JPH05246949A - New cinnamic acid derivative, its production and ultraviolet-absorbing agent composed of the same compound - Google Patents
New cinnamic acid derivative, its production and ultraviolet-absorbing agent composed of the same compoundInfo
- Publication number
- JPH05246949A JPH05246949A JP4049826A JP4982692A JPH05246949A JP H05246949 A JPH05246949 A JP H05246949A JP 4049826 A JP4049826 A JP 4049826A JP 4982692 A JP4982692 A JP 4982692A JP H05246949 A JPH05246949 A JP H05246949A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- acid derivative
- cinnamic acid
- general formula
- 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.)
- Granted
Links
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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、持続性のある紫外線吸
収効果を有し、耐水及び耐油性に優れ、更には化粧料原
料として有用な桂皮酸誘導体及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cinnamic acid derivative having a long-lasting effect of absorbing ultraviolet rays, excellent in water resistance and oil resistance, and useful as a raw material for cosmetics, and a method for producing the same.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
皮膚疾患の原因の一つとして紫外線が注目を浴びてお
り、日焼け、老化、皮膚癌等の皮膚疾患に紫外線が深く
関わっていることが明らかになりつつある。このような
背景において、皮膚を紫外線から守ることが重要視さ
れ、紫外線防御物質を含む日焼け止め製剤、スキンケ
ア、ファンデーション等の化粧品が数多く市販されてい
る。2. Description of the Related Art In recent years,
Ultraviolet rays are drawing attention as one of the causes of skin diseases, and it is becoming clear that ultraviolet rays are deeply involved in skin diseases such as sunburn, aging, and skin cancer. Against this background, it is important to protect the skin from ultraviolet rays, and many cosmetics such as sunscreen preparations, skin care, foundations, etc. containing ultraviolet protective substances are commercially available.
【０００３】紫外線は、長波長紫外線（以下ＵＶ−Ａと
いう；３２０〜４００nm）、中波長紫外線（以下ＵＶ−
Ｂという；２９０〜３２０nm）、短波長紫外線（以下Ｕ
Ｖ−Ｃという；２９０nm以下）に区別され、中でも地表
に到達するＵＶ−Ａ、ＵＶ−Ｂの皮膚に対する有害性が
明らかにされ、これらの紫外線を防御するために多くの
紫外線防御物質が開発されている。例えば、ＵＶ−Ａ防
御物質としては酸化チタン、酸化鉄、酸化亜鉛等の無機
粉体や、４−ｔ−ブチル−４′−メトキシベンゾイルメ
タン等の油溶性の有機化合物が知られており、微粒子
化、超微粒子化、疎水化表面処理、他物質との複合化な
どの方法により、ＵＶ−Ａ防御効果を高めたり、目的に
応じた化粧品素材として使用可能な素材にする工夫がな
されている。Ultraviolet rays are long-wavelength ultraviolet rays (hereinafter referred to as UV-A; 320 to 400 nm), medium wavelength ultraviolet rays (hereinafter referred to as UV-A).
B; 290-320 nm), short-wave ultraviolet (hereinafter U)
V-C; 290 nm or less), and the harmfulness of UV-A and UV-B reaching the surface to the skin has been clarified, and many UV protection substances have been developed to protect these UV rays. ing. For example, as UV-A protective substances, inorganic powders such as titanium oxide, iron oxide and zinc oxide, and oil-soluble organic compounds such as 4-t-butyl-4′-methoxybenzoylmethane are known, and fine particles are known. The UV-A protective effect has been enhanced by various methods such as denaturation, ultrafine particle formation, hydrophobization surface treatment, and compounding with other substances to make it a material that can be used as a cosmetic material depending on the purpose.
【０００４】また、ＵＶ−Ｂ防御物質としては、パラア
ミノ安息香酸、サリチル酸、メトキシ桂皮酸、ベンゾフ
ェノン等及びそれらの誘導体が知られており、化粧品素
材として利用されている。その中で、上記のＵＶ−Ｂ防
御物質は、特にサンケア化粧料に配合され、暑い夏に使
用される頻度が高いために、汗や皮脂によって流れ落ち
やすい。そのため、耐水・耐油性を高めて皮膚より流れ
落ちにくくして紫外線吸収効果の持続性を高めることへ
のニーズが高まってきており、耐水・耐油性を高めたＵ
Ｖ−Ｂ吸収剤が提案されている。例えば、耐水・耐油性
を高める目的で、ＵＶ吸収基をシリコーンに結合させる
試みが、特公昭４４−２９８６６号公報、特開昭６０−
５８９９１号公報、特開昭６０−１０８４３１号公報、
特公昭６３−１６４１６号公報、特開平２−４１３２２
号公報、特開平２−１１７６１３号公報等に多く提案さ
れている。また、近年ではシリコーン油基剤が広く使用
されてきていることから、シリコーン油基剤との相溶性
を高める点からも、上記の提案がされている。しかしな
がら、シリコーン油基剤及びシリコーンを含むＵＶ吸収
剤は、耐水性は優れるが、耐油性は十分ではないという
欠点があった。Further, as UV-B protective substances, para-aminobenzoic acid, salicylic acid, methoxycinnamic acid, benzophenone and the like and derivatives thereof are known and used as cosmetic materials. Among them, the above-mentioned UV-B protective substance is blended especially in sun care cosmetics and is frequently used in hot summer, so that it easily flows off by sweat or sebum. Therefore, there is a growing need to enhance water resistance and oil resistance so that it does not run off the skin and the durability of the UV absorption effect is enhanced.
V-B absorbers have been proposed. For example, an attempt to bond a UV absorbing group to silicone for the purpose of enhancing water resistance and oil resistance has been made in JP-B-44-29866 and JP-A-60-.
58991, JP-A-60-108431,
JP-B-63-16416, JP-A-2-41322
Many are proposed in Japanese Patent Laid-Open No. 2-117613. In addition, since silicone oil bases have been widely used in recent years, the above proposals have been made also from the viewpoint of enhancing compatibility with silicone oil bases. However, although the silicone oil base and the UV absorber containing silicone have excellent water resistance, they have the drawback of not having sufficient oil resistance.
【０００５】ところで、近年、耐水性及び耐油性を同時
に満足する油剤としてフッ素系のもの、例えば「フォン
ブリン」（モンテフルオス社製）が有用なものとして認
識されつつある。By the way, in recent years, a fluorine-based oil agent, for example, "Fomblin" (manufactured by Montefluos Co., Ltd.) has been recognized as being useful as an oil agent satisfying both water resistance and oil resistance at the same time.
【０００６】そこで、フッ素系油剤との親和性が良好
で、分散、乳化又は溶解が可能であって耐水・耐油性に
優れ、かつ皮膚上に残存しうる、しかも顕著な紫外線吸
収能を有する化合物の開発が望まれていた。Therefore, a compound having a good affinity with a fluorinated oil agent, capable of being dispersed, emulsified or dissolved, excellent in water resistance and oil resistance, capable of remaining on the skin, and having a remarkable ultraviolet ray absorbing ability. Was desired to be developed.
【０００７】[0007]
【課題を解決するための手段】本発明者は、かかる実情
に鑑み鋭意検討した結果、桂皮酸誘導体のうちの特定の
ものが上記要求される性能を満足するものであることを
見出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies in view of such circumstances, the present inventor has found that a particular one of cinnamic acid derivatives satisfies the above-mentioned required performance, and the present invention Has been completed.
【０００８】すなわち、本発明は、下記一般式（１）で
表わされる桂皮酸誘導体を提供するものである。That is, the present invention provides a cinnamic acid derivative represented by the following general formula (1).
【０００９】[0009]
【化６】 [Chemical 6]
【００１０】（式中、Ｒｆ；直鎖又は分岐鎖の炭素数３
〜２１のパーフルオロアルキル基を示す、 Ａ；炭素数２〜３のアルキレン基を示す、 Ｒ；水素原子又は直鎖若しくは分岐鎖の炭素数１〜１０
のアルキル基を示す、 ｍ；０〜６の数を示す、 ｎ；０〜１０の数を示す、 ｐ；０〜３の数を示す）(In the formula, Rf is a linear or branched carbon number 3
To 21 showing a perfluoroalkyl group, A; showing an alkylene group having 2 to 3 carbon atoms, R; a hydrogen atom or a linear or branched chain having 1 to 10 carbon atoms
Represents an alkyl group of m; represents the number of 0 to 6, n; represents the number of 0 to 10, p; represents the number of 0 to 3)
【００１１】本発明は、また、下記一般式（３）で表わ
される化合物を、下記一般式（４）で表わされる化合物
と酸触媒存在下に、下記一般式（５）で表わされる化合
物と塩基触媒存在下に、下記一般式（６）で表わされる
化合物と第三級アミン及び／又は含窒素芳香族化合物存
在下にそれぞれ反応させる上記桂皮酸誘導体（１）の製
造方法を提供するものである。The present invention also provides a compound represented by the following general formula (3), a compound represented by the following general formula (5) and a base in the presence of an acid catalyst together with the compound represented by the following general formula (4). The present invention provides a process for producing the cinnamic acid derivative (1), which comprises reacting a compound represented by the following general formula (6) with a tertiary amine and / or a nitrogen-containing aromatic compound in the presence of a catalyst. ..
【００１２】[0012]
【化７】 [Chemical 7]
【００１３】（式中、Ｅは直鎖又は分岐鎖の炭素数１〜
５のアルキル基を示し、Ｘは塩素原子又は臭素原子を示
し、Ｒｆ、Ａ、Ｒ、ｍ、ｎ及びｐは前記と同義である）(In the formula, E is a linear or branched carbon number of 1 to
5 represents an alkyl group, X represents a chlorine atom or a bromine atom, and Rf, A, R, m, n, and p are as defined above)
【００１４】本発明は、更に、桂皮酸誘導体（１）から
なる紫外線吸収剤を提供するものである。The present invention further provides an ultraviolet absorber comprising the cinnamic acid derivative (1).
【００１５】本発明の一般式（１）で表わされるパーフ
ルオロアルキル基Ｒｆを有する桂皮酸誘導体（１）の具
体例としては、ヘプタフルオロペンチル−４−メトキシ
シンナメート、ノナフルオロヘキシル−４−メトキシシ
ンナメート、ウンデカフルオロヘプチル−４−メトキシ
シンナメート、トリデカフルオロオクチル−４−メトキ
シシンナメート、ヘプタデカフルオロデシル−４−メト
キシシンナメート、ヘンイコサフルオロドデシル−４−
メトキシシンナメート、ノナコサフルオロヘキサデシル
−４−メトキシシンナメート、ペンタデカフルオロノニ
ル−４−メトキシシンナメート、ノナデカフルオロウン
デシル−４−メトキシシンナメート、ペンタコサフルオ
ロテトラデシル−４−メトキシシンナメート、トリトリ
アコンタフルオロオクタデシル−４−メトキシシンナメ
ート、ペプタトリアコンタフルオロヘンイコシル−４−
メトキシシンナメート、トリデカフルオロオクチロキシ
エチル−４−メトキシシンナメート、２−トリデカフル
オロオクチロキシ−２′−メチル−エチル−４−メトキ
シシンナメート、ヘプタデカフルオロデシロキシエチル
−４−メトキシシンナメート、トリデカフルオロオクチ
ロキシエトキシエチル−４−メトキシシンナメート、ヘ
プタデカフルオロデシロキシエトキシエトキシエチル−
４−メトキシシンナメート、ヘプタフルオロイソプロピ
ル−４−メトキシシンナメート、ヘプタフルオロイソプ
ロポキシエチル−４−メトキシシンナメート、ヘプタデ
カフルオロドデシル−４−メトキシシンナメート、ヘプ
タデカフルオロテトラデシル−４−メトキシシンナメー
ト、トリデカフルオロデシル−４−メトキシシンナメー
ト、トリデカフルオロドデシル−４−メトキシシンナメ
ート、ヘンイコサフルオロテトラデシル−４−メトキシ
シンナメート、ヘンイコサフルオロヘキサデシル−４−
メトキシシンナメート、ヘプタデカフルオロデシル−４
−エトキシシンナメート、ヘプタデカフルオロデシル−
４−イソプロポキシシンナメート、ヘプタデカフルオロ
デシル−４−ｎ−ブトキシシンナメート、Specific examples of the cinnamic acid derivative (1) having a perfluoroalkyl group Rf represented by the general formula (1) of the present invention include heptafluoropentyl-4-methoxycinnamate and nonafluorohexyl-4-methoxy. Cinnamate, undecafluoroheptyl-4-methoxycinnamate, tridecafluorooctyl-4-methoxycinnamate, heptadecafluorodecyl-4-methoxycinnamate, henicosafluorododecyl-4-
Methoxycinnamate, nonacosafluorohexadecyl-4-methoxycinnamate, pentadecafluorononyl-4-methoxycinnamate, nonadecafluoroundecyl-4-methoxycinnamate, pentacosafluorotetradecyl-4-methoxycinnamate , Tritriacontafluorooctadecyl-4-methoxycinnamate, peptatriacontafluorohenicosyl-4-
Methoxycinnamate, tridecafluorooctyloxyethyl-4-methoxycinnamate, 2-tridecafluorooctyloxy-2'-methyl-ethyl-4-methoxycinnamate, heptadecafluorodecyloxyethyl-4-methoxycinnamate , Tridecafluorooctyloxyethoxyethyl-4-methoxycinnamate, heptadecafluorodecyloxyethoxyethoxyethyl-
4-methoxycinnamate, heptafluoroisopropyl-4-methoxycinnamate, heptafluoroisopropoxyethyl-4-methoxycinnamate, heptadecafluorododecyl-4-methoxycinnamate, heptadecafluorotetradecyl-4-methoxycinnamate , Tridecafluorodecyl-4-methoxycinnamate, tridecafluorododecyl-4-methoxycinnamate, henicosafluorotetradecyl-4-methoxycinnamate, henicosafluorohexadecyl-4-
Methoxycinnamate, heptadecafluorodecyl-4
-Ethoxycinnamate, heptadecafluorodecyl-
4-isopropoxycinnamate, heptadecafluorodecyl-4-n-butoxycinnamate,
【００１６】ウンデカフルオロヘプチル−２，４−ジメ
トキシシンナメート、トリデカフルオロオクチル−２，
４−ジメトキシシンナメート、ヘプタデカフルオロデシ
ル−２，４−ジメトキシシンナメート、ヘンイコサフル
オロドデシル−２，４−ジメトキシシンナメート、トリ
デカフルオロオクチロキシエトキシエチル−２，４−ジ
メトキシシンナメート、ウンデカフルオロヘプチル−
３，４−ジメトキシシンナメート、トリデカフルオロオ
クチル−３，４−ジメトキシシンナメート、ヘプタデカ
フルオロデシル−３，４−ジメトキシシンナメート、ヘ
ンイコサフルオロドデシル−３，４−ジメトキシシンナ
メート、トリデカフルオロオクチロキシエトキシエチル
−２，４−ジメトキシシンナメート、ウンデカフルオロ
ヘプチル−３，４，５−トリメトキシシンナメート、ト
リデカフルオロオクチル−３，４，５−トリメトキシシ
ンナメート、ヘプタデカフルオロデシル−３，４，５−
トリメトキシシンナメート、ヘンイコサフルオロドデシ
ル−３，４，５−トリメトキシシンナメート、トリデカ
フルオロオクチロキシエトキシエチル−３，４，５−ト
リメトキシシンナメート等が挙げられる。これらのう
ち、下記一般式（２）Undecafluoroheptyl-2,4-dimethoxycinnamate, tridecafluorooctyl-2,
4-dimethoxycinnamate, heptadecafluorodecyl-2,4-dimethoxycinnamate, henicosafluorododecyl-2,4-dimethoxycinnamate, tridecafluorooctyloxyethoxyethyl-2,4-dimethoxycinnamate, Decafluoroheptyl-
3,4-dimethoxycinnamate, tridecafluorooctyl-3,4-dimethoxycinnamate, heptadecafluorodecyl-3,4-dimethoxycinnamate, henicosafluorododecyl-3,4-dimethoxycinnamate, trideca Fluorooctyloxyethoxyethyl-2,4-dimethoxycinnamate, undecafluoroheptyl-3,4,5-trimethoxycinnamate, tridecafluorooctyl-3,4,5-trimethoxycinnamate, heptadecafluorodecyl -3,4,5-
Examples thereof include trimethoxycinnamate, henicosafluorododecyl-3,4,5-trimethoxycinnamate, tridecafluorooctyloxyethoxyethyl-3,4,5-trimethoxycinnamate and the like. Of these, the following general formula (2)
【００１７】[0017]
【化８】 [Chemical 8]
【００１８】（式中、Ｒｆ、Ａ、ｍ及びｎは前記と同義
である）で表わされる化合物が好ましい。A compound represented by the formula (wherein Rf, A, m and n have the same meanings as defined above) is preferable.
【００１９】本発明の桂皮酸誘導体（１）は、例えば下
記方法Ａ〜Ｃのそれぞれの方法により製造される。The cinnamic acid derivative (1) of the present invention is produced, for example, by each of the following methods A to C.
【００２０】製造方法Ａ 化合物（３）と化合物（４）とを酸触媒存在下に反応さ
せる。化合物（３）の具体例としては、ヘプタフルオロ
ペンチルアルコール、ノナフルオロヘキシルアルコー
ル、ウンデカフルオロヘプチルアルコール、トリデカフ
ルオロオクチルアルコール、ペンタデカフルオロノニル
アルコール、ヘプタデカフルオロデシルアルコール、ノ
ナデカフルオロウンデシルアルコール、ヘンイコサフル
オロデシルアルコール、トリトリアコンタフルオロオク
タデシルアルコール、トリデカフルオロオクチロキシエ
チルアルコール、ヘプタデカフルオロデシロキシエチル
アルコール等が挙げられる。Production Method A Compound (3) and compound (4) are reacted in the presence of an acid catalyst. Specific examples of the compound (3) include heptafluoropentyl alcohol, nonafluorohexyl alcohol, undecafluoroheptyl alcohol, tridecafluorooctyl alcohol, pentadecafluorononyl alcohol, heptadecafluorodecyl alcohol, nonadecafluoroundecyl alcohol. , Henicosafluorodecyl alcohol, tritriacontafluorooctadecyl alcohol, tridecafluorooctyloxyethyl alcohol, heptadecafluorodecyloxyethyl alcohol, and the like.
【００２１】化合物（４）においては、ＯＲは、例えば
メトキシ、エトキシ、イソプロポキシ、オクチロキシ、
ヘキシロキシ等の基を表わすが、入手の容易さから特に
メトキシ基が好ましい。ｐは０〜３の数を示すが、入手
の容易さの点からｐ＝１が特に好ましい。ＯＲの芳香族
環への置換位置については特に制限はないが、特に、パ
ラ位即ち４位が好ましい。In the compound (4), OR is, for example, methoxy, ethoxy, isopropoxy, octyloxy,
It represents a group such as hexyloxy, but a methoxy group is particularly preferable because it is easily available. Although p represents a number of 0 to 3, p = 1 is particularly preferable from the viewpoint of easy availability. The substitution position of OR on the aromatic ring is not particularly limited, but the para position, that is, the 4-position is particularly preferable.
【００２２】上記反応においては、化合物（３）の化合
物（４）に対するモル比は０．３〜５．０であることが
好ましい。In the above reaction, the molar ratio of the compound (3) to the compound (4) is preferably 0.3 to 5.0.
【００２３】上記反応に使用される酸触媒は、特に限定
されないが、パラトルエンスルホン酸、硫酸等が好まし
い。その使用量は化合物（４）に対し０．１〜５重量％
（以下単に％という）であることが好ましい。The acid catalyst used in the above reaction is not particularly limited, but paratoluenesulfonic acid, sulfuric acid and the like are preferable. The amount used is 0.1 to 5% by weight based on the compound (4).
(Hereinafter simply referred to as “%”) is preferable.
【００２４】また、本反応において生成する水を反応系
外へ除去することにより反応を促進することが好まし
い。通常その目的のためには、反応に不活性でかつ生成
された水と共沸可能な溶媒を反応系中に共存させ、生成
水を該溶媒と共沸させることにより反応系外へと除去す
る。Further, it is preferable to promote the reaction by removing the water produced in this reaction from the reaction system. Usually, for that purpose, a solvent that is inert to the reaction and is azeotropic with the produced water is allowed to coexist in the reaction system, and the produced water is azeotroped with the solvent to remove it outside the reaction system. ..
【００２５】上記目的のため好ましく使用される溶媒と
しては、例えば、ベンゼン、トルエン、キシレン、ヘキ
サン等が挙げられる。反応温度は、使用する溶媒の沸点
程度が適当である。Examples of the solvent preferably used for the above purpose include benzene, toluene, xylene, hexane and the like. The reaction temperature is appropriately around the boiling point of the solvent used.
【００２６】反応により得られる桂皮酸誘導体（１）の
精製方法は、特に限定されないが、通常触媒を中和、水
洗して溶媒を減圧下留去し、その後再結晶により精製す
る。再結晶用の好ましい溶媒例としては、メタノール、
エタノール、イソプロパノール、ブタノール等の低級ア
ルコール類が挙げられる。The purification method of the cinnamic acid derivative (1) obtained by the reaction is not particularly limited, but usually the catalyst is neutralized, washed with water, the solvent is distilled off under reduced pressure, and then purified by recrystallization. As a preferable solvent example for recrystallization, methanol,
Lower alcohols such as ethanol, isopropanol, butanol and the like can be mentioned.
【００２７】製造方法Ｂ 化合物（３）と化合物（５）とを塩基触媒存在下に反応
させる。化合物（５）の基Ｅの好ましい例としては、メ
チル基、エチル基、イソプロピル基、ブチル基、アシル
基等が挙げられる。Production Method B Compound (3) and compound (5) are reacted in the presence of a base catalyst. Preferred examples of the group E of the compound (5) include a methyl group, an ethyl group, an isopropyl group, a butyl group and an acyl group.
【００２８】上記反応における化合物（３）の化合物
（５）に対するモル比は０．３〜５．０であることが好
ましい。The molar ratio of the compound (3) to the compound (5) in the above reaction is preferably 0.3 to 5.0.
【００２９】本反応に好ましく使用される塩基触媒例と
しては、ＮａＯＨ、ＫＯＨ等のアルカリ金属水酸化物、
ＮａＯＣＨ3 、ＮａＯＣ2Ｈ5、ＫＯＣＨ3 、ＫＯＣ
4Ｈ9、ＬｉＯＣ4Ｈ9等のアルコラートなどが挙げられ
る。Examples of base catalysts preferably used in this reaction include alkali metal hydroxides such as NaOH and KOH,
NaOCH 3 , NaOC 2 H 5 , KOCH 3 , KOC
Examples thereof include alcoholates such as 4 H 9 and LiOC 4 H 9 .
【００３０】これらの使用量は、化合物（５）に対し
０．１〜５％程度が好ましい。The amount of these used is preferably about 0.1 to 5% with respect to the compound (5).
【００３１】上記反応は、６０〜１５０℃で、アルコー
ルＥＯＨ（Ｅは前記と同義である）を反応系外へ除去す
る条件下（常圧下でも減圧下でもよい）で行われる。The above reaction is carried out at 60 to 150 ° C. under the conditions (although it may be either normal pressure or reduced pressure) for removing the alcohol EOH (E has the same meaning as described above) outside the reaction system.
【００３２】製造方法Ｃ 化合物（３）と化合物（６）とを第三級アミン及び／又
は含窒素芳香族化合物存在下に反応させる。Production Method C Compound (3) and compound (6) are reacted in the presence of a tertiary amine and / or a nitrogen-containing aromatic compound.
【００３３】上記反応における化合物（３）の化合物
（６）に対するモル比は０．８〜２．０であることが好
ましい。The molar ratio of the compound (3) to the compound (6) in the above reaction is preferably 0.8 to 2.0.
【００３４】上記反応に好ましく使用される第三級アミ
ン例としては、トリエチルアミンが、また含窒素芳香族
化合物例としてはピリジン等が挙げられる。Examples of tertiary amines preferably used in the above reaction include triethylamine, and examples of nitrogen-containing aromatic compounds include pyridine and the like.
【００３５】これらの使用量は、化合物（６）に対し等
モル以上であることが好ましい。The amount of these used is preferably equimolar or more to the compound (6).
【００３６】また、反応に不活性な触媒、例えばベンゼ
ン、トルエン、キシレン、ヘキサン等を適宜使用しても
よい。Further, a catalyst inert to the reaction, such as benzene, toluene, xylene, hexane, etc., may be appropriately used.
【００３７】反応温度は０〜１２０℃、より好ましくは
２５〜９０℃である。この範囲より低温では反応速度が
十分でなく、より高温では、副反応が増加し、着色、純
度低下の原因となる。The reaction temperature is 0 to 120 ° C, more preferably 25 to 90 ° C. If the temperature is lower than this range, the reaction rate is not sufficient, and if the temperature is higher than this range, side reactions increase, causing coloration and deterioration of purity.
【００３８】本発明の桂皮酸誘導体（１）は、フッ素系
の油剤、例えば「フォンブリン」（モンテフルオス社
製）に常法に従い配合することにより日焼け止め製剤、
スキンケア、ファンデーション等の化粧料とすることが
できる。The cinnamic acid derivative (1) of the present invention is incorporated into a fluorinated oil agent such as "Fomblin" (manufactured by Montefluos Co.) according to a conventional method to give a sunscreen preparation.
It can be used as cosmetics such as skin care and foundation.
【００３９】[0039]
【発明の効果】本発明の桂皮酸誘導体は、特にフッ素系
油剤との親和性が良好で、該油剤との乳化、ゲル化、分
散又は溶解が容易であり、その結果皮膚への塗布が可能
である。また、本発明の桂皮酸誘導体は、耐水・耐油性
が良好で皮膚上に長く残存するため、持続性に優れる紫
外線吸収剤として有用である。本発明桂皮酸誘導体を各
種化粧料に配合させることにより該化粧料に上記特性を
付与することができる。The cinnamic acid derivative of the present invention has a particularly good affinity with a fluorinated oil agent and is easily emulsified, gelled, dispersed or dissolved with the oil agent, so that it can be applied to the skin. Is. Further, the cinnamic acid derivative of the present invention has good water resistance and oil resistance and remains on the skin for a long time, and thus is useful as an ultraviolet absorber having excellent durability. By incorporating the cinnamic acid derivative of the present invention into various cosmetics, the above properties can be imparted to the cosmetics.
【００４０】[0040]
【実施例】以下に本発明を実施例により具体的に説明す
るが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.
【００４１】実施例１Example 1
【００４２】[0042]
【化９】 [Chemical 9]
【００４３】温度計、攪拌棒、脱水管付の４つ口フラス
コに、４−メトキシ桂皮酸５３．４５ｇ（０．３mo
l）、ｎ−Ｃ8Ｆ17ＣＨ2ＣＨ2ＯＨ １５３．１ｇ（０．
３３mol）、パラトルエンスルホン酸２ｇ、トルエン３
００mlを仕込み、トルエン還流をさせながら生成水を反
応系外に除去した。１０時間反応後、５０〜７０℃に冷
却し、同温度にて炭酸水素ナトリウム水溶液で中和、分
層し、更に同温度にて３回水洗した。上層の溶媒を減圧
下留去し、メタノールにて再結晶した。結晶を濾過乾燥
し、白色の針状結晶１１５ｇを得た。In a four-necked flask equipped with a thermometer, a stirring rod and a dehydration tube, 53.45 g (0.3 mol) of 4-methoxycinnamic acid was added.
l), n-C 8 F 17 CH 2 CH 2 OH 153.1g (0.
33 mol), paratoluenesulfonic acid 2 g, toluene 3
00 ml was charged, and the produced water was removed from the reaction system while refluxing with toluene. After reacting for 10 hours, the mixture was cooled to 50 to 70 ° C., neutralized with an aqueous sodium hydrogen carbonate solution at the same temperature to separate layers, and further washed with water at the same temperature three times. The solvent in the upper layer was distilled off under reduced pressure, and the residue was recrystallized from methanol. The crystals were filtered and dried to obtain 115 g of white needle crystals.
【００４４】以下に示すＧＣ−ＭＳ、1Ｈ+−ＮＭＲ、Ｉ
Ｒ各データ及び図１に示すＵＶスペクトル（測定濃度；
１７ppm ，溶媒；エタノール）より、このものが上記化
合物であると同定した。 ＧＣ−ＭＳ：Ｍ+ ６２４1 Ｈ+−ＮＭＲ（δ値；ＣＤＣｌ3中）：7.65(1H,d), 7.4
7(2H,d), 6.92(2H,d), 6.30(1H,d), 4.50(2H,t),3.85(3
H,s), 2.57(2H,t) ＩＲ（cm-1）：1700, 1630, 1600, 1515, 1340, 1250,
1200, 1160, 1140,1000, 820, 650The following GC-MS, 1 H + -NMR, I
R data and UV spectrum shown in FIG. 1 (measured concentration;
It was identified as the above compound from 17 ppm, solvent; ethanol). GC-MS: M + 624 1 H + -NMR (δ value; in CDCl 3 ): 7.65 (1H, d), 7.4
7 (2H, d), 6.92 (2H, d), 6.30 (1H, d), 4.50 (2H, t), 3.85 (3
H, s), 2.57 (2H, t) IR (cm -1 ): 1700, 1630, 1600, 1515, 1340, 1250,
1200, 1160, 1140, 1000, 820, 650
【００４５】実施例２Example 2
【００４６】[0046]
【化１０】 [Chemical 10]
【００４７】ｎ−Ｃ8Ｆ17ＣＨ2ＣＨ2ＯＨ １５３．１
ｇ（０．３３mol ）の代わりに、ＲｆＣＨ2ＣＨ2ＯＨ
（Ｒｆ＝ＣqＨ2q+1としてｑ＝６：３％、ｑ＝８：６８
％、ｑ＝１０：２３％、ｑ＝１２：６％の組成）１６
３．７ｇ（０．３３mol ）を使用した以外は実施例１と
同様にして、白色粉末１２５ｇを得た。N-C 8 F 17 CH 2 CH 2 OH 153.1
Instead of g (0.33 mol), RfCH 2 CH 2 OH
(When Rf = C q H 2q + 1 , q = 6: 3%, q = 8: 68
%, Q = 10: 23%, q = 12: 6%) 16
125 g of a white powder was obtained in the same manner as in Example 1 except that 3.7 g (0.33 mol) was used.
【００４８】このものは下記の分析値により同定した。 ＧＣ−ＭＳ：Ｍ+ ５２４，６２４，７２４，８２４1 Ｈ+−ＮＭＲ（δ値；ＣＤＣｌ3中）：7.65(1H,d), 7.4
7(2H,d), 6.92(2H,d), 6.30(1H,d), 4.50(2H,t),3.85(3
H,s), 2.57(2H,t) ＩＲ（cm-1）：1700, 1630, 1600, 1515, 1340, 1250,
1200, 1160, 1140,1000, 820, 650This product was identified by the following analytical values. GC-MS: M + 524, 624, 724, 824 1 H + -NMR (δ value; in CDCl 3 ): 7.65 (1H, d), 7.4
7 (2H, d), 6.92 (2H, d), 6.30 (1H, d), 4.50 (2H, t), 3.85 (3
H, s), 2.57 (2H, t) IR (cm -1 ): 1700, 1630, 1600, 1515, 1340, 1250,
1200, 1160, 1140, 1000, 820, 650
【００４９】実施例３Example 3
【００５０】[0050]
【化１１】 [Chemical 11]
【００５１】４−メトキシ桂皮酸５３．４５ｇ（０．３
mol ）の代わりに、３，４−ジメトキシ桂皮酸６２．５
ｇ（０．３mol ）用いた以外は実施例１と同様にして、
白色粉末１３３ｇを得た。53.45 g of 4-methoxycinnamic acid (0.3
mol) instead of 3,4-dimethoxycinnamic acid 62.5
g (0.3 mol) was used in the same manner as in Example 1, except that
133 g of white powder was obtained.
【００５２】このものは下記の分析値により同定した。 ＧＣ−ＭＳ：Ｍ+ ６５４1 Ｈ+−ＮＭＲ（δ値；ＣＤＣｌ3中）：7.65(1H,d), 7.1
0(1H,d), 7.05(1H,s), 6.85(1H,d), 6.30(1H,d),4.50(2
H,t), 3.90(6H,s), 2.57(2H,t)This product was identified by the following analytical values. GC-MS: M + 654 1 H + -NMR (δ value; in CDCl 3 ): 7.65 (1H, d), 7.1
0 (1H, d), 7.05 (1H, s), 6.85 (1H, d), 6.30 (1H, d), 4.50 (2
H, t), 3.90 (6H, s), 2.57 (2H, t)
【００５３】比較例１Comparative Example 1
【００５４】[0054]
【化１２】 [Chemical 12]
【００５５】特開昭６０−５８９９１号公報に記載の実
施例１に従って、４−メトキシ桂皮酸４９ｇ（０．２７
５mol ）、エポキシ変性シリコーンとしては、エポキシ
当量１９０（ｎ＝約１０，ｍ＝約０）の上記構造に対応
するエポキシ変性シリコーン（ＴＳＦ４７３１：東芝シ
リコーン社製）を４７ｇ及びトルエン１４６ｇをコンデ
ンサー及び温度計を備えた５００mlフラスコへ投入し
た。反応混合物の表面上に窒素を導入し、窒素でガスシ
ールし、次に該反応混合物を１１０℃に加熱した。トル
エン４ｇ中のＮ，Ｎ−ジメチルエタノールアミン０．８
ｇを前記フラスコに添加し、反応混合物を１０５〜１１
５℃に４．５時間保持した。次に、反応混合物を６０℃
に放冷し、濾過により４−メトキシ桂皮酸を除去した。
濾液を減圧下に揮発物を留去し、淡褐色の粘稠な液体で
ある上記化合物８５ｇを得た。According to Example 1 described in JP-A-60-58991, 49 g of 4-methoxycinnamic acid (0.27
5 mol), as the epoxy-modified silicone, 47 g of epoxy-modified silicone (TSF4731: manufactured by Toshiba Silicone Co., Ltd.) corresponding to the above structure having an epoxy equivalent of 190 (n = about 10, m = about 0) and 146 g of toluene are used as a condenser and a thermometer. It was charged into a 500 ml flask equipped with. Nitrogen was introduced over the surface of the reaction mixture and blanketed with nitrogen, then the reaction mixture was heated to 110 ° C. 0.8 g of N, N-dimethylethanolamine in 4 g of toluene
g to the flask and added the reaction mixture to 105-11
Hold at 5 ° C. for 4.5 hours. Then, the reaction mixture is heated to 60 ° C.
After cooling to room temperature, 4-methoxycinnamic acid was removed by filtration.
The filtrate was evaporated under reduced pressure to remove volatiles to obtain 85 g of the above compound as a light brown viscous liquid.
【００５６】試験例１（フッ素系油剤との親和性） 「フォンブリンＨＣ／０４」（フッ素系油剤，モンテフ
ルオス社製）への溶解性を調べるため、上記フッ素系油
剤に対し、実施例１、２及び比較例１の化合物並びに４
−メトキシ桂皮酸−２−エチルヘキシル（比較例２）を
それぞれ別個に５％となるように混合し、各液の溶解性
を観察した。結果を表１に示す。Test Example 1 (Affinity with Fluorine-Based Oil Agent) In order to examine the solubility in “Fomblin HC / 04” (fluorine-based oil agent, manufactured by Montefluos), Example 1 was added to the above-mentioned fluorine-based oil agent. 2 and the compound of Comparative Example 1 and 4
2-Ethylhexyl methoxycinnamate (Comparative Example 2) was mixed separately so as to be 5%, and the solubility of each solution was observed. The results are shown in Table 1.
【００５７】[0057]
【表１】 [Table 1]
【００５８】表１に示されるように本発明化合物はフッ
素系油剤に対する親和性が良好であり、混合可能であっ
た。As shown in Table 1, the compound of the present invention had a good affinity for the fluorinated oil agent and could be mixed.
【００５９】試験例２（スクワランとの親和性） 皮脂成分であるスクワランへの溶解性を調べるため、上
記スクワランに対し、実施例１、２、比較例１及び２の
化合物をそれぞれ別個に５％となるように混合し、各液
の溶解性を観察した。結果を表２に示す。Test Example 2 (Affinity with Squalane) In order to examine the solubility in squalane as a sebum component, the compounds of Examples 1 and 2 and Comparative Examples 1 and 2 were separately added to the above squalane at 5%. And the solubility of each solution was observed. The results are shown in Table 2.
【００６０】[0060]
【表２】 [Table 2]
【００６１】表２に示されるように、本発明化合物は皮
脂成分であるスクワランに不溶であった。As shown in Table 2, the compound of the present invention was insoluble in squalane, which is a sebum component.
【００６２】試験例３（耐油性試験） 皮脂に対する耐油性を、皮膚の代わりにカバーグラスを
用いて、カバーグラス上に試験化合物を存在させて、ス
クワランによる流されやすさを下記方法により比較し
た。Test Example 3 (Oil resistance test) The oil resistance to sebum was compared by using the method described below, in which a cover glass was used instead of the skin, a test compound was present on the cover glass, and the squalane was easily washed away. ..
【００６３】試験方法 試験に供する化合物をクロロホルムに濃度約０．０２ m
ol／ｌ（Ｃ mol／ｌとする）になるように溶解する。こ
の溶液を２５μl 注射器にてカバーグラスに垂らす。カ
バーグラス上のクロロホルムを蒸発させた後、カバーグ
ラスを３０mlのスクワランに室温で約１分間浸漬し、取
り出す。取り出したカバーグラスを２０mlのクロロホル
ムに入れ、カバーグラスに付着している化合物を溶解す
る。得られたクロロホルム溶液のＵＶスペクトル吸光度
（Ａ）測定を行う。Test Method The compound to be used in the test was added to chloroform at a concentration of about 0.02 m.
Dissolve so that it becomes ol / l (C mol / l). This solution is dropped onto a coverslip with a 25 μl syringe. After the chloroform on the cover glass is evaporated, the cover glass is immersed in 30 ml of squalane for about 1 minute at room temperature and taken out. The removed cover glass is put in 20 ml of chloroform to dissolve the compound attached to the cover glass. The UV spectrum absorbance (A) of the obtained chloroform solution is measured.
【００６４】一方、試験に供する化合物をクロロホルム
に濃度約０．０２ mol／ｌ（Ｃ0mol ／ｌとする）にな
るよう溶解する。この溶液を２５μl 注射器にてカバー
グラスに垂らす。カバーグラス上のクロロホルムを蒸発
させた後、このカバーグラスを２０mlのクロロホルムに
入れ、カバーグラスに付着している化合物を溶解し、得
られたクロロホルム溶液のＵＶスペクトル吸光度
（Ａ0 ）測定を行う。試験に供する化合物のカバーグラ
スへの残存率は下記の式で表わされる。On the other hand, the compound to be tested is dissolved in chloroform to a concentration of about 0.02 mol / l (C 0 mol / l). This solution is dropped onto a coverslip with a 25 μl syringe. After the chloroform on the cover glass is evaporated, the cover glass is put into 20 ml of chloroform to dissolve the compound adhering to the cover glass, and the UV spectrum absorbance (A 0 ) of the obtained chloroform solution is measured. The residual rate of the compound used in the test on the cover glass is represented by the following formula.
【００６５】[0065]
【数１】 [Equation 1]
【００６６】結果を表３に示す。The results are shown in Table 3.
【００６７】[0067]
【表３】 [Table 3]
【００６８】表３に示されるように、本発明化合物はス
クワランに流されにくい、すなわち、耐油性に優れるこ
とがわかる。As shown in Table 3, it is understood that the compound of the present invention is hard to be washed by squalane, that is, excellent in oil resistance.
【図１】実施例１で得られた化合物の紫外部波長に対す
る吸光度を示すグラフである。FIG. 1 is a graph showing the absorbance of the compound obtained in Example 1 with respect to the ultraviolet wavelength.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年３月１９日[Submission date] March 19, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３６[Correction target item name] 0036
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３６】また、反応に不活性な溶媒、例えばベンゼ
ン、トルエン、キシレン、ヘキサン等を適宜使用しても
よい。Further, a solvent inert to the reaction , such as benzene, toluene, xylene, hexane and the like may be appropriately used.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 67/03 8018−4Ｈ 69/08 8018−4Ｈ 69/732 9279−4Ｈ 69/734 9279−4Ｈ Ｃ０９Ｋ 3/00 １０４ 9049−4Ｈ // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display area C07C 67/03 8018-4H 69/08 8018-4H 69/732 9279-4H 69/734 9279-4H C09K 3/00 104 9049-4H // C07B 61/00 300
Claims (6)
フルオロアルキル基を示す、 Ａ；炭素数２〜３のアルキレン基を示す、 Ｒ；水素原子又は直鎖若しくは分岐鎖の炭素数１〜１０
のアルキル基を示す、 ｍ；０〜６の数を示す、 ｎ；０〜１０の数を示す、 ｐ；０〜３の数を示す）で表わされる桂皮酸誘導体。1. The following general formula (1): (In the formula, Rf represents a straight-chain or branched-chain C3-21 perfluoroalkyl group, A: represents a C2-C3 alkylene group, R: hydrogen atom or straight-chain or branched carbon Number 1-10
The cinnamic acid derivative represented by the formula: m; showing the number of 0 to 6; n; showing the number of 0 to 10; p; showing the number of 0 to 3).
フルオロアルキル基を示す、 Ａ；炭素数２〜３のアルキレン基を示す、 ｍ；０〜６の数を示す、 ｎ；０〜１０の数を示す）で表わされる請求項１記載の
桂皮酸誘導体。2. The following general formula (2): (In the formula, Rf represents a straight-chain or branched-chain perfluoroalkyl group having 3 to 21 carbon atoms, A; represents an alkylene group having 2 to 3 carbon atoms, m; represents a number of 0 to 6, n; The cinnamic acid derivative according to claim 1, which is represented by a number from 0 to 10).
下記一般式（４）で表わされる化合物とを酸触媒存在下
に反応させることを特徴とする請求項１記載の桂皮酸誘
導体の製造方法。 【化３】 （式中、Ｒｆ；直鎖又は分岐鎖の炭素数３〜２１のパー
フルオロアルキル基を示す、 Ａ；炭素数２〜３のアルキレン基を示す、 Ｒ；水素原子又は直鎖若しくは分岐鎖の炭素数１〜１０
のアルキル基を示す、 ｍ；０〜６の数を示す、 ｎ；０〜１０の数を示す、 ｐ；０〜３の数を示す）3. A cinnamic acid derivative according to claim 1, wherein the compound represented by the following general formula (3) and the compound represented by the following general formula (4) are reacted in the presence of an acid catalyst. Method. [Chemical 3] (In the formula, Rf represents a straight-chain or branched-chain C3-21 perfluoroalkyl group, A: represents a C2-C3 alkylene group, R: hydrogen atom or straight-chain or branched carbon Number 1-10
Represents an alkyl group of m; represents the number of 0 to 6, n; represents the number of 0 to 10, p; represents the number of 0 to 3)
一般式（５）で表わされる化合物とを塩基触媒存在下に
反応させることを特徴とする請求項１記載の桂皮酸誘導
体の製造方法。 【化４】 （式中、Ｅ；直鎖又は分岐鎖の炭素数１〜５のアルキル
基を示す、 Ｒ；水素原子又は直鎖若しくは分岐鎖の炭素数１〜１０
のアルキル基を示す、 ｐ；０〜３の数を示す）4. The method for producing a cinnamic acid derivative according to claim 1, wherein the compound represented by the general formula (3) and the compound represented by the following general formula (5) are reacted in the presence of a base catalyst. .. [Chemical 4] (In the formula, E: a linear or branched alkyl group having 1 to 5 carbon atoms, R: hydrogen atom or a linear or branched carbon number 1 to 10
Represents an alkyl group, p; represents the number of 0 to 3)
一般式（６）で表わされる化合物とを第三級アミン及び
／又は含窒素芳香族化合物存在下に反応させることを特
徴とする請求項１記載の桂皮酸誘導体の製造方法。 【化５】 （式中、Ｘ；塩素原子又は臭素原子を示す、 Ｒ；水素原子又は直鎖若しくは分岐鎖の炭素数１〜１０
のアルキル基を示す、 ｐ；０〜３の数を示す）5. A compound represented by the general formula (3) and a compound represented by the following general formula (6) are reacted in the presence of a tertiary amine and / or a nitrogen-containing aromatic compound. Item 2. A method for producing a cinnamic acid derivative according to Item 1. [Chemical 5] (In the formula, X represents a chlorine atom or a bromine atom, R; a hydrogen atom, or a linear or branched carbon number of 1 to 10
Represents an alkyl group, p; represents the number of 0 to 3)
外線吸収剤。6. An ultraviolet absorber comprising the cinnamic acid derivative according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04982692A JP3155325B2 (en) | 1992-03-06 | 1992-03-06 | Novel cinnamic acid derivative, method for producing the same, and ultraviolet absorber comprising the compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04982692A JP3155325B2 (en) | 1992-03-06 | 1992-03-06 | Novel cinnamic acid derivative, method for producing the same, and ultraviolet absorber comprising the compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05246949A true JPH05246949A (en) | 1993-09-24 |
| JP3155325B2 JP3155325B2 (en) | 2001-04-09 |
Family
ID=12841906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04982692A Expired - Fee Related JP3155325B2 (en) | 1992-03-06 | 1992-03-06 | Novel cinnamic acid derivative, method for producing the same, and ultraviolet absorber comprising the compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3155325B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008018683A1 (en) * | 2006-08-10 | 2008-02-14 | Amorepacific Corporation | Hydroxycinnamic acid derivatives and preparation method thereof and cosmetic composition containing it |
| US11021431B2 (en) | 2017-06-15 | 2021-06-01 | Tohoku University | Method for producing cinnamic acid ester compound |
-
1992
- 1992-03-06 JP JP04982692A patent/JP3155325B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008018683A1 (en) * | 2006-08-10 | 2008-02-14 | Amorepacific Corporation | Hydroxycinnamic acid derivatives and preparation method thereof and cosmetic composition containing it |
| US11021431B2 (en) | 2017-06-15 | 2021-06-01 | Tohoku University | Method for producing cinnamic acid ester compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3155325B2 (en) | 2001-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102404300B1 (en) | Ultraviolet radiation absorbing polyethers | |
| EP0138321B1 (en) | Organosilicon compounds and preparation and use thereof | |
| EP0255157B1 (en) | Novel sunscreen agents, sunscreen compositions and methods for preventing sunburn | |
| US4584190A (en) | Novel chalcone derivatives and ultraviolet absorbers comprising the same | |
| AU622195B2 (en) | New liposoluble unsaturated benzalmalonate derivatives and their use as absorbers for ultraviolet radiation in cosmetics | |
| EP0350314A2 (en) | Silicone type cinnamic acid derivative, preparation method thereof, uv-ray absorber, and external skin treatment agent. | |
| JP4053676B2 (en) | Silanyl-triazine as a light shielding composition | |
| JPS6316416B2 (en) | ||
| CA1310912C (en) | Use in cosmetics of diorganopolysiloxanes with a compositions containing these compounds, for ues in skin and hair protection products | |
| JP3155325B2 (en) | Novel cinnamic acid derivative, method for producing the same, and ultraviolet absorber comprising the compound | |
| US5004594A (en) | Benzylidenecamphor sulphonamides derived from amino acids and their application in cosmetics, particularly as sunscreens | |
| GB2081716A (en) | Quaternary dibenzoylmethane derivatives and their use as sun filters | |
| US5146002A (en) | Aroyl ketone derivative, uv ray absorber comprising the same, and cosmetic composition containing the same | |
| JPS6112612A (en) | Sun-screening agent-containing composition | |
| US5191121A (en) | Aroyl ketone derivative, UV ray absorber comprising the same, and cosmetic composition containing the same | |
| GB2185396A (en) | Cosmetic compositions designed to protect the skin against the adverse effects of ultraviolet radiation | |
| JP3497246B2 (en) | Benzylidene hydantoin derivative, ultraviolet absorber and external preparation for skin containing the same | |
| JP4105845B2 (en) | Novel pyrimidine-2,4,6-trione compound | |
| EP0528380B1 (en) | Alkyl-aryl 1,3-propanedion silicone derivative and an external preparation for skin with the derivative compounded therein | |
| JP3022008B2 (en) | Composition comprising a mixture of t-butoxy carbonates of trisphenols | |
| JP3213366B2 (en) | Cinnamic acid derivatives | |
| JPH0717892A (en) | 1,3-butadienyl ketone derivative, ultraviolet ray absorber and skin external preparation containing the same blended therein | |
| JP3122465B2 (en) | Optical screening agent | |
| JPH03220153A (en) | Benzoyl pinacolone derivative, uv ray absorbent containing the same and cosmetic containing the same | |
| EP0450892A1 (en) | Cinnamic acid derivative and external skin treatment preparation containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |