JP3133506B2 - UV absorber - Google Patents
UV absorberInfo
- Publication number
- JP3133506B2 JP3133506B2 JP04241185A JP24118592A JP3133506B2 JP 3133506 B2 JP3133506 B2 JP 3133506B2 JP 04241185 A JP04241185 A JP 04241185A JP 24118592 A JP24118592 A JP 24118592A JP 3133506 B2 JP3133506 B2 JP 3133506B2
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet
- biphenyl
- measurement
- present
- ketone
- 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.)
- Expired - Fee Related
Links
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- Cosmetics (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、塗料、プラスチック、
合成繊維等に配合され紫外線吸収能を付与する化合物と
して、また皮膚外用剤において日焼け止め剤として極め
て有用な紫外線吸収剤に関するものである。The present invention relates to paints, plastics,
The present invention relates to an ultraviolet absorbent which is extremely useful as a compound imparted to a synthetic fiber or the like to impart ultraviolet absorbing ability and as a sunscreen in an external preparation for skin.
【0002】[0002]
【従来の技術及び発明が解決しようとする課題】紫外線
吸収剤は、塗料、プラスチック、合成繊維等に添加さ
れ、太陽光に含まれる紫外線による劣化及び変色を防止
し、その被添加材料自体を保護している。また、化粧料
などの皮膚外用剤においても、皮膚に対して種々の影響
を与える紫外線から皮膚を防御する目的で紫外線吸収剤
が使用されている。紫外線は、その波長の大きさにより
280nm未満の短波長紫外線領域(UV−C)、28
0nm以上320nm未満の中波長紫外線領域(UV−
B)、320nm以上400nm未満の長波長紫外線領
域(UV−A)に分類される。2. Description of the Related Art Ultraviolet absorbers are added to paints, plastics, synthetic fibers and the like to prevent deterioration and discoloration due to ultraviolet rays contained in sunlight and protect the added material itself. are doing. Also, in external preparations for skin such as cosmetics, ultraviolet absorbers are used for the purpose of protecting the skin from ultraviolet rays which have various effects on the skin. The ultraviolet light has a short wavelength ultraviolet region (UV-C) of less than 280 nm depending on the size of the wavelength,
Medium wavelength ultraviolet region (UV-
B), a long wavelength ultraviolet region (UV-A) of 320 nm or more and less than 400 nm.
【0003】従来の紫外線吸収剤は、紅斑や水泡の形成
を引き起こすUV−Bを主として吸収するものとしてベ
ンゾフェノン系、パラアミノ安息香酸系、ケイ皮酸系、
サリチル酸系等、また皮膚の黒化を促すことや、シミ、
ソバカスの発生や皮膚の老化の一因とされているUV−
Aを吸収するものとしてジベンゾイルメタン系、ケイ皮
酸系、カルコン系及びヒダントイン系の化合物が知られ
ている。(コスメチックス アンド トイレタリーズ
21頁,102巻,1987年、色材協会誌298頁,
65巻,1992年、西独特許公開第2728241号
公報、同2728243号公報、特開昭51−6164
1号公報、同52−46056号公報、同57−598
40号公報、同57−197209号公報、同60−1
09544号公報、同63−101371号公報、同6
3−101372号公報)しかしながら、これらの紫外
線吸収剤は、その紫外線吸収能、安全性、安定性や溶剤
などへの溶解性の全てにおいて十分な物はなかった。Conventional UV absorbers mainly absorb UV-B, which causes erythema and blister formation, as benzophenones, paraaminobenzoic acids, cinnamic acids, and the like.
Salicylic acid, etc.
UV- which is considered to be a cause of buckwheat and skin aging
Dibenzoylmethane, cinnamic acid, chalcone and hydantoin compounds are known to absorb A. (Cosmetics and toiletries
21, page 102, 1987, Journal of the Society of Color Materials, 298 pages,
65, 1992, West German Patent Publication Nos. 2728241 and 2728243, JP-A-51-6164.
No. 1, No. 52-46056, No. 57-598
Nos. 40, 57-197209 and 60-1
JP-A-09544, JP-A-63-101371, and JP-A-6-101371
However, none of these ultraviolet absorbers has sufficient ultraviolet absorbing ability, safety, stability, and solubility in solvents and the like.
【0004】一方、ビフェニル構造を有する化合物とし
てデヒドロジオイゲノール、デヒドロジグアイアコー
ル、デヒドロジジヒドロオイゲノール等が高い安全性
(感作性を有しない)であることが知られている。(特
願平3−38089号) また、そのUV吸収能に関す
る報告もあるが、その吸収波長領域は280nmから2
90nmであり紫外線吸収剤としての用途に用いるには
十分ではない。更にビフェニルケトン誘導体として、デ
ヒドロジバニリン、デヒドロジアセトバニロンやデヒド
ロ−ジグアイアシルエチルケトン(4,4’−ジプロピ
オニル−6,6’−ビガアイアコール)が報告されてい
るが、これらの紫外線吸収能に関する報告はない。(ジ
ャーナル オブ オーガニック ケミストリィ 第28
巻 1048頁、1963年、同 第34巻 585
頁、1969年)On the other hand, as compounds having a biphenyl structure, dehydrodieugenol, dehydrodiguaiacol, dehydrodidihydroeugenol and the like are known to be highly safe (have no sensitization). (Japanese Patent Application No. 3-38089) There is also a report on its UV absorbing ability, but its absorption wavelength range is from 280 nm to 2 nm.
It is 90 nm, which is not enough for use as an ultraviolet absorber. Further, as biphenyl ketone derivatives, dehydrodivanillin, dehydrodiacetvanilone, and dehydro-diaguayl ethyl ketone (4,4'-dipropionyl-6,6'-bigiacol) have been reported. There is no report on ultraviolet absorbing ability. (Journal of Organic Chemistry 28
Volume 1048, 1963, Vol. 34, 585
P. 1969)
【0005】即ち、本発明の目的は、UV−B及びUV
−A領域の紫外線を効果的に吸収しうる紫外線吸収剤を
提供することにある。[0005] An object of the present invention, UV-B及beauty U V
An object of the present invention is to provide an ultraviolet absorber capable of effectively absorbing ultraviolet light in the A region.
【0006】[0006]
【課題を解決するための手段】本発明者等は、ビフェニ
ル化合物について鋭意検討を行った結果、後記特定のビ
フェニルケトン誘導体が、UV−B及び/またはUV−
B領域の紫外線を効果的に吸収することを見いだし本発
明を完成した。The present inventors have conducted intensive studies on biphenyl compounds, and as a result, a specific biphenyl ketone derivative described below was converted to UV-B and / or UV-B.
The present inventors have found that the ultraviolet light in the region B is effectively absorbed, and completed the present invention.
【0007】即ち、本発明はUV−B及びUV−A領域
の紫外線を効果的に吸収しうる下記一般式で表されるビ
フェニルケトン誘導体を含有することを特徴とする紫外
線吸収剤に関する。Namely, the present invention relates to an ultraviolet absorber characterized by containing a biphenyl ketone derivative represented by the following general formula can effectively absorb UV rays in the UV-B及beauty U V-A region.
【化2】 (但しRは炭素数1から12の直鎖又は側鎖の炭化水素
基。)Embedded image (Although hydrocarbon straight or side chain of R is from carbon number 1 12
Base . )
【0008】本発明のビフェニルケトン誘導体であるデ
ヒドロジアセトバニリンはバニリンやアセトバニリンよ
りJ.C.Pewらの方法により二量体化することによ
り用意に入手することが可能である。(ジャーナル オ
ブ オーガニック ケミストリィ 第28巻 1048
頁、1963年)また、その他のビフェニルケトン誘導
体は、グアイアコールを出発原料として公知の方法によ
りアルキルエステル体を得た後、ニトロベンゼン中にお
いて塩化アルミニウムと反応させることにより単量体で
あるグアイアシルアルキルケトン体を得る。(オーガニ
ック リアクション 第1巻 342頁 1942年、
ジャーナル オブ オーガニック ケミストリィ 第5
巻 645頁、1940年) 得られたグアイアシルア
ルキルケトンを先の方法に従って容易に入手することが
可能である。[0008] biphenyl ketone derivative der Lud <br/> hydro diacetoxy vanillin of the invention J. than vanillin and acetoacetic vanillin C. It can be easily obtained by dimerization according to the method of Pew et al. (Journal of Organic Chemistry Vol. 28 1048
P. 1963) Further, other biphenyl ketone derivatives are obtained by using guaiacol as a starting material to obtain an alkyl ester compound by a known method, and then reacting it with aluminum chloride in nitrobenzene to obtain a guaiacyl alkyl ketone as a monomer. Get the body. (Organic Reaction Vol. 1, p. 342, 1942,
Journal of Organic Chemistry 5
Vol. 645, 1940) The obtained guaiacylalkyl ketone can be easily obtained according to the above method.
【0009】本発明で用いるビフェニルケトン誘導体は
高い紫外線吸収能を有するだけでなく、皮膚刺激や感作
性がなく安全であり、かつ通常の皮膚外用剤に用いられ
る基剤に易溶であることから、応用範囲が広く、その用
途に応じて適宜その配合量を選択することができる。The biphenyl ketone derivative used in the present invention not only has a high ultraviolet absorbing ability, is safe without skin irritation and sensitization, and is easily soluble in a base used in a usual external preparation for skin. Therefore, the range of application is wide, and the compounding amount can be appropriately selected according to the application.
【0010】[0010]
【実施例】以下、実施例について説明する。尚、実施例
に示す%は、重量%を意味する。実施例に示したビフェ
ニルケトン誘導体は、以下の通りである。フェニルケト
ン誘導体のRがC2 H5 の場合をBP−C2、C5 H11
の場合をBP−C5そしてC8 H17の場合をBP−C8
と以下略称した。また、紫外線防御能の試験方法は下記
の通りである。Embodiments will be described below. In addition,% shown in an Example means weight%. The biphenyl ketone derivatives shown in the examples are as follows. When R of the phenyl ketone derivative is C 2 H 5 , BP-C 2, C 5 H 11
In the case of BP-C5 and BP-C8 a case of C 8 H 17
Abbreviated below. The test method of the ultraviolet protection ability is as follows.
【0011】(1)紫外線防御能の試験方法 光源としてマルチポートソーラーUVシュミレーター6
00型(ソーラーライト社製)を用い、以下の方法に従
って最少紅斑量値(MED値)及び各試料の紫外線防御
指数値(SPF値)を得た。 (i)MED測定 体重450g〜500gのハートレー系モルモット
(雌)の背部を除毛クリームを用いて処理した。24時
間後にシェーバーにて軽く剃毛した後、上記紫外線照射
装置を用いて2.20,1.76,1.41,1.1
3,0.90,0.72MED/minの強度でUVA
及びUVBを照射した。24時間後、紅斑の現れた最小
照射量を1MEDとした。(1) Test method of ultraviolet protection ability Multiport solar UV simulator 6 as a light source
The minimum erythema value (MED value) and the UV protection index value (SPF value) of each sample were obtained using Model 00 (manufactured by Solar Light) according to the following methods. (I) MED Measurement The back of a Hartley-type guinea pig (female) weighing 450 g to 500 g was treated with a depilatory cream. Twenty-four hours later, the hair was lightly shaved with a shaver, and then, using the above-mentioned ultraviolet irradiation device, 2.20, 1.76, 1.41, 1.1.
UVA at 3,0.90,0.72 MED / min intensity
And UVB. 24 hours later, the minimum irradiation dose at which erythema appeared was 1 MED.
【0012】(ii)SPF測定 体重450g〜500gのハートレー系モルモット
(雌)の背部を前記方法にて処理した後、各試験サンプ
ルを2μl/cm2 に均一に塗布した。紫外線照射装置
を用いてMED測定時と同様の強度でUVA及びUVB
を2分間照射した。24時間後のMEDを求め、下記の
式よりSPF値を算出した。(Ii) SPF Measurement After the back of a Hartley-type guinea pig (female) weighing 450 g to 500 g was treated by the above-described method, each test sample was uniformly applied to 2 μl / cm 2 . UVA and UVB with the same intensity as the MED measurement using an ultraviolet irradiation device
For 2 minutes. The MED after 24 hours was determined, and the SPF value was calculated from the following equation.
【0013】サンプルSPF値=(サンプル塗布時のM
ED値/未塗布時のMED値)Sample SPF value = (M at the time of sample application)
(ED value / MED value when not applied)
【0014】実施例1(BP−C2の合成) 常法により得たグアイアシルエチルケトン3gを30m
lのエタノールに溶解した後、撹拌下約15mlの水を
加えた。この水溶液にペロキシダーゼ(起源;西洋わさ
び)水溶液(25mg/50ml)を加えた。更に3%
過酸化水素水溶液12mlを約30分間かけて徐々に滴
下した。滴下終了後、約30分間撹拌を行った。 エタ
ノールを減圧下において除去した後、50mlの酢酸エ
チルを用いて有機層を抽出した。酢酸エチル層を硫酸ナ
トリウムを用いて乾燥後、減圧濃縮する事により、2.
9gの淡黄色油状物を得た。この油状物をシリカゲルク
ロマトグラフィー(展開溶媒:ベンゼン/アセトン=1
0/1)により薄層クロマトグラフィー(展開溶媒:ベ
ンゼン/アセトン=6/1)におけるRf値0.3付近
のスポットを含むフラクションを得た。展開溶媒を減圧
濃縮することにより除去した後、結晶化溶媒としたアセ
トンを用いることにより1.3gの白色結晶を得た。Example 1 (Synthesis of BP-C2) 3 g of guaiacyl ethyl ketone obtained by a conventional method was added to 30 m
After dissolving in 1 l of ethanol, about 15 ml of water was added with stirring. To this aqueous solution was added a peroxidase (origin; horseradish) aqueous solution (25 mg / 50 ml). 3% more
12 ml of an aqueous hydrogen peroxide solution was gradually dropped over about 30 minutes. After the completion of the dropwise addition, the mixture was stirred for about 30 minutes. After removing the ethanol under reduced pressure, the organic layer was extracted with 50 ml of ethyl acetate. 1. The ethyl acetate layer was dried using sodium sulfate, and then concentrated under reduced pressure.
9 g of a pale yellow oil was obtained. The oily substance is subjected to silica gel chromatography (developing solvent: benzene / acetone = 1).
0/1), a fraction containing a spot having an Rf value of about 0.3 in thin layer chromatography (developing solvent: benzene / acetone = 6/1) was obtained. After the developing solvent was removed by concentration under reduced pressure, 1.3 g of white crystals were obtained by using acetone as a crystallization solvent.
【0015】得られた白色結晶の13C−NMR(内部標
準物質:TMS、測定溶媒:重クロロホルム)において
199.4ppmにカルボニル炭素、147.7,14
7.2,129.5,125.3,122.6,10
9.4ppmに芳香族炭素、56.4ppmにメチルエ
ーテル炭素、30.8,8.6ppmにエチル基炭素シ
グナルを確認した。また、MS測定においてm/z35
8,344,329,223にピークを確認したことか
ら得られた白色結晶が、本発明のBP−C2であること
を確認した。なおBP−C2のIRスペクトラム及び紫
外線吸収スペクトルの一例を図1及び図2に示した。ま
た、その紫外線吸収スペクトルを測定した結果を表1に
示した。According to 13 C-NMR (internal standard substance: TMS, measuring solvent: deuterated chloroform) of the obtained white crystal, carbonyl carbon was added to 197.7 ppm at 147.7,14.
7.2, 129.5, 125.3, 122.6, 10
An aromatic carbon was detected at 9.4 ppm, a methyl ether carbon at 56.4 ppm, and an ethyl group carbon signal at 30.8 and 8.6 ppm. Also, m / z 35 in MS measurement.
The peaks at 8,344, 329 and 223 confirmed that the white crystals obtained were BP-C2 of the present invention. Examples of the IR spectrum and ultraviolet absorption spectrum of BP-C2 are shown in FIGS. Table 1 shows the results of measuring the ultraviolet absorption spectrum.
【0016】実施例2(BP−C5の合成) 実施例1で用いた3gのグアイアシルエチルケトンを
3.5gのグアイアシルアミルケトンに変え、同様の方
法を用いてRf値0.33付近のスポットより1.5g
の白色結晶を得た。13C−NMR測定(内部標準物質:
TMS、測定溶媒:重クロロホルム)において199.
1ppmにカルボニル炭素、147.6,147.1,
129.7,125.4,122.5,109.4pp
mに芳香族炭素、56.4ppmにメチルエーテル炭
素、38.2,31.6,24.4,22.6,13.
9ppmにアミル基炭素シグナルを確認した。また、M
S測定においてm/z442,386,371,330
にピークを確認したことから得られた白色結晶が、本発
明のBP−C5であることを確認した。なおBP−C5
の13C−NMRスペクトラムを図3に示した。また、そ
の紫外線吸収スペクトルを測定した結果を表1に示し
た。Example 2 (Synthesis of BP-C5) 3 g of guaiacyl ethyl ketone used in Example 1 was changed to 3.5 g of guaiacyl amyl ketone, and an Rf value of about 0.33 was obtained using the same method. 1.5g from spot
Was obtained as white crystals. 13 C-NMR measurement (internal standard:
199. TMS, measurement solvent: deuterated chloroform).
Carbonyl carbon, 147.6, 147.1, 1 ppm
129.7, 125.4, 122.5, 109.4 pp
m, aromatic carbon; 56.4 ppm, methyl ether carbon; 38.2,31.6,24.4,22.6,13.
An amyl group carbon signal was confirmed at 9 ppm. Also, M
M / z 442, 386, 371, 330 in S measurement
It was confirmed that the white crystal obtained from the confirmation of the peak was BP-C5 of the present invention. BP-C5
FIG. 3 shows the 13 C-NMR spectrum. Table 1 shows the results of measuring the ultraviolet absorption spectrum.
【0017】実施例3(BP−C8の合成) 実施例1で用いた3gのグアイアシルエチルケトンを
4.0gのグアイアシルオクチルケトンに変え、同様の
方法を用いてRf値0.33付近のスポットより1.2
gの白色結晶を得た。MS測定においてm/z526,
418にピークを確認したことから得られた白色結晶
が、本発明のBP−C8であることを確認した。また、
その紫外線吸収スペクトルを測定した結果を表1に示し
た。Example 3 (Synthesis of BP-C8) 3 g of guaiacyl ethyl ketone used in Example 1 was changed to 4.0 g of guaiacyl octyl ketone, and an Rf value of about 0.33 was obtained using the same method. 1.2 from the spot
g of white crystals were obtained. M / z 526 in MS measurement
It was confirmed that the white crystal obtained by confirming the peak at 418 was BP-C8 of the present invention. Also,
Table 1 shows the results of measurement of the ultraviolet absorption spectrum.
【0018】実施例4(紫外線吸収能力測定) 本発明のビフェニルケトン誘導体の紫外線吸収スペクト
ルを測定した結果を表1に示した。Example 4 (Measurement of UV Absorbing Ability) Table 1 shows the results of measuring the ultraviolet absorption spectrum of the biphenyl ketone derivative of the present invention.
【0019】[0019]
【表1】 [Table 1]
【0020】表1から明かなごとく、本発明のビフェニ
ルケトン誘導体は、UV−B及び/またはUV−A領域
に優れた紫外線吸収能を有している。As apparent from Table 1, the biphenyl ketone derivative of the present invention has an excellent ultraviolet absorbing ability in the UV-B and / or UV-A region.
【0021】実施例5(UV防御能の測定) 表2の処方に従って、実施例5及び比較例1,2の紫外
線吸収剤溶液を調製し、前記UV防御能に従いSPF値
を測定した。その結果を表3に示した。尚、パラソルM
CX及びASL−24は従来より紫外線吸収剤として用
いられている代表的なものである。Example 5 (Measurement of UV protection ability) According to the formulation in Table 2, the UV absorber solutions of Example 5 and Comparative Examples 1 and 2 were prepared, and the SPF value was measured according to the UV protection ability. Table 3 shows the results. In addition, parasol M
CX and ASL-24 are typical ones conventionally used as ultraviolet absorbers.
【0022】[0022]
【表2】 [Table 2]
【0023】表3から明かなごとく本発明のビフェニル
ケトン誘導体BP−C2は比較例と同様に優れた紫外線
防御能を有している。As is clear from Table 3, the biphenyl ketone derivative BP-C2 of the present invention has excellent ultraviolet protection ability as in the comparative example.
【0024】[0024]
【表3】 [Table 3]
【0025】[0025]
【発明の効果】本発明によりUV−B及びUV−Aの領
域を効果的に吸収しうる紫外線吸収剤を提供できる。According to the present invention can provide a UV-B及beauty ultraviolet absorber can effectively absorb the region of U V-A.
【図1】実施例1に記載した新規ビフェニル化合物BP
−C2のIRスペクトラムを示す。FIG. 1 is a novel biphenyl compound BP described in Example 1.
3 shows an IR spectrum of C2.
【図2】実施例1に記載した新規ビフェニル化合物BP
−C2の紫外線吸収スペクルを示す。FIG. 2 shows the novel biphenyl compound BP described in Example 1.
3 shows the ultraviolet absorption spectrum of C2.
【図3】実施例2に記載した新規ビフェニル化合物BP
−C5の13C−NMRのスペクトラムを示す。CDCl
3 は測定溶媒の重トリクロロホルム、TMSは内部標準
物質のテトラメチルシランを示す。FIG. 3 shows a novel biphenyl compound BP described in Example 2.
3 shows the 13 C-NMR spectrum of —C5. CDCl
3 indicates deuterated trichloroform as a measurement solvent, and TMS indicates tetramethylsilane as an internal standard substance.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特許2968067(JP,B2) 特公 平6−65136(JP,B2) Chemical Abstract s,Vol.90:192461(1979) (58)調査した分野(Int.Cl.7,DB名) A61K 7/00 - 7/50 C09K 3/00 104 CA(STN) REGISTRY(STN)────────────────────────────────────────────────── ─── Continuation of front page (56) References Patent No. 2968067 (JP, B2) Japanese Patent Publication No. 6-65136 (JP, B2) Chemical Abstracts, Vol. 90: 192461 (1979) (58) Fields investigated (Int. Cl. 7 , DB name) A61K 7/ 00-7/50 C09K 3/00 104 CA (STN) REGISTRY (STN)
Claims (2)
誘導体を含有することを特徴とする紫外線吸収剤。 【化1】 (但しRは炭素数1から12の直鎖又は側鎖の炭化水素
基。)1. An ultraviolet absorber comprising a biphenyl ketone derivative represented by the following general formula. Embedded image (Although hydrocarbon straight or side chain of R is from carbon number 1 12
Base . )
水素基である請求項1記載の紫外線吸収剤。 2. R is a straight or side chain carbon having 2 to 8 carbon atoms.
The ultraviolet absorbent according to claim 1, which is a hydrogen group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04241185A JP3133506B2 (en) | 1992-08-17 | 1992-08-17 | UV absorber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04241185A JP3133506B2 (en) | 1992-08-17 | 1992-08-17 | UV absorber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0665037A JPH0665037A (en) | 1994-03-08 |
JP3133506B2 true JP3133506B2 (en) | 2001-02-13 |
Family
ID=17070494
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP04241185A Expired - Fee Related JP3133506B2 (en) | 1992-08-17 | 1992-08-17 | UV absorber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3133506B2 (en) |
-
1992
- 1992-08-17 JP JP04241185A patent/JP3133506B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
Chemical Abstracts,Vol.90:192461(1979) |
Also Published As
Publication number | Publication date |
---|---|
JPH0665037A (en) | 1994-03-08 |
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