JPH0753861B2 - UV absorber - Google Patents
UV absorberInfo
- Publication number
- JPH0753861B2 JPH0753861B2 JP8346886A JP8346886A JPH0753861B2 JP H0753861 B2 JPH0753861 B2 JP H0753861B2 JP 8346886 A JP8346886 A JP 8346886A JP 8346886 A JP8346886 A JP 8346886A JP H0753861 B2 JPH0753861 B2 JP H0753861B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- parts
- benzoyl
- acid
- absorber
- 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 - Lifetime
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Classifications
-
- 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
-
- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、特定の構造を有するα−デヒドロアミノ酸誘
導体を有効成分とする紫外線吸収剤に関し、さらに詳し
くは、日焼け止め、繊維や樹脂等の黄変防止、容器及び
包材や、その内容物の紫外線からの保護等に有効であ
り、塗料、樹脂、医薬、食品、化粧品といった広い分野
に対し適応できる紫外線吸収剤に関するものである。TECHNICAL FIELD The present invention relates to an ultraviolet absorbent containing an α-dehydroamino acid derivative having a specific structure as an active ingredient, and more specifically, to a sunscreen, a fiber, a resin or the like. The present invention relates to an ultraviolet absorber which is effective in preventing yellowing, protecting containers and packaging materials, and the contents thereof from ultraviolet rays, and which can be applied to a wide range of fields such as paints, resins, medicines, foods and cosmetics.
［従来の技術］ 従来、化粧品の分野では紫外線の皮膚に対する有害作用
を防ぐため、紫外線吸収剤が早くから注目され、数多く
開発されてきた。[Prior Art] Conventionally, in the field of cosmetics, in order to prevent harmful effects of ultraviolet rays on the skin, ultraviolet absorbers have been attracting attention from an early stage and many have been developed.
紫外線吸収剤としてはベンドフェノン系吸収剤、サリチ
ル酸系吸収剤、ケイ皮酸系吸収剤、パラアミノ安息香酸
系吸収剤などが用いられている。しかしながら、これら
の紫外線吸収剤のうち、効果、安全性、溶解性、安定性
等を兼備するものは非常に少ない。As the UV absorber, a bendphenone-based absorber, a salicylic acid-based absorber, a cinnamic acid-based absorber, a para-aminobenzoic acid-based absorber and the like are used. However, very few of these UV absorbers have the effects, safety, solubility, stability and the like.
例えばベンゾフェノン系吸収剤は、320〜400nmの長波長
紫外線には吸収効果を有するが、火ぶくれなどの原因と
考えられる中波長紫外線（290〜320nm）に対しては吸収
能が低い。For example, a benzophenone-based absorber has an absorption effect on long-wavelength ultraviolet rays of 320 to 400 nm, but has a low absorption ability for medium-wavelength ultraviolet rays (290 to 320 nm), which is considered to cause blistering.
パラアミノ安息香酸系、ケイ皮酸系吸収剤は吸収効果は
高いが、安定性に問題があるといわれている。またサリ
チル酸系吸収剤は吸収効果が弱く、大量に用いなければ
効果が期待できない。Para-aminobenzoic acid-based and cinnamic acid-based absorbents have a high absorption effect, but are said to have stability problems. Further, the salicylic acid-based absorbent has a weak absorption effect, and the effect cannot be expected unless it is used in a large amount.
上述の紫外線吸収剤の他に、紫外線を物理的に反射、散
乱させる機能を有する二酸化チタン、酸化亜鉛、酸化鉄
などの無機粉体も用いられる。しかしながら、無機粉体
は配合できる化粧品のタイプが限定され、また多量に配
合すると着色するという問題点がある。In addition to the above-mentioned ultraviolet absorber, inorganic powders such as titanium dioxide, zinc oxide, and iron oxide, which have a function of physically reflecting and scattering ultraviolet rays, are also used. However, the types of cosmetics that can be blended with inorganic powders are limited, and there is a problem that coloring occurs when a large amount is blended.
一方、樹脂への添加剤としては、サリチル酸系、ベンゾ
フェノン系吸収剤の他、トリアゾール系、シアノアクリ
レート系紫外線吸収剤が使用されている。しかしなが
ら、サリチル酸系及びベンゾフェノン系吸収剤では、ポ
リエチレンやポリプロピレン、塩化ビニル樹脂に影響を
およぼすといわれている300〜320nm付近の吸収が弱く、
トリアゾール系吸収剤は安全性上問題があるといわれて
いる。またシアノアクリレート系吸収剤は高価値である
などの問題点がある。On the other hand, as additives to the resin, in addition to salicylic acid-based and benzophenone-based absorbers, triazole-based and cyanoacrylate-based UV absorbers are used. However, with salicylic acid-based and benzophenone-based absorbents, absorption at around 300 to 320 nm, which is said to affect polyethylene, polypropylene, and vinyl chloride resins, is weak,
Triazole-based absorbents are said to have safety problems. Further, the cyanoacrylate-based absorbent has a problem that it has a high value.
［本発明が解決しようとする問題点］ 上述したように、化粧品及び樹脂の分野などで種々の紫
外線吸収剤が開発されてはいるが、紫外線吸収能、安全
性、溶剤や樹脂への溶解性及び安定性をすべて満足する
ものは未だ見いだされていないというのが実情であり、
これらを兼備した新しい紫外線吸収剤が望まれている。[Problems to be Solved by the Present Invention] As described above, although various ultraviolet absorbers have been developed in the fields of cosmetics and resins, their ultraviolet absorbing ability, safety, and solubility in solvents and resins have been developed. And, the fact is that nothing satisfying all of the stability has been found yet,
There is a demand for a new ultraviolet absorber that combines these.
［問題点を解決するための手段］ 本発明者らは、かかる実情に鑑み、鋭意研究を行った結
果、下記一般式（１）で表わされるα−デヒドロアミノ
酸誘導体が中波長紫外線領域（240〜360nm）に多きな吸
収効果を有し、水、各種動植物油、油脂及び有機溶剤に
可溶であり、皮膚の紅斑防止、樹脂の劣化防止等に有効
な紫外線吸収剤であることを見いだし、本発明を完成し
た。[Means for Solving Problems] As a result of earnest studies in view of such circumstances, the inventors have found that the α-dehydroamino acid derivative represented by the following general formula (1) has an intermediate wavelength ultraviolet region (240 to We found that it is a UV absorber that is effective in preventing erythema of the skin, preventing deterioration of resin, etc., having a large absorption effect at 360 nm) and being soluble in water, various animal and vegetable oils, oils and fats and organic solvents. Completed the invention.
（式中、Ａはフェニル基、イミダゾリル基、インドリル
基、フリル基、ピロリル基、チオフリル基またはピリジ
ル基であり、R1は水素原子、ヒドロキシ基またはアルコ
キシ基であり、COR2はカルボキシル基もしくはその塩ま
たはエステル基であり、そしてR3はアシル基またはベン
ジルオキシカルボニル基である。） α−デヒドロアミノ酸は例えばOrganic Reactions第10
巻、198〜239頁（1959年）によりその合成法が研究され
た既知化合物であるが、これまで紫外線吸収剤として用
いられた例はない。 (In the formula, A is a phenyl group, an imidazolyl group, an indolyl group, a furyl group, a pyrrolyl group, a thiofuryl group or a pyridyl group, R 1 is a hydrogen atom, a hydroxy group or an alkoxy group, and COR 2 is a carboxyl group or a carboxyl group thereof. A salt or ester group, and R 3 is an acyl group or a benzyloxycarbonyl group.) Α-dehydroamino acids are, for example, Organic Reactions No. 10
Vol., Pp. 198-239 (1959), a known compound whose synthetic method was studied, but it has never been used as an ultraviolet absorber.
上記一般式（１）で表わされる化合物は、例えば、アル
デヒドとアシルグリシンまたはそのアズラクトンと縮合
した後、加水分解、アルコリシスまたはアミノリシスす
ることにより得ることができる（式１）。The compound represented by the above general formula (1) can be obtained by, for example, condensing an aldehyde with an acylglycine or its azlactone and then subjecting it to hydrolysis, alcoholysis or aminolysis (formula 1).
また、α−ケト酸あるいはそのエステルをホスフィンイ
ミンと縮合（式２）、またはアミドもしくはニトリルと
縮合（式３）することにより得ることができる。It can also be obtained by condensing an α-keto acid or its ester with phosphinimine (formula 2) or with an amide or nitrile (formula 3).
さらには、Ｎ−ヒドロキシアミノ酸エステルの脱水によ
っても得ることができる（式４）。Further, it can be obtained by dehydration of N-hydroxy amino acid ester (formula 4).
（上記式中、Ａ、R1、COR2、R3は前記と同じである。ま
たR4はアルキル基またはアリール基である。） このようにして得られる化合物を例示するならば、Ｎ−
ベンゾイル−Ｏ−メチル−α−デヒドロチロシン、Ｎ−
ベンゾイル−Ｏ−メチル−α−デヒドロチロシンエチル
エステル、Ｎ−ベンゾイル−α−デヒドロトリプトファ
ンメチルエステル、Ｎ−ベンゾイル−β−フラニル−α
−デヒドロアラニン、Ｎ−ベンゾイル−β−フラニル−
α−デヒドロアラニンナトリウム塩、Ｎ−ベンゾイル−
β−チオフラニル−α−デヒドロアラニン、Ｎ−ベンジ
ルオキシカルボニル−β−チオフラニル−α−デヒドロ
アラニンカルシウム塩、Ｎ−アセチル−β−ピリジル−
α−デヒドロアラニンマグネシウム塩等が挙げられる。 (In the above formula, A, R 1 , COR 2 and R 3 are the same as above. Further, R 4 is an alkyl group or an aryl group.) If the compound thus obtained is exemplified, N-
Benzoyl-O-methyl-α-dehydrotyrosine, N-
Benzoyl-O-methyl-α-dehydrotyrosine ethyl ester, N-benzoyl-α-dehydrotryptophan methyl ester, N-benzoyl-β-furanyl-α
-Dehydroalanine, N-benzoyl-β-furanyl-
α-dehydroalanine sodium salt, N-benzoyl-
β-thiofuranyl-α-dehydroalanine, N-benzyloxycarbonyl-β-thiofuranyl-α-dehydroalanine calcium salt, N-acetyl-β-pyridyl-
Examples include α-dehydroalanine magnesium salt and the like.
［実施例］ 次に、本発明を、合成例、配合例ならびに実施例を挙
げ、更に詳細に説明するが、本発明はそれによって限定
されるものではない。[Examples] Next, the present invention will be described in more detail with reference to Synthesis Examples, Formulation Examples and Examples, but the present invention is not limited thereto.
参考例１ ２−フェニル−４−（４−メトキシベンジリデン）−５
−オキサゾロンの合成 アニスアルデヒド20ml、無水酢酸50ml、馬尿酸33.7gお
よび酢酸ナトリウム6.7gを、よく混合し、水浴で30分加
熱した。析出した結晶は、温水で洗浄後、ろ過した。ベ
ンゼンより再結晶し、乾燥することで、２−フェニル−
４−（４−メトキシベンジリデン）−５−オキサゾロン
40gを得た。収率83％。Reference Example 1 2-Phenyl-4- (4-methoxybenzylidene) -5
-Synthesis of oxazolone 20 ml of anisaldehyde, 50 ml of acetic anhydride, 33.7 g of hippuric acid and 6.7 g of sodium acetate were mixed well and heated in a water bath for 30 minutes. The precipitated crystals were washed with warm water and then filtered. By recrystallizing from benzene and drying, 2-phenyl-
4- (4-methoxybenzylidene) -5-oxazolone
I got 40g. Yield 83%.
合成例１ Ｎ−ベンゾイル−Ｏ−メチル−α−デヒドロチロシンの
合成 参考例１で得られた２−フェニル−４−（４−メトキシ
ベンジリデン）−５−オキサゾロン10gを、温アルコー
ルに溶解し、２％水酸化ナトリウム水溶液100mlを加
え、水浴で15分間加熱した。冷却後、希硫酸で反応液を
酸性にし、析出した結晶をろ過し、水で洗浄した。水−
メタノールより再結晶し、乾燥することで、Ｎ−ベンゾ
イル−Ｏ−メチル−α−デヒドロチロシン9.5gを得た。
収率89％。Synthesis Example 1 Synthesis of N-benzoyl-O-methyl-α-dehydrotyrosine 10 g of 2-phenyl-4- (4-methoxybenzylidene) -5-oxazolone obtained in Reference Example 1 was dissolved in warm alcohol to prepare 2 100% aqueous sodium hydroxide solution was added and heated in a water bath for 15 minutes. After cooling, the reaction solution was acidified with dilute sulfuric acid, and the precipitated crystals were filtered and washed with water. Water −
It was recrystallized from methanol and dried to obtain 9.5 g of N-benzoyl-O-methyl-α-dehydrotyrosine.
Yield 89%.
参考例２ ２−フェニル−４−インドラール−５−オキサゾロンの
合成 インドールアルデヒド18g、馬尿酸25.5g、酢酸ナトリウ
ム9.9gを粉砕混合し、無水酢酸45mlを加え、100℃で15
分間加熱した。冷却後、析出した結晶をろ取し、水洗、
乾燥することにより、２−フェニル−４−インドラール
−５−オキサゾロン29gを得た。収率80％。Reference Example 2 Synthesis of 2-phenyl-4-indolar-5-oxazolone 18 g of indole aldehyde, 25.5 g of hippuric acid and 9.9 g of sodium acetate were pulverized and mixed, 45 ml of acetic anhydride was added, and the mixture was mixed at 100 ° C. for 15 minutes.
Heated for minutes. After cooling, the precipitated crystals were collected by filtration, washed with water,
By drying, 29 g of 2-phenyl-4-indolal-5-oxazolone was obtained. Yield 80%.
合成例２ Ｎ−ベンゾイル−α−デヒドロトリプトファンの合成 参考例２で得られた２−フェニル−４−インドラール−
５−オキサゾロン14.4gを、１％水酸化ナトリウム水溶
液に加熱溶解させた。希塩酸で反応液を酸性にし、析出
した結晶をろ取、水洗後、メタノールより再結晶し、乾
燥することで、Ｎ−ベンゾイル−α−デヒドロトリプト
ファン11gを得た。収率70％。Synthesis Example 2 Synthesis of N-benzoyl-α-dehydrotryptophan 2-phenyl-4-indolal-obtained in Reference Example 2
14.4 g of 5-oxazolone was dissolved by heating in a 1% sodium hydroxide aqueous solution. The reaction solution was acidified with diluted hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, recrystallized from methanol, and dried to obtain 11 g of N-benzoyl-α-dehydrotryptophan. Yield 70%.
配合例１ 日焼け止め油 Ｎ−ベンゾイル−α−デヒドロチロシンメチルエステル
1部 流動パラフィン 60部 オリーブ油 39 配合例２ 日焼け、ふけ防止ヘアークリーム 流動パラフィン 40部 セチルアルコール 1部 蜜ロウ 3部 ミリスチル酸イソプロピル 1部 ステアリン酸グリセリンエステル 2.13部 セチルエーテルポリオキシエチレン 2.87部 プロピレングリコール 5部 Ｎ−ベンゾイル−α−デヒドロチロシンアミド 1部 精製水 44部 配合例３ 起泡性エアスプレー ステアリン酸 7部 プロピレングリコール 7部 トリエタノールアミン 6部 オリーブ油 2部 Ｎ−ベンゾイル−α−デヒドロチロシン 0.3部 精製水 77.7部 を混合し、該混合液90部とフレオンガス（F21/F114＝40
/60）10部を耐圧容器に装入した。Formulation 1 Sunscreen oil N-benzoyl-α-dehydrotyrosine methyl ester
1 part Liquid paraffin 60 parts Olive oil 39 Formulation 2 Sunburn and dandruff hair cream Liquid paraffin 40 parts Cetyl alcohol 1 part Beeswax 3 parts Isopropyl myristate 1 part Glycerin stearate 2.13 parts Cetyl ether polyoxyethylene 2.87 parts Propylene glycol 5 Parts N-benzoyl-α-dehydrotyrosine amide 1 part purified water 44 parts formulation example 3 foaming air spray 7 parts stearic acid 7 parts propylene glycol 7 parts triethanolamine 6 parts olive oil 2 parts N-benzoyl-α-dehydrotyrosine 0.3 parts Purified water (77.7 parts) is mixed, and 90 parts of the mixed solution and Freon gas (F21 / F114 = 40
/ 60) 10 parts were charged into a pressure vessel.
配合例４ 無起泡性ローションエアスプレー プロピレングリコール 10部 99％エタノール 30部 Ｎ−ベンゾイル−α−デヒドロチロシン 1部 精製水 50部 を混合し、該混合液30部とフレオンガス（F12/F114＝40
/60）70部を耐圧容器に装入した。Formulation 4 Non-foaming lotion air spray Propylene glycol 10 parts 99% Ethanol 30 parts N-benzoyl-α-dehydrotyrosine 1 part Purified water 50 parts are mixed, and the mixed solution 30 parts and Freon gas (F12 / F114 = 40) are mixed.
/ 60) 70 parts were placed in a pressure vessel.
実施例１ 合成例１、２ならびにこれに準拠した方法により合成し
た化合物について最大吸収波長並びに、その他の物性値
を測定しその結果を表１に示した。Example 1 The maximum absorption wavelength and other physical properties of the compounds synthesized by Synthesis Examples 1 and 2 and the method based thereon were measured, and the results are shown in Table 1.
実施例２ 100gの高密度ポリエチレンを250mgのＮ−ベンゾイル−
Ｏ−メチル−α−デヒドロチロシンと混合し、且つ、12
0℃の温度でロールミキサーで加工して無色、透明なシ
ートにした。このシートを0.2mmの一様な厚さにプレス
し、次にゼノテスター中で2000時間、紫外線放射に晒し
た。 Example 2 100 g of high density polyethylene was added to 250 mg of N-benzoyl-
Mixed with O-methyl-α-dehydrotyrosine and
It was processed with a roll mixer at a temperature of 0 ° C. to obtain a colorless and transparent sheet. The sheet was pressed to a uniform thickness of 0.2 mm and then exposed to UV radiation for 2000 hours in a Xenotester.
シートの劣化の測定は、プラスチックテクノロジー（Pl
astic Technology）５月号、1958年、第427頁の方法に
よって行なった。即ち、露光前及び後の、被試験シート
の赤外スペクトル（透過スペクトル）を測定し、そのケ
トン性カルボニル吸収帯の増加をもって劣化の尺度とし
た。Deterioration of the seat is measured by the plastic technology
astic Technology) May issue, 1958, p. 427. That is, the infrared spectrum (transmission spectrum) of the test sheet before and after exposure was measured, and the increase in the ketonic carbonyl absorption band was used as a measure of deterioration.
約1720〜1730cm-1に劣化カルボニルのピークが測定され
た。無添加シートでは露光前のカルボニル吸収強度は0.
11であり、露光後は0.40であった。Ｎ−ベンゾイル−Ｏ
−メチル−α−デヒドロチロシンで安定化したシートで
は、露光前、露光後ともに0.12であり、明らかに劣化が
抑制された。A peak of degraded carbonyl was measured at about 1720 to 1730 cm -1 . In the additive-free sheet, the carbonyl absorption intensity before exposure is 0.
11 and 0.40 after exposure. N-benzoyl-O
In the sheet stabilized with -methyl-α-dehydrotyrosine, the deterioration was obviously suppressed before and after the exposure was 0.12.
実施例３ 配合例１に従い調製した日焼け止め油ａと、流動パラフ
ィン60部、オリーブ油39部の混合油ｂの夫々0.1gをエタ
ノール／ヘキサン（1:1）混合液100mlに溶解した際の吸
光度を図２に示す。Example 3 Absorbances obtained by dissolving 0.1 g each of sunscreen oil a prepared according to Formulation Example 1 and mixed oil b of 60 parts of liquid paraffin and 39 parts of olive oil in 100 ml of an ethanol / hexane (1: 1) mixed solution were measured. As shown in FIG.
［発明の効果］ 本発明に用いられるα−デヒドロアミノ酸誘導体は、27
0〜330nmで、104以上の高い分子吸光係数を有し、皮膚
の紅斑の原因と考えられる290〜320nm、およびポリエチ
レン、ポリプロピレン、ポリ塩化ビニル等の樹脂の劣化
原因と考えられている300〜320nmの紫外線に対し、高い
吸収能を持つ。[Effect of the invention] The α-dehydroamino acid derivative used in the present invention is 27
It has a high molecular extinction coefficient of 10 4 or more at 0 to 330 nm and is considered to be the cause of erythema of the skin 290 to 320 nm, and 300 to 300 which is considered to be the cause of deterioration of polyethylene, polypropylene, polyvinyl chloride and other resins. It has a high absorption ability for 320 nm ultraviolet light.
一般式（１）で表わされるα−デヒドロアミノ酸誘導体
のうちCOR2がカルボキシル基のものは、エタノール等の
アルコールに対し、良好な溶解性を示し、又COR2がカル
ボキシル基の塩（例えばナトリウム塩、トリエタノール
アミン塩）のものは、水に対し高い溶解性を示す。更
に、COR2がエステル基の場合は、オリーブ油、流動パラ
フィン等の有機溶剤に良く溶解する。このように、COR2
を適宜、選択することにより、水、動植物油、有機溶剤
夫々に良く溶解させることができ、化粧水、ヘアークリ
ーム、日焼け止め油等の化粧料に添加した際、安定な配
合物を得ることができる。Among the α-dehydroamino acid derivatives represented by the general formula (1), those in which COR 2 is a carboxyl group have good solubility in alcohol such as ethanol, and COR 2 is a salt of a carboxyl group (for example, sodium salt). , Triethanolamine salt) has high solubility in water. Furthermore, when COR 2 is an ester group, it dissolves well in organic solvents such as olive oil and liquid paraffin. Thus, COR 2
Can be dissolved in water, animal and vegetable oils, organic solvents, respectively, by appropriate selection, and when added to cosmetics such as lotion, hair cream, sunscreen oil, a stable formulation can be obtained. it can.
また、本発明で用いられるα−デヒドロアミノ酸誘導体
は190〜240℃という高い融点を持つ為、樹脂へ配合した
場合は、混練、成型温度で安定で、熱安定性に優れた成
型品を得ることができる。Moreover, since the α-dehydroamino acid derivative used in the present invention has a high melting point of 190 to 240 ° C., when blended into a resin, it is stable at kneading and molding temperatures, and a molded product excellent in thermal stability is obtained. You can
本発明の紫外線吸収剤を市販のもの（例えば、ベンゾフ
ェノン系、トリアゾール系、サリチル酸系吸収剤）と比
較した場合、殊に酸素存在下に於ける紫外線の作用に
対して優れた抑制効果を有する。熱安定性、光安定性
が高く、効果の持続性が良い。２〜10倍の紫外線分子
吸光係数を有する。各種重合体材料との相溶性が良好
である為、繊維、樹脂などの可塑剤として使用される一
方、黄変防止剤としても用いることができる等の効果が
ある。When the ultraviolet absorber of the present invention is compared with commercially available ones (for example, benzophenone-based, triazole-based, salicylic acid-based absorbers), it has an excellent suppressing effect on the action of ultraviolet rays, especially in the presence of oxygen. It has high thermal stability and light stability, and has a long-lasting effect. It has a UV molecular extinction coefficient of 2 to 10 times. Since it has good compatibility with various polymer materials, it can be used not only as a plasticizer for fibers, resins, etc., but also as an anti-yellowing agent.
上述したごとく、本発明の用途範囲は、香粧品工業、プ
ラスチック工業、有機薬品工業、写真工業、食品工業、
繊維工業などであり、極めて広い。As described above, the application range of the present invention includes the cosmetics industry, the plastics industry, the organic chemicals industry, the photography industry, the food industry,
It is extremely wide, such as in the textile industry.
殊に、紫外線吸収波長が、240〜360nm（最大吸収波長30
0〜340nm）にあり、香粧品に用いた場合は、他に比類の
ない選択的吸収性をもった日焼け、紅斑防止化粧品とな
り、また、ポリエチレン、ポリプロピレン、ポリ塩化ビ
ニルなど、重合体中に、混入した場合、紫外線による劣
化を、著しく軽減する。Especially, the ultraviolet absorption wavelength is 240 to 360 nm (maximum absorption wavelength 30
0 to 340 nm), when used in cosmetics, it provides sunburn and erythema-preventing cosmetics with unparalleled selective absorbability, and also in polymers such as polyethylene, polypropylene and polyvinyl chloride. When mixed, the deterioration due to ultraviolet rays is significantly reduced.
α−デヒドロアミノ酸誘導体エタノール溶液の分子吸光
係数と波長の関係を図１に示す。 α−デヒドロアミノ酸誘導体を配合した日焼け止め油の
吸光度と波長の関係を図２に示す。The relationship between the molecular extinction coefficient and the wavelength of the ethanol solution of the α-dehydroamino acid derivative is shown in FIG. FIG. 2 shows the relationship between the absorbance and the wavelength of the sunscreen oil containing the α-dehydroamino acid derivative.
Claims (1)
ロアミノ酸誘導体を有効成分とする紫外線吸収剤。 （式中、Ａはフェニル基、イミダゾリル基、インドリル
基、フリル基、ピロリル基、チオフリル基またはピリジ
ル基であり、R1は水素原子、ヒドロキシ基またはアルコ
キシ基であり、COR2はカルボキシル基もしくはその塩ま
たはエステル基であり、そしてR3はアシル基またはベン
ジルオキシカルボニル基である。）1. An ultraviolet absorber containing an α-dehydroamino acid derivative represented by the following general formula (1) as an active ingredient. (In the formula, A is a phenyl group, an imidazolyl group, an indolyl group, a furyl group, a pyrrolyl group, a thiofuryl group or a pyridyl group, R 1 is a hydrogen atom, a hydroxy group or an alkoxy group, and COR 2 is a carboxyl group or its A salt or ester group, and R 3 is an acyl group or a benzyloxycarbonyl group.)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7993485 | 1985-04-15 | ||
| JP60-79934 | 1985-04-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6236484A JPS6236484A (en) | 1987-02-17 |
| JPH0753861B2 true JPH0753861B2 (en) | 1995-06-07 |
Family
ID=13704145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8346886A Expired - Lifetime JPH0753861B2 (en) | 1985-04-15 | 1986-04-11 | UV absorber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753861B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5085903A (en) * | 1990-06-11 | 1992-02-04 | Ppg Industries, Inc. | Coatings for the protection of products in light-transmitting containers |
| EP0852137B1 (en) * | 1996-11-29 | 2005-08-10 | Basf Aktiengesellschaft | Cosmetic compositions containing a photostable UV-A filter |
| EP1407756B2 (en) * | 2002-09-13 | 2016-09-28 | Kao Corporation | Hair dye composition comprising methine dye |
| WO2007014848A2 (en) * | 2005-07-29 | 2007-02-08 | Ciba Specialty Chemicals Holding Inc. | Stabilization of body-care and household products against degradation by uv radiation using merocyanine derivatives |
| GB0914287D0 (en) * | 2009-08-14 | 2009-09-30 | Pci Biotech As | Compositions |
-
1986
- 1986-04-11 JP JP8346886A patent/JPH0753861B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6236484A (en) | 1987-02-17 |
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