JPH01308476A - Ultraviolet ray absorber - Google Patents
Ultraviolet ray absorberInfo
- Publication number
- JPH01308476A JPH01308476A JP13913688A JP13913688A JPH01308476A JP H01308476 A JPH01308476 A JP H01308476A JP 13913688 A JP13913688 A JP 13913688A JP 13913688 A JP13913688 A JP 13913688A JP H01308476 A JPH01308476 A JP H01308476A
- Authority
- JP
- Japan
- Prior art keywords
- quercetin
- rutin
- water
- groups
- formulas
- 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
- 239000006096 absorbing agent Substances 0.000 title abstract description 8
- 150000003244 quercetin derivatives Chemical class 0.000 claims abstract description 5
- 150000003306 rutin derivatives Chemical class 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract 4
- 239000002184 metal Substances 0.000 claims abstract 4
- 150000002892 organic cations Chemical class 0.000 claims abstract 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 5
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 abstract description 12
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 abstract description 12
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 abstract description 12
- 229960001285 quercetin Drugs 0.000 abstract description 12
- 235000005875 quercetin Nutrition 0.000 abstract description 12
- IKGXIBQEEMLURG-NVPNHPEKSA-N rutin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-NVPNHPEKSA-N 0.000 abstract description 12
- JMGZEFIQIZZSBH-UHFFFAOYSA-N Bioquercetin Natural products CC1OC(OCC(O)C2OC(OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5)C(O)C2O)C(O)C(O)C1O JMGZEFIQIZZSBH-UHFFFAOYSA-N 0.000 abstract description 11
- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 abstract description 11
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 abstract description 11
- 235000005493 rutin Nutrition 0.000 abstract description 11
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 abstract description 11
- 229960004555 rutoside Drugs 0.000 abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 235000013824 polyphenols Nutrition 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 16
- 239000002537 cosmetic Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 210000003491 skin Anatomy 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 4
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 4
- -1 2,3-dihydroxypropyl Chemical group 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 2
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 2
- 229960002216 methylparaben Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940032094 squalane Drugs 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- 201000006082 Chickenpox Diseases 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 206010014970 Ephelides Diseases 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000003351 Melanosis Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000012641 Pigmentation disease Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 206010046980 Varicella Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 230000003412 degenerative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 230000001744 histochemical effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960003232 troxerutin Drugs 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
- A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
Abstract
Description
【発明の詳細な説明】
（Ｉ）産業上の利用分野
この発明は、紫外線吸収剤、とくに長波長域の紫外線（
約３２０〜４００ｎｍ）を吸収し化粧料に有効な紫外線
吸収剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION (I) Industrial Application Field This invention relates to ultraviolet absorbers, especially ultraviolet rays in the long wavelength range (
The present invention relates to an ultraviolet absorber that absorbs wavelengths of about 320 to 400 nm) and is effective in cosmetics.
（２）従来の技術
紫外線は皮膚科学的な作用波長に基いて区分され、一般
に、長波長紫外線（約３２０〜４００ｎｍ）をＵＶ−Ａ
、中波長紫外線（約２８０〜３２０ｎＩ１１）をＵＶ−
Ｂ、短波長紫外線（２８０ｎＩ１１以下）をＵＶ−Ｃと
呼んでいる。このうち、ＵＶ−Ｃはそのほとんどがオゾ
ン層において吸収されてしまい、地上に到達する量は少
ない。地上に到達する紫外線のうち、ＵＶ−Ｂは紅斑や
水痘を形成し、またメラニンの形成を冗進し、色素沈着
を起こさせる等、皮膚に対して悪影響を及ぼすことが明
らかであったため、ＵＶ−Ｂ吸収剤の開発はかなり進ん
でいる。これに対し、従来、ＵＶ−Ａは皮膚にあまり大
きな変化を生じさせないと考えられていた。しかしなが
ら、電子顕微鏡や組織化学的な手法によりＵＶ−Ａ照射
によっても皮膚は変化を受けることが近年明らかにされ
てきた。特にＵＶ−ＡはＵＶ−Ｂと異なり、そのエネル
ギーは真皮にまでも到達し、血管壁や結合組織中の弾性
繊維に悪影響を及ぼし、これらの変化が皮膚の老化促進
につながると考えられている。また、ＵＶ−Ａは照射直
後に皮膚・を黒化させる作用（即時黒化）を有すること
やＵＶ−Ｂの皮膚に対する変性作用を増強することが知
られており、シミ、ソバカスの発生や悪化の一因子にな
っていると考えられる。(2) Conventional technology Ultraviolet rays are classified based on their dermatological action wavelengths, and generally long-wavelength ultraviolet rays (approximately 320 to 400 nm) are classified into UV-A
, UV-
B. Short wavelength ultraviolet light (280 nI11 or less) is called UV-C. Of these, most of the UV-C is absorbed by the ozone layer, and only a small amount reaches the ground. Among the ultraviolet rays that reach the ground, UV-B forms erythema and chickenpox, and it is clear that UV-B has an adverse effect on the skin, such as accelerating the formation of melanin and causing pigmentation. -The development of B absorbers has progressed considerably. On the other hand, it was conventionally believed that UV-A does not cause much change in the skin. However, in recent years, it has been revealed through electron microscopy and histochemical techniques that UV-A irradiation also causes changes in the skin. In particular, unlike UV-B, UV-A energy reaches the dermis and has a negative effect on the elastic fibers in blood vessel walls and connective tissue, and these changes are thought to lead to accelerated skin aging. . In addition, it is known that UV-A has the effect of blackening the skin immediately after irradiation (immediate blackening) and that it enhances the degenerative effect of UV-B on the skin, causing the appearance and worsening of age spots and freckles. This is thought to be one of the factors.
したがってＵＶ−Ｂだけではなく、ＵＶ−Ａからも皮膚
を保護することが重要となる。Therefore, it is important to protect the skin not only from UV-B but also from UV-A.
植物界に広く存在するフラボノイドであるケルセチンお
よびルチンは、ＵＶ−Ａ領域に大きな吸収をもつことが
知られており、これらの化合物をＵＶ−Ａ吸収剤として
化粧料に配合する試みは従来から行なわれている（特開
昭６０−２０８９０８）。Quercetin and rutin, which are flavonoids widely present in the plant kingdom, are known to have large absorption in the UV-A region, and there have been no attempts to incorporate these compounds into cosmetics as UV-A absorbers. (Japanese Patent Application Laid-Open No. 60-208908).
ところが、ケルセチンおよびルチンは、いずれも水にほ
とんど溶けないので、化粧水や乳液等のように処方中に
水を含む化粧料に配合することが極めて困難である。こ
うした事情から、ＵＶ−Ａ吸収剤として、有効濃度のケ
ルセチンあるいはルチンを化粧料に配合する場合は、粉
体のまま添加する方法あるいは無機顔料の粒子表面に析
出保持させる方法等に限定されるので、ファンデーショ
ンやパウダーのような固形の化粧料にしか配合できない
のが現状である。However, since both quercetin and rutin are almost insoluble in water, it is extremely difficult to incorporate them into cosmetics that contain water in their formulations, such as lotions and emulsions. For these reasons, when incorporating quercetin or rutin at an effective concentration into cosmetics as a UV-A absorber, it is limited to methods such as adding it as a powder or depositing and retaining it on the surface of inorganic pigment particles. Currently, it can only be incorporated into solid cosmetics such as foundations and powders.
（３）発明が解決しようとする問題点
上記の事情にかんがみ、本発明者らは、ケルセチンおよ
びルチンがすぐれたＵＶ−Ａ吸収特性をもちながら化粧
料への配合が困難で応用範囲が狭いのは、水に対する溶
解度が極めて低いという重要な問題点をもっためである
と考えた。(3) Problems to be Solved by the Invention In view of the above circumstances, the present inventors have discovered that although quercetin and rutin have excellent UV-A absorption properties, they are difficult to incorporate into cosmetics and have a narrow range of application. This was thought to be due to the important problem of extremely low solubility in water.
したがって、ケルセチンおよびルチンのすぐれたＵＶ−
Ａ吸収特性をそこなうことなく、水に対する溶解度を改
善するのが、本発明の目的である。Therefore, the excellent UV-
It is an object of the present invention to improve the water solubility without compromising the A absorption properties.
（４） 問題点を解決するための手段本発明者らは、
上記目的を達成するために、ケルセチンおよびルチンの
フェノール性水酸基に、水溶性基を導入することを考え
、種々検討を行なった。(4) Means for solving the problem The inventors
In order to achieve the above object, various studies were conducted with the idea of introducing water-soluble groups into the phenolic hydroxyl groups of quercetin and rutin.
しかし、一般に水溶性を向上させるために使用される官
能基がいずれも有効であるとは限らず、予期に反して、
全く水溶性が発現しない場合もあることが、検討を重ね
るうちに明らかとなった。However, not all functional groups commonly used to improve water solubility are effective, and contrary to expectations,
Through repeated studies, it became clear that there are cases where water solubility is not expressed at all.
たとえば、トロキセルチン（弐■）が水溶性であること
は公知であるが、ケルセチンに２−ヒドロキシエチル基
を導入した化合物は、４官能基導入したもの（式■）で
も水溶性が発現しなかった。For example, it is known that troxerutin (2■) is water-soluble, but a compound in which a 2-hydroxyethyl group was introduced into quercetin did not exhibit water solubility even when a tetrafunctional group was introduced (formula ■). .
０ＨＯＨＨＯＨ
本発明者らは、種々の水溶性官能基について、ケルセチ
ンおよびルチンへの導入を試み、水溶性が発現するかど
うかを鋭意検討した。その結果、一般式（Ｉ）および（
ｎ）
Ｒ
Ｒ
ＯＨＯＨＨＯＨ
で示される化合物が、水に極めて溶けやすく、しかもケ
ルセチンおよびルチンのすぐれたＵＶ−Ａ吸収特性を保
持していることを見出し、本発明を完成するに到った。0HOHHOH The present inventors attempted to introduce various water-soluble functional groups into quercetin and rutin, and intensively investigated whether water-solubility would be exhibited. As a result, the general formula (I) and (
The present inventors have discovered that the compound represented by R R OHOHHOH is extremely soluble in water and retains the excellent UV-A absorption properties of quercetin and rutin, and has completed the present invention.
本発明は一般式（Ｉ）および（ＩＩ）で示されるケルセ
チン誘導体あるいはルチン誘導体を有効成分として含有
する紫外線吸収剤を提供するものである。The present invention provides ultraviolet absorbers containing quercetin derivatives or rutin derivatives represented by formulas (I) and (II) as active ingredients.
本発明に用いられるケルセチン誘導体あるいはルチン誘
導体は、一般式（Ｉ）あるいは（ＩＩ）に含まれる化合
物ならば、単一化合物でもよいし、それらの混合物であ
ってもよい。The quercetin derivative or rutin derivative used in the present invention may be a single compound or a mixture thereof as long as it is a compound included in general formula (I) or (II).
本発明にかかる紫外線吸収剤中のケルセチン誘導体ある
いはルチン誘導体の配合量は、その使用形態により変動
させることができるので特に限定されないが、−船釣に
は組成物中０．０１〜２０重−％、好ましくは０．１〜
１０重量％配合するのがよい。The amount of the quercetin derivative or rutin derivative in the ultraviolet absorber according to the present invention is not particularly limited, as it can be varied depending on the form of use; , preferably 0.1~
It is preferable to mix 10% by weight.
（５）作 用
ケルセチンおよびルチンのフェノール性水酸基に水溶性
基を導入した化合物のうち、一般式（Ｉ）および（ＩＩ
）で示されるような、２，３−ジヒドロキシプロピルま
たはホスフェート（またはその塩）を導入したものは、
特に水溶性が高い。この理由は定かではないが、これら
の官能基の極性が、たとえば、２−ヒドロキシエチル等
よりも高いことなどが考えられる。(5) Action Among compounds with water-soluble groups introduced into the phenolic hydroxyl groups of quercetin and rutin, general formulas (I) and (II
) into which 2,3-dihydroxypropyl or phosphate (or its salt) is introduced,
Especially highly water soluble. Although the reason for this is not clear, it is thought that the polarity of these functional groups is higher than that of, for example, 2-hydroxyethyl.
また、フェノール性水酸基に導入された２、３−ジヒド
ロキシプロピルまたはホスフェート（またはその塩）は
、ケルセチンおよびルチンの共役系に電子的な影響をほ
とんど及ぼさないので、母体化合物であるケルセチンお
よびルチンのすぐれたＵＶ−Ａ吸収特性が、そのまま保
持されてい、るものと推定する。In addition, 2,3-dihydroxypropyl or phosphate (or its salt) introduced into the phenolic hydroxyl group has almost no electronic influence on the conjugated system of quercetin and rutin, so it is an excellent It is presumed that the UV-A absorption characteristics that were obtained are maintained as they are.
（６）実施例
本発明化合物の代表例および比較化合物を以下にあげる
が、これによって官能基の数および置換位置は何ら制約
されるものではない。(6) Examples Representative examples of the compounds of the present invention and comparative compounds are listed below, but the number of functional groups and the substitution positions are not restricted thereby.
（以下余白） 本発明化合物 ＯＨＯＨ 本発明化合物 ＯＨ０ 本発明化合物 ＯＨＯＨＨＯＨ 比較化合物 ＊１１ 実施例（Ｉ）化粧水 下記組成を常法に従って配合し、化粧水を調製した。(Margin below) Compound of the present invention OHOH Compound of the present invention OH0 Compound of the present invention OHOHOHOH comparative compound *11 Example (I) Lotion A lotion was prepared by blending the following composition according to a conventional method.
本発明化合物＊ １ ２．０ （重量％）エ
タノール １０．０
プロピレングリコール ５．０グリセリン
２．０
ポリオキシエチレン（２０）
セチルエーテル １．０
メチルパラベン ０．１香 料
適量
色素 微量
精製水 残量
実施例（２）乳 液
下記組成を常法に従って配合し、乳液を調製した。Compound of the present invention* 1 2.0 (wt%) Ethanol 10.0 Propylene glycol 5.0 Glycerin
2.0 Polyoxyethylene (20) Cetyl ether 1.0 Methylparaben 0.1 Fragrance
Appropriate amount of pigment, trace amount of purified water, remaining amount Example (2) Emulsion The following composition was blended according to a conventional method to prepare an emulsion.
本発明化合物＊４ ３．０（重量％）ステア
リン酸 １．５セタノール
１．０
オレイン酸モノグリセリド ０．５１量％）ワ セ
リ ン ２．０流
動パラフイン ６．０
スクワラン ６．０
トリエタノールアミン １．２
ジプロピレングリコール ５．０
グリセリン ２．０
カルボキシビニルポリマー ０．２
メチルパラベン ０．１
香料 適量
精製水 残量
実施例（３） クリーム
下記組成を常法に従って配合し、クリームを調製した。Compound of the present invention *4 3.0 (wt%) stearic acid 1.5 cetanol
1.0 Oleic acid monoglyceride 0.51% by weight) Wase
Phosphorus 2.0 Liquid paraffin 6.0 Squalane 6.0 Triethanolamine 1.2 Dipropylene glycol 5.0 Glycerin 2.0 Carboxyvinyl polymer 0.2 Methylparaben 0.1 Fragrance Appropriate amount of purified water Remaining amount example (3 ) Cream A cream was prepared by blending the following composition according to a conventional method.
本発明化合物＊４ ２．０（ｆｆｌ量％）セ
スキオレイン酸ソルビタン ４．０
ステアリン酸アルミニウム ０．５
セチルアルコール ４，０
流動パラフイン １６．０
スクワラン １０．０ （重量％）ミ
リスチン酸イソプロピル ５．０
安臭香酸ナトリウム ０．３グリセリン
ｌ０１０
香料 適量
精製水 残量
なお、本発明にかかる化粧料には、皮膚刺激性、アレル
ギー性は認められず、皮膚に対する安全性は極めて高い
ものであった。Compound of the present invention *4 2.0 (ffl%) Sorbitan sesquioleate 4.0 Aluminum stearate 0.5 Cetyl alcohol 4.0 Liquid paraffin 16.0 Squalane 10.0 (% by weight) Isopropyl myristate 5.0 Sodium benbrozoate 0.3 glycerin
1010 Perfume Appropriate amount Purified water Remaining amount The cosmetics according to the present invention were not found to have any skin irritation or allergy, and were extremely safe for the skin.
（７）効 果
本発明化合物は試験例に示したように、すぐれたＵＶ−
Ａ吸収特性をもち、かつ、水溶性（Ｉ％以上、可溶）で
ある。この特徴により、実施例＜１） 、 （２） 、
（３）のような、処方中に水を含む化粧料に、容品に
配合することができるので、すぐれたＵＶ−Ａ吸収効果
をもつ安定な化粧水、乳液、クリーム等を生産すること
ができる。(7) Effects As shown in the test examples, the compound of the present invention has excellent UV-
It has A absorption characteristics and is water soluble (I% or more, soluble). Due to this feature, Examples <1), (2),
Since it can be incorporated into cosmetics and containers that contain water in the formulation, such as (3), it is possible to produce stable lotions, milky lotions, creams, etc. with excellent UV-A absorption effects. can.
Claims (1)
体あるいはルチン誘導体を有効成分として含有する紫外
線吸収剤。 ▲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） 〔式中、ＲはＨ、▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼からなる群から選ばれる。 Ｘ＿１は、Ｈ、１価金属カチオンまたは１価有機カチオ
ンであり、Ｘ＿２は２価金属カチオンまたは２価有機カ
チオンである。 ただし、ＲがすべてＨである場合を除く。〕[Claims] An ultraviolet absorber containing a quercetin derivative or a rutin derivative represented by formula (I) or (II) as an active ingredient. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, R is H, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲mathematical formulas, chemical formulas,
Selected from the group consisting of ▼. X_1 is H, a monovalent metal cation or a monovalent organic cation, and X_2 is a divalent metal cation or a divalent organic cation. However, this does not apply when all R's are H. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13913688A JPH01308476A (en) | 1988-06-06 | 1988-06-06 | Ultraviolet ray absorber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13913688A JPH01308476A (en) | 1988-06-06 | 1988-06-06 | Ultraviolet ray absorber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01308476A true JPH01308476A (en) | 1989-12-13 |
Family
ID=15238378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13913688A Pending JPH01308476A (en) | 1988-06-06 | 1988-06-06 | Ultraviolet ray absorber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01308476A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000026399A3 (en) * | 1998-10-30 | 2000-08-10 | Merck Patent Gmbh | Method for the production of quercetin and isoquercetin derivatives |
| JP2004507505A (en) * | 2000-08-29 | 2004-03-11 | コグニス・フランス・ソシエテ・アノニム | Use of an extract of the plant Cassiaalata |
| JP2008532951A (en) * | 2005-03-11 | 2008-08-21 | ハワード フローリー インスティチュート オブ エクスパーリメンタル フィジオロジー アンド メディシン | Flavonoid compounds and uses thereof |
| JP2009046486A (en) * | 1996-06-27 | 2009-03-05 | Celleron Therapeutics Ltd | Analogue or derivative of quercetin (prodrug) |
| JP2009533361A (en) * | 2006-04-13 | 2009-09-17 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Use of flavonoids |
| US7947733B2 (en) | 2007-07-31 | 2011-05-24 | Limerick Biopharma | Phosphorylated pyrone analogs and methods |
-
1988
- 1988-06-06 JP JP13913688A patent/JPH01308476A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009046486A (en) * | 1996-06-27 | 2009-03-05 | Celleron Therapeutics Ltd | Analogue or derivative of quercetin (prodrug) |
| WO2000026399A3 (en) * | 1998-10-30 | 2000-08-10 | Merck Patent Gmbh | Method for the production of quercetin and isoquercetin derivatives |
| JP2004507505A (en) * | 2000-08-29 | 2004-03-11 | コグニス・フランス・ソシエテ・アノニム | Use of an extract of the plant Cassiaalata |
| JP2013121968A (en) * | 2000-08-29 | 2013-06-20 | Basf Beauty Care Solutions France Sas | Use of extract of cassia alata plant |
| JP2008532951A (en) * | 2005-03-11 | 2008-08-21 | ハワード フローリー インスティチュート オブ エクスパーリメンタル フィジオロジー アンド メディシン | Flavonoid compounds and uses thereof |
| JP2009533361A (en) * | 2006-04-13 | 2009-09-17 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Use of flavonoids |
| US7947733B2 (en) | 2007-07-31 | 2011-05-24 | Limerick Biopharma | Phosphorylated pyrone analogs and methods |
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