipropylene glycol 10.0 11.1,3-butylene glycol 10.0 12. Purified water Remaining amount Note 6. KSG-43 (manufactured by Shin-Etsu Chemical Co., Ltd.) ((vinyl dimethicone / lauryl dime Thicon) 30% crosspolymer mixed with 70% glyceryl 2-ethylhexanoate (Product) (Prescription compounded amount is (vinyl dimethicone / lauryl dimethicone) cross polymer (Listed as the net content) Note 7. ABIL EM90 (Gold Schmidt)

(Manufacturing method) A: Components (1) to (8) are uniformly mixed at room temperature. B: Components (9) to (12) are uniformly mixed at room temperature. C: B was added to A and emulsified to obtain a pack cosmetic.

The pack cosmetic of Example 12 was excellent in the feeling of use and the effect of improving wrinkles, and did not have odor or discoloration due to the separation of the preparation or the deterioration of vitamin A over time, and was extremely excellent in storage stability. there were.

[0042] Example 13: Sunscreen     (Component) (%) 1. Mica (Methylpolysiloxane 5% treatment) 2.0 2. Fine Particle Titanium Oxide (Methylpolysiloxane 5% Treatment) 5.0 3. Fine particle zinc oxide (methyl polysiloxane 5% treatment) 5.0 4. Vitamin A palmitate 0.5 5. Tocopherol 0.3 6. Ascorbyl tetra-2-hexyldecanoate 0.2 7. Isostearyl pivalate 3.0 8. Decamethylcyclotetrasiloxane 10.0 9. Phenyltrimethicone 5.0 10. Cross-linked methylphenyl polysiloxane (Note 2) 3.0 11. PEG-9 polydimethylsiloxyethyl dimethicone       (Note 8) 2.0 12. Octyl paramethoxycinnamate 3.0 13. Sodium chloride 1.0 14. Dipropylene glycol 10.0 15. Purified water Remaining amount Note 8. KF-6028 (made by Shin-Etsu Chemical Co., Ltd.)

(Manufacturing method) A: Components (1) to (12) are uniformly mixed at room temperature. B: Components (13) to (15) are mixed uniformly at room temperature. C: B was added to A and emulsified to obtain a sunscreen.

The sunscreen of Example 13 is excellent in the feeling of use and the effect of improving wrinkles, and has excellent storage stability without discoloration or discoloration due to separation of the preparation or deterioration of vitamin A over time. there were.

[0045]

The water-in-oil type emulsion cosmetic of the present invention has excellent storage stability over time, and has a wrinkle improving effect and a good feeling during use.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) A61K 7/00 A61K 7/00 WF term (reference) 4C083 AB212 AB242 AB332 AB432 AC122 AC342 AC352 AC402 AC422 AC472 AD042 AD151 AD152 AD161 AD162 AD172 AD621 AD622 AD661 AD662 BB04 BB32 BB47 BB51 CC01 CC02 CC05 CC07 DD32 EE01 EE06 EE12 EE17 FF05

Claims (3)

[Claims] 1. The following components (a) to (c): (A) Crosslinked silicone (B) Vitamin A and / or its fatty acid ester (C) Oil-soluble antioxidant A water-in-oil type emulsified cosmetic composition characterized by containing. 2. The water-in-oil type emulsified cosmetic composition according to claim 1, which contains a silicone oil as the component (d). 3. The water-in-oil type emulsified cosmetic composition according to claim 1, which contains a silicone-based surfactant as the component (e).