JPH04149117A - Skin-beautifying cosmetic - Google Patents
Skin-beautifying cosmeticInfo
- Publication number
- JPH04149117A JPH04149117A JP2274819A JP27481990A JPH04149117A JP H04149117 A JPH04149117 A JP H04149117A JP 2274819 A JP2274819 A JP 2274819A JP 27481990 A JP27481990 A JP 27481990A JP H04149117 A JPH04149117 A JP H04149117A
- Authority
- JP
- Japan
- Prior art keywords
- ascorbic acid
- skin
- formula
- formulas
- acid derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002537 cosmetic Substances 0.000 title claims abstract description 20
- 230000002087 whitening effect Effects 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 5
- 125000003289 ascorbyl group Chemical class [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 17
- 150000000996 L-ascorbic acids Chemical class 0.000 abstract description 14
- 229960005070 ascorbic acid Drugs 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 8
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 6
- 239000002211 L-ascorbic acid Substances 0.000 abstract description 5
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 abstract description 4
- 229930003268 Vitamin C Natural products 0.000 abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 229930003799 tocopherol Natural products 0.000 abstract description 4
- 239000011732 tocopherol Substances 0.000 abstract description 4
- 235000019154 vitamin C Nutrition 0.000 abstract description 4
- 239000011718 vitamin C Substances 0.000 abstract description 4
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 abstract description 3
- 235000010384 tocopherol Nutrition 0.000 abstract description 3
- 229960001295 tocopherol Drugs 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 150000003977 halocarboxylic acids Chemical class 0.000 abstract description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 2
- 125000006239 protecting group Chemical group 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract 3
- POXUQBFHDHCZAD-UHFFFAOYSA-N 2-(2,2-dimethyl-1,3-dioxolan-4-yl)-3,4-dihydroxy-2h-furan-5-one Chemical compound O1C(C)(C)OCC1C1C(O)=C(O)C(=O)O1 POXUQBFHDHCZAD-UHFFFAOYSA-N 0.000 abstract 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012346 acetyl chloride Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 235000015320 potassium carbonate Nutrition 0.000 abstract 1
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011668 ascorbic acid Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 8
- 102000003425 Tyrosinase Human genes 0.000 description 7
- 108060008724 Tyrosinase Proteins 0.000 description 7
- 235000010323 ascorbic acid Nutrition 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- -1 fatty acid ester Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 206010014970 Ephelides Diseases 0.000 description 3
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 3
- 208000003351 Melanosis Diseases 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 206010042496 Sunburn Diseases 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 208000012641 Pigmentation disease Diseases 0.000 description 2
- 229940087168 alpha tocopherol Drugs 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002884 skin cream Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229960000984 tocofersolan Drugs 0.000 description 2
- 229960004441 tyrosine Drugs 0.000 description 2
- 235000004835 α-tocopherol Nutrition 0.000 description 2
- 239000002076 α-tocopherol Substances 0.000 description 2
- 241000700199 Cavia porcellus Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000010044 Hernandia moerenhoutiana Nutrition 0.000 description 1
- 244000084296 Hernandia moerenhoutiana Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000819999 Nymphes Species 0.000 description 1
- 206010064127 Solar lentigo Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- VJNCICVKUHKIIV-UHFFFAOYSA-N dopachrome Chemical compound O=C1C(=O)C=C2NC(C(=O)O)CC2=C1 VJNCICVKUHKIIV-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 201000001441 melanoma Diseases 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- UJQMLHKSZKBMMO-UHFFFAOYSA-N n,n-diethylethanamine;pyridine Chemical compound C1=CC=NC=C1.CCN(CC)CC UJQMLHKSZKBMMO-UHFFFAOYSA-N 0.000 description 1
- GINQYTLDMNFGQP-UHFFFAOYSA-N n,n-dimethylformamide;methylsulfinylmethane Chemical compound CS(C)=O.CN(C)C=O GINQYTLDMNFGQP-UHFFFAOYSA-N 0.000 description 1
- NWKYZYGOSPOKDY-UHFFFAOYSA-N n,n-dimethylformamide;pyridine Chemical compound CN(C)C=O.C1=CC=NC=C1 NWKYZYGOSPOKDY-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 231100000245 skin permeability Toxicity 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000002640 tocopherol group Chemical class 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- HTJNEBVCZXHBNJ-XCTPRCOBSA-H trimagnesium;(2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;diphosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O HTJNEBVCZXHBNJ-XCTPRCOBSA-H 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Cosmetics (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野〕
本発明は新規な美白化粧料に関する。さらに詳しくは、
ビタミンＣ−Ｅ誘導体を含有することを特徴とする、美
白効果及び保存安定性に優れた美白化粧１に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel whitening cosmetic. For more details,
The present invention relates to whitening makeup 1 which is characterized by containing a vitamin C-E derivative and has excellent whitening effects and storage stability.
（従来の技術〕
−ＦＩＱにノミ、ソバカス、日焼けなどに見られる皮膚
の色素沈着は、皮膚内に存在するチロシンがチロ７ナー
ゼの作用により酸化されてメラニンとなり、このメラニ
ンが過剰に生成することに基因するとされてル）る。(Prior art) - Skin pigmentation seen in FIQ due to fleas, freckles, sunburn, etc. is caused by tyrosine present in the skin being oxidized to melanin by the action of tyro-7nase, and this melanin being produced in excess. It is said to be caused by
従来より、この色素沈着の予防或いは治療を目的として
、アスコルビン酸が使用されている。Conventionally, ascorbic acid has been used for the purpose of preventing or treating pigmentation.
しかし、アスコルビン酸は、熱や光に対して極めて不安
定で、酸化され昌り、特に水系の化粧料中においては、
分解して変臭１着色を招く原因となる。However, ascorbic acid is extremely unstable to heat and light and easily oxidized, especially in water-based cosmetics.
It decomposes and causes odor and discoloration.
これらの問題点を解決する為、アスコルビン酸高級脂肪
酸エステル、アスコルビン酸硫酸エステル、Ｌ−アスコ
ルビン酸りん酸マグＺシウム、トコフェロール−し一ア
スコルビン酸−２−リン酸エステル １−コツエロール
ーし一アスコルビン酸−６−ジカルボン酸ジエステル等
の各種のアスコルビン酸誘導体が使用されている。In order to solve these problems, we developed ascorbic acid higher fatty acid ester, ascorbic acid sulfate ester, L-ascorbic acid magzium phosphate, tocopherol-mono-ascorbic acid-2-phosphate ester, 1-cotzerol-mono-ascorbic acid- Various ascorbic acid derivatives such as 6-dicarboxylic acid diesters have been used.
しかし、アスコルビン酸高級脂肪酸エステルは、安定性
は改善されているものの、美白効果が弱い。However, although ascorbic acid higher fatty acid ester has improved stability, it has a weak whitening effect.
アスコルビン酸硫酸エステルは、水溶性である為、油系
の化粧料に配合しづらく、美白効果も弱い。Because ascorbic acid sulfate is water-soluble, it is difficult to incorporate into oil-based cosmetics and has a weak whitening effect.
Ｌ−アスコルビン酸りん酸マグふシウムは、美白効果に
は優れているが、皮膚透過性が不十分であるため、美白
効果を得る為には、配合料を多くしなければならない。L-ascorbic acid magfusium phosphate has an excellent whitening effect, but its skin permeability is insufficient, so in order to obtain a whitening effect, a large amount of the ingredient must be added.
トコフェロール−し−アスコルビンＭ−２−４１ん酸エ
ステルの塩は、塩の種類によっては水に不溶のものがあ
る為、処方を組みにくい。Salts of tocopherol-ascorbic M-2-41 phosphate are difficult to formulate because some salts are insoluble in water.
上記の欠点を克服するものとして、トコフェロール−Ｌ
−アスコルビン酸−６−ジカルボン酸ジエステルがｌｘ
されている（特開昭６２１８７４７０）。しかしこの化
合物はビタミンＣの油溶性が高められており、高い美白
効果を有しているものの、保存によって分解し易く、活
性の低下が著しいという問題点がある。Tocopherol-L
-Ascorbic acid-6-dicarboxylic acid diester is lx
(Japanese Patent Application Laid-Open No. 62187470). However, although this compound has increased oil solubility of vitamin C and has a high whitening effect, it has the problem that it is easily decomposed during storage and its activity is significantly reduced.
［発明が解決しようとする課題〕
従って本発明の目的は、美白効果に優れ、ビタミンＣの
熔解性が改善されており、しかもビタミンＣの保存安定
性に優れた、美白化粧料を従供することにある。[Problems to be Solved by the Invention] Accordingly, an object of the present invention is to provide a whitening cosmetic that has excellent whitening effects, improved solubility of vitamin C, and excellent storage stability of vitamin C. It is in.
本発明は、
（１） 下記−船人（１）又は（ＩＩ）で表されるア
スコルビン酸誘導体を含有することを特徴とする美白化
粧料。The present invention provides: (1) A whitening cosmetic containing an ascorbic acid derivative represented by the following - Shipin (1) or (II).
じ： （式 ％式％） を表し、Ｒ，、Ｒ４は、Ｈ又ハＣＨ、を表す。character: (formula %formula%) R,, R4 represents H or CH.
Ｒ６は、炭素数１〜２ｏの直鎖又は分岐鎖の、飽和又は
不飽和の炭化水素基、又は−Ｒ，−Ａ、−Ｒ，−基を表
す。R6 represents a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 2 carbon atoms, or a -R, -A, -R, - group.
Ｒ，、Ｒ，は、炭素数１〜１ｏの直鎖又は分岐鎖の、飽
和又は不飽和の炭化水素基、Ａは、−ｏ−１−ｃｏ−−
ｏｃ。R,, R, is a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 1 carbon atoms, and A is -o-1-co--
oc.
−ＣＨ（ＯＨ）−、−ＣＨ（ＮＲ，Ｒ，）ＮＲ，−、−
ＮＲｚＣＯ−、（Ｄいずれがを表し、Ｒ１１−ＲＩ＋は
、水素もしくは炭素数１〜４の飽和炭化水素基を表す。-CH(OH)-, -CH(NR,R,)NR,-,-
NRzCO-, (D either represents, and R11-RI+ represents hydrogen or a saturated hydrocarbon group having 1 to 4 carbon atoms.
）
（２） 下記−船人（Ｉ［ｌ）又は（■）で表される
アスコルビン酸誘導体を含有することを特徴とする美白
化粧料。) (2) A whitening cosmetic characterized by containing an ascorbic acid derivative represented by the following - Funato (I [l) or (■).
Ｈ○’ ”０Ｒ１
（但し、Ｒ，、Ｒ，は、（］）、 （ＩＩ）の場合と
同しである。）
である。H○' ”0R1 (However, R,, R, are the same as in the case of (]) and (II).)
本発明に用いられる一般式（１）〜（八１）で表される
アスコルビン酸誘導体は、例えば次のようにして製造す
ることができる。The ascorbic acid derivatives represented by general formulas (1) to (81) used in the present invention can be produced, for example, as follows.
ハロカルボン酸とトコフェロールを、炭酸カリウム 水
酸化ナトリウム等の塩基の存在下、ＤＭＦ ＤＭＳＯ
等の７容媒中で反応させる。Halocarboxylic acids and tocopherols are dissolved in DMF DMSO in the presence of a base such as potassium carbonate and sodium hydroxide.
The reaction is carried out in a 7-volume medium such as
次に、Ｌ−アスコルビン酸をアセトン溶媒中でアセデル
クロライｌと反応させ、室温下で懸濁した後、冷却する
。得られた結晶を、冷やしたアセトンで洗浄し、乾燥す
ることによって、５．６０−イソプロピリデン−Ｌ−ア
スコルビン酸を調製する。Next, L-ascorbic acid is reacted with acedelchloride 1 in an acetone solvent, suspended at room temperature, and then cooled. 5.60-isopropylidene-L-ascorbic acid is prepared by washing the obtained crystals with chilled acetone and drying.
得られた５、６−０−イソプロピリデン−しアスコルビ
ン酸と先に調製した、トコフェロールのカルボン酸エー
テルを、ピリジン ＤＭＦ等の溶媒中、塩基性触媒（必
要に応して、ピリジントリエチルアミン等を加える）、
脱水剤（Ｎ、 Ｎジシクロヘキノル力ルポジイミド
チオニルクロライド等）の存在下で反応させることによ
って、−船人（ｍ）又は（ＴＶ）で表される化合物を製
造することができる。The obtained 5,6-0-isopropylidene-ascorbic acid and the previously prepared carboxylic acid ether of tocopherol are mixed in a solvent such as pyridine DMF with a basic catalyst (if necessary, pyridine triethylamine, etc.) ),
Dehydrating agent (N, N dicyclohexynol lupodiimide
thionyl chloride, etc.), a compound represented by -Funenin (m) or (TV) can be produced.
−ｉ式（１’ｌ又は（Ｉｔ）で表される化合物は、化合
物（ｍ）又は（ＴＶ）をＴ ＨＦ等の溶媒に溶かし、Ｉ
Ｎ塩酸等の酸を加えて撹拌し、アスコルビン酸の５．６
位の保護基をはずすことによって得ることができる。-i The compound represented by formula (1'l or (It)) can be obtained by dissolving compound (m) or (TV) in a solvent such as THF,
Add an acid such as N-hydrochloric acid and stir to reduce the amount of ascorbic acid to 5.6.
It can be obtained by removing the protecting group at position.
一般式（１）〜（■）で表される化合物を製造する為に
用いられるジハロゲン化炭化水素としては、例えば以下
のようなものが挙げられるが、これらに限定されるもの
ではない。Examples of the dihalogenated hydrocarbons used to produce the compounds represented by formulas (1) to (■) include, but are not limited to, the following.
Ｏ
Ｉ ＩＩ
ＨＯ（、−ＣＨ２−Ｘ、ＨＯＣ−ＣＨ２ＣＨ２−Ｘｏ
ＣＨ３
０Ｃ（ＣＨｔ）ｚ ＣＨ（Ｃ
Ｈ２）２
ＣＨ＝
Ｃ
２−Ｃ
Ｈ（ＣＨｆｆｉ）ｆｆ−Ｘ
Ｈ２
ＣＨ（Ｃ
Ｈｚ）ｚ−
０Ｃ
（ＣＨｚ）ｚ
Ｎ（ＣＨ３）。O I II HO(, -CH2-X, HOC-CH2CH2-Xo
CH3 0C(CHt)z CH(CH2)2 CH= C2-CH(CHffi)ff-X H2 CH(C Hz)z- 0C(CHz)z N(CH3).
ＣＩ（（Ｃ Ｈ２）３ ］ｊ ＨＯＣ−ＣＨＥＮ Ｈ（ＣＨり。CI((C H2)3 】j HOC-CHEN H (CHri.
ＨＯＣ ○ Ｃ［Ｎ ＨＣ（ＣＨ２）３ ＯＯＨＣＨ。H.O.C. ○ C[N HC(CH2)3 OOHCH.
（Ｉ
ＨＯＣ−ＣＨ，ＣＨ（ＣＨ，）２ＣＨ（ＣＨり２−Ｘ○
ＨＯＣ−ＣＨ，ＣＨ＝ＣＨ（ＣＨ，）、ＯＣＨ，−Ｘ（
但し、Ｘはハロゲンを表す。）
以上のようにして製造したアスコルビン酸誘導体の、チ
ロソナーゼ活性阻害率を、後述する方法によって測定し
、その結果を第１表に示した。(I HOC-CH,CH(CH,)2CH(CHri2-X○ HOC-CH,CH=CH(CH,),OCH,-X(
However, X represents halogen. ) The tyrosonase activity inhibition rate of the ascorbic acid derivative produced as described above was measured by the method described below, and the results are shown in Table 1.
尚、試料中の化合物（１）、（Ｉｆ）の濃度は、本発明
の美白化粧料における、−船人（１）〜（ＩＶ）で表さ
れるし一アスコルビン酸誘導体の含有量は、該当化粧料
の総量に対して０．１〜１０重量％（以下重量％をＷＬ
％と略記する。）が好ましい。In addition, the concentrations of compounds (1) and (If) in the sample are represented by -Funenin (1) to (IV) in the whitening cosmetic of the present invention, and the content of mono-ascorbic acid derivatives is as follows: 0.1 to 10% by weight based on the total amount of cosmetics (hereinafter referred to as WL)
Abbreviated as %. ) is preferred.
０、１ ｗ ｔ％未満だとあまり効果が得られず、１０
ｗｔ％を越えても効果の大きな増加は望めない
本発明の美白化粧料の剤型は、特に限定されるものでな
く、クリーム状、乳液状、ローション状。If it is less than 0.1 wt%, it will not be very effective, and 10
The dosage form of the whitening cosmetic of the present invention is not particularly limited, and may be cream-like, milky lotion-like, or lotion-like.
パウダー状等々の通常の化粧料の剤型を適用することが
出来る。Usual cosmetic formulations such as powder can be used.
又、他の成分として、香料、防腐剤１着色料皮膚栄養剤
などを、本発明の目的を達成する範囲内で適宜配合し得
る。Further, as other ingredients, fragrances, preservatives, colorants, skin nutrients, etc. may be appropriately incorporated within the scope of achieving the object of the present invention.
［実施例］ 以下、実施例にて本発明を説明する。[Example] The present invention will be explained below with reference to Examples.
実施例に記載の■保存安定性試験（チロンナーゼ活性阻
害率の安定性）■メラニン形成抑制試験。■ Storage stability test (stability of thyronase activity inhibition rate) ■ Melanin formation inhibition test described in Examples.
■皮膚色明度回復試験、■美白実用試験は、下記の通り
に実施した。■Skin color brightness recovery test and ■Whitening practical test were conducted as follows.
■ 保存安定性試験
下記の方法にて、本発明の美白化粧料の、調製直後、２
０°Ｃ３ケ月保存後１４５°Ｃ３ケ月保存後のチロシナ
ーゼ活性阻害率を測定し、保存安定性を評価した。■ Storage stability test Immediately after preparation of the whitening cosmetic of the present invention, 2
The inhibition rate of tyrosinase activity was measured after storage at 0°C for 3 months and at 145°C for 3 months to evaluate storage stability.
ハーデイングーパノセイ（Ｈａｒｄｉｎｇ−Ｐａｓｓａ
ｙ ）マウスメラノーマから抽出した酵素チロシナーゼ
を使用し、その酵素活性をドーパ−クロームの４７５ｎ
ｍの吸光度を測定するフォトメトリー法によってしらべ
た。Harding-Passa
y) Using the enzyme tyrosinase extracted from mouse melanoma, its enzyme activity was determined by 475n of dopachrome.
This was investigated by photometry, which measures the absorbance of m.
本発明の美白化粧１！１４（以下試料と称す。）０．９
ｍｌを採取し、Ｌ−チロシン溶液（０，３ｍ ｇ ／ｍ
ｆｆ１）を１ｍｌとマンクルペイン氏の緩衝液（ｐ Ｈ
６，８）を１ｍｎ加え、３７°Ｃの恒温水槽中で１０分
間インキュへ−トシた後、これにチロシナーゼ？８ｆｌ
（１ｍｇ／ｍｆｆ）を０．１ ｍ Ｒ加えてよく攪拌し
、３７°Ｃに保って１０分後、４７５ｎｍで吸光度（Ｄ
ｌ）を測定する。加熱失活させたチロシナーゼを用いて
同様に反応させた吸光度（Ｄ２）および、試料の代わり
に水のみを用いた対照試験品の吸光度（Ｄ３）を測定し
、次式からチロシナーゼ活性阻害率を算出する。Whitening makeup of the present invention 1!14 (hereinafter referred to as sample) 0.9
ml was collected and L-tyrosine solution (0.3 mg/m
ff1) and Munklepain's buffer (pH
6, 8) was added and incubated for 10 minutes in a constant temperature water bath at 37°C. 8fl
(1mg/mff) was added at 0.1 mR, stirred well, and kept at 37°C for 10 minutes.
l). Measure the absorbance (D2) of a similar reaction using heat-inactivated tyrosinase and the absorbance (D3) of a control test product using only water instead of the sample, and calculate the tyrosinase activity inhibition rate from the following formula. do.
チロシナーゼ活性阻害率（％）
■ メラニン形成抑制試験
Ｆ１系黒色モルモット（雄、約８間合、平均体重３５０
ｇ）の背部皮膚を刺毛後、脱毛クリームにより完全除毛
し、翌日より各試料を除毛部皮膚に毎日−回、４ｃｍ”
当り０．２ ｇ ’！布し、閉塞貼布した。尚１試料
に対して動物は一群１０匹使用した。Tyrosinase activity inhibition rate (%) ■Melanin formation inhibition test F1 black guinea pig (male, about 8 years old, average weight 350
After pricking the dorsal skin of (g), completely remove the hair using hair removal cream, and from the next day, apply each sample to the skin of the hair-removed area once a day for a distance of 4 cm.
0.2 g' per hit! The area was covered with cloth and an occluded patch was applied. A group of 10 animals was used for each sample.
メラニン形成抑制効果の評価は、試験開始後１ケ月後に
実施し、高速分光色彩計を用いて塗布部の明度（Ｙア）
と非塗布部の明度（Ｙｏ＞との比の値■ 皮膚色明度回
復試験
被試験者２０名の背部皮膚に試料塗布部位と非塗布部位
とを設定し、両部位にｔＪＶ−Ｂ領域の紫外線を最小紅
斑量の２倍量照射し、１週間の後、各々の皮膚の基準明
度（Ｙｏ値、Ｖｏ’（＋りを測定した。引続いて塗布部
位には試料を１日１回ずつ３ケ月間連続塗布し、３，７
．１３週間後の塗布部位及び非塗布部位の皮膚の回復明
度（Ｖ、・・・値Ｖ、、′・・・（ｌｉ）を測定して、
第２表の判定基準により、皮膚色の回復評価を実施した
。The melanin formation inhibitory effect was evaluated one month after the start of the test, and the brightness (YA) of the applied area was evaluated using a high-speed spectrocolorimeter.
and the brightness of the non-applied area (Yo>) Skin color brightness recovery test A sample application area and a non-application area were set on the back skin of 20 test subjects, and both areas were exposed to ultraviolet rays in the tJV-B range. After one week, the standard brightness (Yo value, Vo' (+)) of each skin was measured. Apply continuously for 3 to 7 months.
．． After 13 weeks, the recovery brightness (V, ... value V,,'...(li) of the skin of the application site and non-application site was measured,
Skin color recovery evaluation was performed according to the criteria shown in Table 2.
尚、皮膚の明度（■値）は高速分光色彩計で測定して得
られたマンセル値より算出した。In addition, the brightness of the skin (■ value) was calculated from the Munsell value obtained by measuring with a high-speed spectrocolorimeter.
被試験者２０名の評価点の平均値を求め、皮膚第
表
■ 美白実用試験
ソミ、ソバカス、日焼は等を訴える被試験者各２０名の
顔面に試料を朝夕１回ずつ３ケ月間連続塗布した後の改
善効果を調査した。評価はシミソバカス、日焼けが各々
改善されたと回答した被試験者の数で示した。The average value of the evaluation scores of 20 test subjects was calculated, and the sample was applied to the faces of 20 test subjects who complained of sun spots, freckles, sunburn, etc., once in the morning and once in the evening for 3 consecutive months. The improvement effect after application was investigated. The evaluation was expressed by the number of test subjects who answered that their freckles and sunburn were improved.
実施例１〜８．比較例１〜４
（二層型ローション）
下記の組成に於いて第３表に示す通りにＬ−アスコルビ
ン酸誘導体の種類及び含有量を変えて、実施例、比較例
である二層型ローションを調製して詩誌験を実施した。Examples 1-8. Comparative Examples 1 to 4 (Two-layer lotion) Two-layer lotions as Examples and Comparative Examples were prepared by changing the type and content of the L-ascorbic acid derivative as shown in Table 3 in the composition below. I prepared it and conducted a poetry review.
その結果を第３表に示した。The results are shown in Table 3.
（１） 組成
（２） 調製方法
（Ａ）成分の内、油溶性のものは（Ｂ）成分（ン由相）
中に、また水溶性のものは（Ｃ）成分（水キロ）中に、
必要に応じて加熱して均一に溶解する。(1) Composition (2) Preparation method Among the (A) components, the oil-soluble one is the (B) component (Nymph phase)
In addition, water-soluble ones are in component (C) (kg of water),
Heat as necessary to uniformly dissolve.
次いで、（Ｂ）成分子＠ＷＬ、 （Ｃ）成分溶液を均一
に混合攪拌分散した後、容器に充填する。Next, the (B) component @WL and the (C) component solution are uniformly mixed, stirred and dispersed, and then filled into a container.
使用時には内容物を均一に振盪分散して使用す（３）
特性
第３表に示す如く、アスコルビン酸誘導体を含有しない
比較例１は、チロシナーゼの活性を阻害しない為、メラ
ニン形成を抑制せず（Ｙ ｖ ／ Ｙ ｏ ＜１）皮膚
色の明度回復効果もほとんどなく、実用試験の結果も悪
かった。 アスコルビン酸誘導体として、Ｌ−アスコル
ビン酸リン酸マグネシウムを含有する比較例２は、保存
安定性は良好であるが、メラニン形成抑制効果、皮膚色
明度回復効果に乏しく、実用試験の結果も良くなかった
。When using, shake and disperse the contents evenly (3)
As shown in Table 3, Comparative Example 1, which does not contain ascorbic acid derivatives, does not inhibit tyrosinase activity, does not inhibit melanin formation (Y v / Y o <1), and has almost no effect on restoring skin color brightness. The results of practical tests were also poor. Comparative Example 2 containing L-ascorbic acid magnesium phosphate as an ascorbic acid derivative had good storage stability, but had poor melanin formation inhibiting effect and skin color brightness recovery effect, and the results of practical tests were also poor. .
アスコルビン酸誘導体として、α−トコフェロルーし一
アスコルビン酸−６−コハク酸ジエステルを含有する比
較例３は、比較例１．２に比べてメラニン形成抑制効果
、皮膚色明度回復効果は多少ア・ノブしているものの、
保存安定性が悪く、実用試験の結果も良くなかった。Comparative Example 3, which contains α-tocopherol monoascorbic acid-6-succinic acid diester as an ascorbic acid derivative, had a slightly lower melanin formation inhibiting effect and skin color brightness recovery effect than Comparative Example 1.2. Although
The storage stability was poor, and the results of practical tests were also poor.
アスコルビン酸誘導体としてα−トコフェロール−し−
アスコルビン酸−２−リン酸エステルを含有する比較例
４も、メラニン形成抑制効果２皮膚色明度回復効果は不
十分であり、実用試験の結果も良くなかった。α-tocopherol as an ascorbic acid derivative
In Comparative Example 4 containing ascorbic acid-2-phosphate ester, the melanin formation inhibiting effect 2 skin color brightness restoring effect was also insufficient, and the results of the practical test were also poor.
それに比べてアスコルビン酸誘導体として、般弐（１）
〜（ＩＶ）で表される化合物を含有する実施例１〜８は
、高いチロシナーゼ活性阻害率を有し、しかも保存安定
性が良好で、メラニン形成抑制効果及び皮膚色明度回復
効果に優れており、しかも実用試験の結果も良かった。In comparison, as an ascorbic acid derivative, Huni (1)
Examples 1 to 8 containing the compounds represented by (IV) have a high tyrosinase activity inhibition rate, good storage stability, and excellent melanin formation inhibiting effect and skin color brightness recovery effect. Moreover, the results of practical tests were also good.
実施例９〜１６．比較例５〜８
（スキンクリーム）
実施例１と同様に、下記の組成に於いて種々の実施例、
比較例のスキンクリームを調製して詩誌（］）
組成
（２） 調製方法
（Ａ）成分の内、油溶性のものは（Ｂ）成分中に、また
水溶性のものは（Ｃ）成分中に混合し、（Ｂ）成分と（
Ｃ）成分を各す均一に加熱熔解して温度を８０°Ｃにす
る。次いで、（Ｂ）成分中に（Ｃ）成分を注入攪拌混合
した後、
攪拌しながら温度を３
°Ｃ
（３）特性
第４表に示す如く、比較例５〜８に対して本発明の美白
化粧料である実施例９〜１６は諸試験に於いて全て良好
な結果を示し、美白効果も優れている。Examples 9-16. Comparative Examples 5 to 8 (Skin Cream) Similar to Example 1, various Examples with the following composition,
Comparative example skin cream was prepared and published as Shishi (]) Composition (2) Preparation method Of the (A) ingredients, oil-soluble ones are included in (B) ingredient, and water-soluble ones are included in (C) ingredient. Component (B) and (
C) Heat and melt each component uniformly to bring the temperature to 80°C. Next, the component (C) was injected into the component (B) and mixed with stirring, and the temperature was increased to 3 °C while stirring. Examples 9 to 16, which are cosmetics, all showed good results in various tests and had excellent whitening effects.
実施例１７〜２４．比較例９〜】２
（乳液）
下記の組成に於いて種々の実施例、比較例の乳液を＃Ｊ
８製して諸試験を実施した。その結果を第５紹成
（２） 調製方法
（Ａ）成分の内、油溶性のものは（Ｂ）成分中に、また
水溶性のものは（Ｃ）成分中に混合し、（Ｂ）成分と（
Ｃ）成分を各々均一に加熱熔解して温度を８０°Ｃにす
る。次いで、（Ｂ）成分中に（Ｃ）成分を注入攪拌混合
した後、
攪拌しながら温度を３
°Ｃ
（３） 特性
第５表に示す如く、比較例９〜１２に対して本発明の美
白化粧料である実施例１７〜２４は、詩誌験に於いて全
て良好な結果を示し、美白効果も優れている。Examples 17-24. Comparative Example 9 ~] 2 (Emulsion) The emulsion of various Examples and Comparative Examples with the following composition was #J
8 was manufactured and various tests were conducted. The results are summarized in Section 5 (2) Preparation method Among the components (A), oil-soluble ones are mixed in the (B) component, water-soluble ones are mixed in the (C) component, and the (B) component and(
C) Heat and melt each component uniformly to bring the temperature to 80°C. Next, the component (C) was injected into the component (B) and mixed with stirring, and then the temperature was raised to 3 °C while stirring. Examples 17 to 24, which are cosmetics, all showed good results in the poetry test and had excellent whitening effects.
以上記載の如く、本発明の美白化粧料は、従来のし一ア
スコルビン酸誘導体を含有する美白化粧料と比較して、
美白効果および保存安定性において顕著に優れているこ
とは明らかである。As described above, the whitening cosmetic of the present invention has the following characteristics compared to the conventional whitening cosmetic containing an ascorbic acid derivative:
It is clear that it is significantly superior in whitening effect and storage stability.
Claims (2)
ルビン酸誘導体を含有することを特徴とする美白化粧料
。 ▲数式、化学式、表等があります▼・・・（ I ） ▲数式、化学式、表等があります▼・・・（II） （式（ I ）、（II）中Ｒ＿１、Ｒ＿２は、 ▲数式、化学式、表等があります▼ を表し、Ｒ＿３、Ｒ＿４は、Ｈ又はＣＨ＿３を表す。 Ｒ＿５は、炭素数１〜２０の直鎖又は分岐鎖の、飽和又
は不飽和の炭化水素基、又は −Ｒ＿６−Ａ−Ｒ＿７−基を表す。 Ｒ＿６、Ｒ＿７は、炭素数１〜１０の直鎖又は分岐鎖の
、飽和又は不飽和の炭化水素基、Ａは、−Ｏ−、−ＣＯ
−、−ＯＣＯ−、 −ＣＨ（ＯＨ）−、−ＣＨ（ＮＲ＿８Ｒ＿９）−、−Ｎ
Ｒ＿１＿０−、−ＮＲ＿１＿１ＣＯ−、のいずれかを表
し、Ｒ＿８〜Ｒ＿１＿１は、水素もしくは炭素数１〜４
の飽和炭化水素基を表す。）(1) A whitening cosmetic characterized by containing an ascorbic acid derivative represented by the following general formula (I) or (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (R_1 and R_2 in formulas (I) and (II) are ▲Mathematical formulas, There are chemical formulas, tables, etc. Represents A-R_7- group. R_6 and R_7 are linear or branched saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, A is -O-, -CO
-, -OCO-, -CH(OH)-, -CH(NR_8R_9)-, -N
R_1_0-, -NR_1_1CO-, R_8 to R_1_1 are hydrogen or carbon atoms 1 to 4
represents a saturated hydrocarbon group. )
ルビン酸誘導体を含有することを特徴とする美白化粧料
。 ▲数式、化学式、表等があります▼・・・（III） ▲数式、化学式、表等があります▼・・・（IV） （但し、Ｒ＿１、Ｒ＿２は、（ I ）、（II）の場合と
同じである。）(2) A whitening cosmetic containing an ascorbic acid derivative represented by the following general formula (III) or (IV). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) (However, R_1 and R_2 are the same as in the case of (I) and (II). are the same)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2274819A JPH04149117A (en) | 1990-10-12 | 1990-10-12 | Skin-beautifying cosmetic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2274819A JPH04149117A (en) | 1990-10-12 | 1990-10-12 | Skin-beautifying cosmetic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04149117A true JPH04149117A (en) | 1992-05-22 |
Family
ID=17547010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2274819A Pending JPH04149117A (en) | 1990-10-12 | 1990-10-12 | Skin-beautifying cosmetic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04149117A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999050258A1 (en) * | 1998-03-27 | 1999-10-07 | Lg Chemical Ltd. | Polyethoxylated ascorbic acid derivatives as a novel antioxidant and process for preparing thereof |
| WO2009025328A1 (en) * | 2007-08-22 | 2009-02-26 | Seiwa Kasei Company, Limited | Ascorbic acid derivative or salt thereof, method for producing the same, and cosmetic preparation |
| US8865228B2 (en) | 2006-02-21 | 2014-10-21 | Mary Kay Inc. | Stable vitamin C compositions |
| EP3092220A4 (en) * | 2013-09-25 | 2017-08-30 | University of Florida Research Foundation, Inc. | Vitamin c prodrugs and uses thereof |
-
1990
- 1990-10-12 JP JP2274819A patent/JPH04149117A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999050258A1 (en) * | 1998-03-27 | 1999-10-07 | Lg Chemical Ltd. | Polyethoxylated ascorbic acid derivatives as a novel antioxidant and process for preparing thereof |
| US6444144B1 (en) * | 1998-03-27 | 2002-09-03 | Lg Chemical Ltd. | Polyethoxylated ascorbic acid derivatives as a novel antioxidant and process for preparing thereof |
| US8865228B2 (en) | 2006-02-21 | 2014-10-21 | Mary Kay Inc. | Stable vitamin C compositions |
| US9968539B2 (en) | 2006-02-21 | 2018-05-15 | Mary Kay Inc. | Stable vitamin C compositions |
| US10912729B2 (en) | 2006-02-21 | 2021-02-09 | Mary Kay Inc. | Stable vitamin c compositions |
| US11771638B2 (en) | 2006-02-21 | 2023-10-03 | Mary Kay Inc. | Stable vitamin C compositions |
| WO2009025328A1 (en) * | 2007-08-22 | 2009-02-26 | Seiwa Kasei Company, Limited | Ascorbic acid derivative or salt thereof, method for producing the same, and cosmetic preparation |
| JPWO2009025328A1 (en) * | 2007-08-22 | 2010-11-25 | 株式会社成和化成 | Ascorbic acid derivative or salt thereof, production method thereof, and cosmetics |
| JP4681670B2 (en) * | 2007-08-22 | 2011-05-11 | 株式会社成和化成 | Ascorbic acid derivative or salt thereof, production method thereof, and cosmetics |
| US8163939B2 (en) | 2007-08-22 | 2012-04-24 | Seikwa Kasei Company, Limited | Ascorbic acid derivative or salt thereof, production method thereof, and cosmetic |
| EP3092220A4 (en) * | 2013-09-25 | 2017-08-30 | University of Florida Research Foundation, Inc. | Vitamin c prodrugs and uses thereof |
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