JP4685716B2 - Whitening cosmetics - Google Patents

Description

  The present invention relates to a whitening cosmetic, and more particularly to a whitening cosmetic having an effect of suppressing skin blackening due to ultraviolet rays and having excellent safety and use feeling.

  When ultraviolet rays are exposed to the skin, the skin is affected in various ways. At that time, active oxygen, lipid peroxide, and the like generated in the skin cause inflammation and cause great damage to the skin tissue. These damages cause loss of moisture, texture, texture, etc. of the skin, and further affect the dermis, forming wrinkles and the like and causing light aging. In addition, as one of the causes of skin color change and darkening, active oxygen generated by ultraviolet rays and various factors released from surrounding cells activate melanocytes and increase tyrosinase activity, resulting in excessive production of melanin. It is thought to be delivered to epidermal cells. Melanin is produced by oxidation of tyrosine, and as a result, the skin tone is changed and blackened.

  Therefore, in order to show the whitening effect, it is important to suppress melanin production. Conventionally, whitening cosmetics containing kojic acid, arbutin, hydroquinone monobenzyl ether, hydrogen peroxide and the like have been proposed in order to prevent skin darkening, spots and freckles and to keep the original white skin. Moreover, vitamin C etc. are proposed in order to suppress the inflammation by ultraviolet rays.

  However, when arbutin, kojic acid, hydroquinone monobenzyl ether, etc. are blended, there is an effect of slightly fading the skin of dark black, but it does not reach the desired level. There may also be problems with the safety of the skin. As described above, it is extremely difficult to obtain a cosmetic having an excellent whitening effect, high skin safety, and sufficient storage stability.

  On the other hand, 2,2′-dihydroxy-5,5′-dialkylbiphenyl is known to have an excellent effect as a melanin production inhibitor (see Patent Document 1). However, application to water-based cosmetics is accompanied by difficulties in terms of solubility, and further improvement in the feeling of use has been demanded.

JP 7-25743 A

  Under such circumstances, an object of the present invention is to provide a whitening cosmetic that is excellent in whitening effect, has high skin safety in the preparation, and has excellent usability.

  In view of such circumstances, the present inventor has conducted extensive research to improve the problems of the prior art, and as a result, 2,2'-dihydroxy-5,5'-dialkylbiphenyl and dicarboxylic acid or a derivative thereof are used in combination. As a result, the present invention was completed by finding that good solubility was obtained and the feeling of use was improved without impairing the whitening effect of the former.

  That is, the whitening cosmetic of the present invention contains 2,2′-dihydroxy-5,5′-dialkylbiphenyl represented by the following general formula (1) and a dicarboxylic acid represented by the general formula (2) or a derivative thereof. It is in the whitening cosmetics characterized by doing.

(In the formula, R is a hydrogen atom, or a saturated or unsaturated hydrocarbon group having a linear or branched chain having 1 to 8 carbon atoms)

(In the formula, R ₁ and R ₂ are each hydrogen or a saturated or hydrocarbon group having 1 to 4 carbon atoms, and n is an integer of 4 to 8)

  Whitening cosmetics containing 2,2′-dihydroxy-5,5′-dialkylbiphenyl and a dicarboxylic acid or a derivative thereof have an excellent whitening effect, high skin safety in the preparation, and excellent usability. Useful as a whitening cosmetic.

  Hereinafter, embodiments of the present invention will be described in detail.

  The 2,2′-dihydroxy-5,5′-dialkylbiphenyl of the present invention is a known substance and can be easily obtained (Nippon Chemical Journal, Vol. 87, No. 6, 603, 1966). . In addition, it can be easily obtained by using magnolol obtained from the bark of a magnoliaceae plant, or further hydrogenating it.

  In 2,2′-dihydroxy-5,5′-dialkylbiphenyl, the alkyl may be a hydrogen atom, and the hydrocarbon group may be linear or branched, It may be a saturated or unsaturated hydrocarbon group. Further, it may be a hydrocarbon group in which a hydrogen atom is substituted with a hydroxyl group. Specific examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, allyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl and the like, but are not limited thereto. Absent. From the viewpoint of stability, a saturated hydrocarbon group is preferable, and among them, a propyl group, an isopropyl group, and an allyl group are preferable in view of the effect, and particularly a propyl group (2,2′-dihydroxy-5,5 ′). -Di-n-propylbiphenyl) is preferred.

  The content of 2,2′-dihydroxy-5,5′-dialkylbiphenyl in the whitening cosmetic is preferably 0.001 to 8.0% by mass (hereinafter simply referred to as “%”), more preferably 0.8. 01-5.0%. If it is less than 0.001%, the expected whitening effect may not be obtained, and if it exceeds 8.0%, an effect commensurate with the content may not be obtained, and formulation tends to be difficult. It is not preferable.

  The dicarboxylic acid and derivatives thereof of the present invention are known substances, and can be easily produced, for example, by esterification of sebacic acid and a lower alcohol, and commercially available products can also be obtained. Among these, diisopropyl sebacate sold by Nikko Chemicals, diethyl sebacate sold by Nippon Seika Co., Ltd., and diisopropyl adipate sold by Cloda Japan are preferred.

  The content of the dicarboxylic acid or its derivative in the whitening cosmetic is preferably 0.001 to 10.0%, more preferably 0.01 to 8.0%. If it is less than 0.001%, it may be difficult to formulate, and if it exceeds 10.0%, an effect commensurate with the content may not be obtained, and it tends to be difficult to formulate. . The amount ratio of 2,2′-dihydroxy-5,5′-dialkylbiphenyl to dicarboxylic acid or a derivative thereof is preferably 1: 0.5 to 1:10, more preferably 1: 3 to 1: 8. It is.

  The whitening cosmetic of the present invention is not particularly limited as long as it is generally applied to the skin, and can be used as a base cosmetic or foundation in addition to normal skin cosmetics. Also good. As the dosage form, it is possible to use a commonly used aqueous solution, W / O type or O / W type emulsion, appropriate excipients, etc. to form granules or other powders, tablets, etc., specifically Examples include creams, emulsions, lotions, packs, gels, sticks, sheets, and pops. For example, in the case of a milky lotion, this whitening cosmetic can be produced by an ordinary method in which an oil phase and an aqueous phase are dissolved by heating, emulsified and dispersed, and then cooled.

In the whitening cosmetic composition of the present invention, it is preferable to further blend other components useful for the whitening cosmetic composition because a better whitening effect can be obtained. For example, other whitening agents include magnesium ascorbate phosphate, water-soluble vitamin C derivatives such as sodium ascorbate phosphate and glucoside ascorbate, placenta extract, fire spine extract, raspberry ketone glucoside, apricot extract, wheat germ An extract, a zinc-containing yeast extract, a gentian extract, an anise extract, an oil-soluble licorice extract, a saicin extract, a flaxseed extract, a Dutch mustard extract and the like can be mentioned. Further, as melanin metabolism improving agent, carrot extract, apricot extract, honeysuckle extract, niacinamide, lactic acid bacteria fermentation liquid, α-hydroxy acid, anti-inflammatory agent, diphenhydramine hydrochloride, glycyrrhizic acids and derivatives thereof, vitamin E and derivatives thereof, allantoin Vitamin As, β-carotene, and other moisturizers include N-methyl-L-serine. Among these, other whitening agents, apricot extract, niacinamide, lactic acid bacteria fermentation liquid, diphenhydramine hydrochloride, glycyrrhizic acids and derivatives thereof are particularly preferable in terms of effects. And it is preferable to use a plant extract other than the above in combination since an excellent effect in terms of touch and moisture retention can be obtained.

  In addition to the above, the whitening cosmetics of the present invention include tar dyes, colored pigments such as iron oxide, preservatives such as parabens, anionic surfactants such as fatty acid soaps, sodium cetyl sulfate, and polyoxyethylene. Nonionic surfactants such as alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene hydrogenated castor oil, polyhydric alcohol fatty acid esters, polyglycerin fatty acid esters, tetraalkylammonium salts, etc. Cationic surfactant, betaine type, sulfobetaine type, sulfoamino acid type, amphoteric surfactant such as sodium N-stearoyl-L-glutamate, natural surfactant such as lecithin, lysophosphatidylcholine, Gelatin, casein, starch, gum arabic, cara Natural polymers such as gum, guar gum, locust bean gum, dragagacanto gum, quince seed, pectin, carrageenan, sodium alginate, semi-synthetic polymers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, polyvinyl Synthetic polymers such as methyl ether and copolymer, polyvinylpyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyethylene oxide polymer, thickeners such as xanthan gum, pigments such as titanium oxide, antioxidants such as dibutylhydroxytoluene, etc. , And can be appropriately blended within a range not impairing the object of the present invention.

  Hereinafter, the present invention will be described in detail based on examples, production examples, and comparative examples. In addition, this invention is not limited to these.

・ Whitening Practical Test For the left forearm bent side skin of 20 subjects under test exposed to summer sunlight for 3 hours (1.5 hours per day for 2 days) The sample was applied from the day exposed to the sun, and the base (base only) was applied to the right forearm flexor side skin once a day in the morning and evening for 13 weeks. The evaluation was shown by the number of subjects whose whitening effect was confirmed in the sample application part from the base application part by visual inspection by a specialist. At the same time, the number of people who answered that a feeling of use (no stickiness, refreshing feeling) was preferable was shown.

Examples 1-3, Comparative Examples 1-4 (skin lotion)
In the raw material composition shown in Table 1, the active ingredients shown in Table 2 were blended to prepare a skin lotion, and the whitening practical test was conducted.

-Preparation method After the B component described in Table 2 was uniformly dissolved in the C component, the A component and the C component were uniformly mixed and stirred, dispersed, and then filled into a container.

[Table 1]
Raw material component amount (%)
(A)
Ethanol 10.0
Polyoxyethylene (20) sorbitan monolaurate 5.0
Dibutylhydroxytoluene 0.01
2,2'-dihydroxy-5,5 '
-Di-n-propylbiphenyl 0.3
Fragrance 0.05
(B)
Listed in Table 2 (C)
Glycerin 5.0
Xanthan gum 0.1
Hydroxyethyl cellulose 0.1
Purified water balance

[Table 2]
(B) Raw material ingredients Blending amount Whitening practical test Usability
(%) (people)
------------------------------------
Example 1 Diisopropyl sebacate 2.0 19 18
Example 2 Diethyl sebacate 2.0 17 16
Example 3 Diisopropyl Adipate 2.0 18 15
Comparative Example 1 − − 14 8
Comparative Example 2 Octyldodecyl myristate 2.0 15 10
Comparative Example 3 Trioctanoin 2.0 15 9
Comparative Example 4 Dibutyloctyl sebacate 2.0 14 10

-The characteristic test results are shown in Table 2. As shown in Table 2, Examples 1 to 3, which are cosmetics of the present invention, showed a good whitening effect and were superior in usability compared to Comparative Examples 1 to 4. In addition, the test subject who showed skin irritation reaction or skin sensitization reaction did not occur.

  A whitening cosmetic preparation was prepared by a conventional method according to the following formulation.

Application example 1 (lotion)
[Table 3]
Raw material component Compounding amount (%) -------------------------------------
Ethanol 10.0
Polyoxyethylene (20) sorbitan monolaurate 3.0
1,3-butylene glycol 4.0
Methylparaben 0.05
Phenoxyethanol 0.3
Fragrance 0.01
2,2′-Dihydroxy-5,5′-di-n-propylbiphenyl 0.1
Diethyl sebacate 0.3
Fire thorn extract (* 1) 0.05
Licorice extract (* 2) 0.01
Purified water balance

* 1; Fire Thorn (Suntory)
* 2: Licorice extract (Maruzen Pharmaceutical Co., Ltd.)

Application example 2 (milky lotion)
[Table 4]
Raw material component Compounding amount (%) -------------------------------------
Ethanol 10.0
Polyoxyethylene oleyl ether (2E.O.) 0.2
Polyoxyethylene cetyl ether (2E.O.) 0.1
Polyoxyethylene hydrogenated castor oil (60 EO) 0.3
Methylphenyl polysiloxane (* 3) 1.0
Dimethylpolysiloxane (* 4) 1.0
Glyceryl tri-2-ethylhexanoate 1.0
Diisopropyl sebacate 5.0
2-Ethylhexyl paramethoxycinnamate 1.0
Fragrance 0.05
2,2′-dihydroxy-5,5′-di-n-propylbiphenyl 1.5
Lauroyl-L-glutamate sodium 1.0
Dipropylene glycol 1.0
Concentrated glycerin 2.0
Carboxyvinyl polymer (* 5) 0.3
Potassium hydroxide 0.15
Edetate disodium 0.01
Raspberry ketone glucoside (* 6) 0.1
Seaweed extract (* 7) 0.01
Purified water balance

* 3: Silicon FZ-209 (Nihon Unicar)
* 4; Silicon KF-96 (300 cs; manufactured by Shin-Etsu Chemical Co., Ltd.)
* 5; CARBOPOL 941 (manufactured by BF Goodrich)
* 6; Raspberry ketone glucoside (Hasegawa Fragrance)
* 7; Marine purge (Ichimaru Falcos)

Application example 3 (milky lotion)
[Table 5]
Raw material component Compounding amount (%) -------------------------------------
Ethanol 10.0
Hydrogenated soybean phospholipid (* 8) 1.0
Cholesterol 0.5
2,2′-Dihydroxy-5,5′-di-n-propylbiphenyl 1.0
Diisopropyl sebacate 4.0
N-methyl-L-serine 0.01
Polyoxyethylene methyl glucoside (* 9) 2.0
Polyglycerin 1.0
Liquid paraffin 1.0
Cyclopentapolysiloxane 1.0
Carboxyvinyl polymer (* 5) 0.2
Triethanolamine 1.0
Xanthan gum 0.1
Methylparaben 0.1
Perfume 0.03
Hakugai hydrolyzed extract (* 10) 0.01
Honeysuckle extract (* 11) 0.01
Soymilk fermented liquid (* 12) 0.01
Purified water balance

* 8: Resinol S-10 (Nikko Chemicals)
* 9; NIKKOL BMG-20 (manufactured by Nikko Chemicals)
* 10: Sina Blanca-WH (Technoble)
* 11: Falco Rex Honeysuckle SB (Ichimaru Falcos)
* 12: Fermented soymilk (made by Sansho Pharmaceutical Co., Ltd.)

Application example 4 (O / W type cream)
[Table 6]
Raw material component Compounding amount (%) -------------------------------------
Cetanol 5.0
Lipophilic glyceryl monostearate 1.0
Polyoxyethylene cetyl ether (2E.O.) 0.1
2,2′-Dihydroxy-5,5′-di-n-propylbiphenyl 2.0
Diisopropyl adipate 7.0
Butylparaben 0.1
Methylphenyl polysiloxane (* 3) 2.0
Squalane 2.0
Sucrose fatty acid ester (* 13) 0.5
Methylparaben 0.1
Perfume 0.03
Sodium L-hyaluronate 0.1
Acrylic acid / alkyl methacrylate copolymer (* 14) 0.1
Sodium hydroxide 0.05
Carrot juice (* 15) 0.1
Orange juice (* 16) 0.1
Dioscorea compositor extract (* 17) 0.1
Yeast extract (* 18) 0.1
Purified water balance

* 13: Sugar wax A-10E (Daiichi Kogyo Seiyaku Co., Ltd.)
* 14; PEMULEN TR-1 (manufactured by BF Goodrich)
* 15: Homofruit Carrot N (Esperis)
* 16: Homofruit Orange N (Esperis)
* 17: Dioscorea compositor root extract (Mitsui Chemicals)
* 18: East Liquid ZB (Ichimaru Falcos)

Application Example 5 (W / O type cream)
[Table 7]
Raw material component Compounding amount (%) -------------------------------------
Sorbitan monoisostearate 1.0
2,2′-Dihydroxy-5,5′-di-n-propylbiphenyl 1.0
Diisopropyl sebacate 4.0
Poly (oxyethylene / oxypropylene)
Methyl polysiloxane copolymer (* 19) 1.0
Cyclopentasiloxane 8.0
Sodium chloride 1.0
Magnesium chloride 1.0
Dipropylene glycol 7.0
Methylparaben 0.1
Perfume 0.03
Fine particle titanium oxide (* 20) 2.0
Apricot juice (* 21) 0.01
Wheat germ extract (* 22) 0.01
Marronie extract (* 23) 0.01
Purified water balance

* 19; BY-22-008 (Toray Dow Corning Silicone)
* 20: Taipei TTO-55 (A) (Ishihara Sangyo Co., Ltd.)
* 21: Apricot extract K (Esperis)
* 22: Clariskin (manufactured by Silab)
* 23: Maronnier extract BG-J (manufactured by Maruzen Pharmaceutical Co., Ltd.)

Application Example 6 (Sunscreen)
[Table 8]
Raw material component Compounding amount (%) -------------------------------------
Methylphenyl polysiloxane (* 3) 1.0
Glyceryl tri-2-ethylhexanoate 2.0
2-Ethylhexyl paramethoxycinnamate 3.0
4-tert-Butyl-4'-methoxybenzoylmethane 1.0
Dimethoxybenzylidene oxoimidazolidine propionic acid
2-Ethylhexyl 1.0
2,2′-dihydroxy-5,5′-di-n-propylbiphenyl 0.5
Diethyl sebacate 4.0
Sodium phenylbenzimidazole sulfonate 3.0
Lipophilic glyceryl monostearate 1.0
Sodium polyoxyethylene oleyl ether phosphate (2EO) 0.3
Butylparaben 0.1
Stearoyl-potassium L-glutamate 0.3
Fine particle titanium oxide (* 20) 3.0
Fine particle zinc oxide (* 24) 7.0
Methylparaben 0.1
Perfume 0.02
Anise extract (* 25) 0.1
Elderberry extract (* 26) 0.01
Honoki extract (* 27) 0.01
Purified water balance

* 24: ZnO-350 (Sumitomo Osaka Cement)
* 25: Anise extract (manufactured by Sansho Pharmaceutical)
* 26; Elderberry extract BG (Maruzen Pharmaceutical Co., Ltd.)
* 27: Falco Rex Honoki B (Ichimaru Falcos)

Application Example 7 (Cosmetic liquid)
[Table 9]
Raw material component Compounding amount (%) -------------------------------------
Lysolecithin 0.5
Polyoxyethylene sorbitan monooleate (2E.O.) 0.3
Polyoxyethylene hydrogenated castor oil (40 EO) 0.5
Ethanol 7.0
Methylphenyl polysiloxane (* 3) 3.0
Fragrance 0.01
2,2′-Dihydroxy-5,5′-di-n-propylbiphenyl 1.0
Diisopropyl sebacate 3.0
1,3-butylene glycol 3.0
Polyethylene glycol 1000 1.0
Ascorbic acid 2-glucoside 2.0
Dipotassium glycyrrhizinate 0.2
Nicotinamide 1.0
N-methyl-L-serine 0.1
Potassium hydroxide 0.15
Lactic acid bacteria fermentation broth (* 28) 0.1
γ-aminobutyric acid (* 29) 0.02
Tea extract (* 30) 0.01
Camellia extract (* 31) 0.01
Juzdama extract (* 32) 0.01
Yukinoshita extract (* 33) 0.01
Giant extract (* 34) 0.01
Cypress water (* 35) 0.01
Rooibos extract (* 36) 0.01
Purified water balance

* 28: Whey CPA (Ichimaru Falcos)
* 29; BIO GABA (manufactured by Kyowa Hakko)
* 30: Tea fruit extract (Maruzen Pharmaceutical Co., Ltd.)
* 31: Camellia seed extract (Maruzen Pharmaceutical Co., Ltd.)
* 32: Yokuinin extract BG-S (Maruzen Pharmaceutical Co., Ltd.)
* 33; Yukinoshita extract (manufactured by Ichimaru Falcos)
* 34: Geoweed extract BG-J (manufactured by Maruzen Pharmaceutical Co., Ltd.)
* 35; Hinoki water B (Maruzen Pharmaceutical Co., Ltd.)
* 36: Falco Rex Rooibos B (N) (Ichimaru Falcos)

  Application examples 1 to 7 were excellent in usability. In addition, the test subject who showed skin irritation reaction or skin sensitization reaction did not occur.

  In addition, the composition of the fragrance | flavor used in said application example is shown below.

Claims (4)

It contains a biphenyl compound represented by the following general formula (1) and a dicarboxylic acid represented by the following general formula (2) or a derivative thereof, and a quantitative ratio between the biphenyl compound and the dicarboxylic acid or a derivative thereof is Whitening cosmetic, characterized in that it is 1: 3 to 1: 8 .

(In the formula, R is a hydrogen atom, or a saturated or unsaturated hydrocarbon group having a linear or branched chain having 1 to 8 carbon atoms)

(In the formula, R ₁ and R ₂ are each hydrogen or a saturated or hydrocarbon group having 1 to 4 carbon atoms, and n is an integer of 4 to 8) The whitening cosmetic according to claim 1, wherein the content of the biphenyl compound represented by the general formula (1) is 0.001 to 8.0% by mass. The whitening cosmetic according to claim 1 or 2, wherein the content of the dicarboxylic acid represented by the general formula (2) or a derivative thereof is 0.001 to 10.0% by mass. The dicarboxylic acid represented by the general formula (2) or a derivative thereof is one or more selected from the group consisting of diisopropyl sebacate, diethyl sebacate and diisopropyl adipate. Whitening cosmetics described in 1.