KR20050026775A - A novel thiophene compound for ultraviolet absorbers - Google Patents

A novel thiophene compound for ultraviolet absorbers Download PDF

Info

Publication number
KR20050026775A
KR20050026775A KR1020030062904A KR20030062904A KR20050026775A KR 20050026775 A KR20050026775 A KR 20050026775A KR 1020030062904 A KR1020030062904 A KR 1020030062904A KR 20030062904 A KR20030062904 A KR 20030062904A KR 20050026775 A KR20050026775 A KR 20050026775A
Authority
KR
South Korea
Prior art keywords
ultraviolet
thiophene compound
compound
formula
derivatives
Prior art date
Application number
KR1020030062904A
Other languages
Korean (ko)
Inventor
박정호
김윤철
Original Assignee
주식회사 코오롱
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 주식회사 코오롱 filed Critical 주식회사 코오롱
Priority to KR1020030062904A priority Critical patent/KR20050026775A/en
Publication of KR20050026775A publication Critical patent/KR20050026775A/en

Links

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
    • A61K8/4986—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with sulfur as the only hetero atom
    • 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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)

Abstract

A thiophene compound for absorbing ultraviolet and a preparation method thereof are provided, which thiophene compound has improved ultraviolet absorbing activity in the UVA(long wavelength UV) region, and improved solubility, miscibility and compatibility to various organic solvents. The thiophene compound for absorbing ultraviolet, represented by formula (1) is provided, wherein R1 is hydrogen, hydroxy or C1-C10 alkyl or alkoxy; and R2 is hydrogen or C1-C10 alkyl. The method for preparing the thiophene compound as an ultraviolet absorber comprises condensing thiophene-2-carbox aldehyde and its derivatives with 2-hydroxyacetophenone and its derivatives through aldol reaction.

Description

신규한 자외선흡수제용 치오펜 화합물 및 그 제조방법{A novel thiophene compound for ultraviolet absorbers}A novel thiophene compound for ultraviolet absorbers}

본 발명은 신규한 자외선흡수제용 치오펜 화합물 및 그 제조방법에 관한 것으로서, 더욱 상세하게는 화장품 원료 등에 유용한 자외선 흡수제로 사용할 수 있는 신규한 치오펜 화합물과 이를 제조하는 방법에 관한 것이다.The present invention relates to a novel UV absorber for a UV absorber and a method for producing the same, and more particularly, to a novel thiphene compound that can be used as a UV absorber useful in cosmetic raw materials and the like and a method for producing the same.

자외선은 사람의 피부에 다양한 영향을 주는 것으로 알려져 있다. Ultraviolet rays are known to have various effects on human skin.

사람의 피부에 도달하는 자외선은 그 대부분이 태양광선으로, 이 태양광선 속에 포함되어 있는 자외선은 그 파장에 따라 구분된다. 일반적으로 장파장 자외선(400∼320nm)을 UVA, 중파장 자외선(320∼280nm)을 UVB, 단파장 자외선(280nm 이하)을 UVC라고 일컫는다. Most of the ultraviolet rays that reach the human skin are sunlight, and the ultraviolet rays contained in these rays are classified according to their wavelength. Generally, long wavelength ultraviolet rays (400-320 nm) are called UVA, medium wavelength ultraviolet rays (320-280 nm) are called UVB, and short wavelength ultraviolet rays (280 nm or less) are called UVC.

UVA는 피부 표면의 환원 멜라민을 산화시켜 일광욕시에 피부를 구리빛으로 태우는 선탠 현상을 일으키고, UVB는 사람의 피부에 홍반과 같은 급성염증이나 화상을 일으키고, UVC는 그 대부분이 대기중의 오존에 흡수되어 지표에 도달하는 양은 극히 미미한 것으로 알려져 있다. UVA oxidizes the reduced melamine on the surface of the skin, causing tanning that burns the skin coppery when sunbathing, UVB causes acute inflammation or burns such as erythema on human skin, and UVC is mostly in the ozone in the air The amount absorbed and reached the surface is known to be minimal.

따라서 기존의 화장품용 자외선 흡수제는 주로 피부 염증 및 화상의 원인이 되는 UVB(290∼320nm) 영역으로부터 피부를 보호하는데 관심을 가져왔다. 그러나 전자현미경 및 조직화학적 기술의 발달에 따라 UVA 파장의 자외선도 피부에 나쁜 영향을 주는 것이 밝혀졌다. 특히 UVA는 UVB와는 달리 그 에너지가 피부 내부의 진피에까지 도달해, 혈관벽, 결합조직 중의 탄성섬유에 영향을 주고 이 영향은 피부노화를 촉진할 뿐만 아니라 UVB에 의한 피부변성을 증진시키는 한 요인임이 밝혀졌다. Therefore, conventional UV absorbers for cosmetics have been of interest for protecting the skin from the UVB (290 ~ 320nm) area that causes skin inflammation and burns. However, with the development of electron microscopy and histochemical techniques, it has been found that ultraviolet rays at the UVA wavelength also adversely affect the skin. In particular, UVA, unlike UVB, reaches its dermis inside the skin, affecting blood vessel walls and elastic fibers in connective tissue, and this effect not only promotes skin aging but also promotes skin degeneration by UVB. lost.

따라서 피부의 노화촉진을 예방하기 위해서는 UVB 뿐만 아니라 UVA로부터도 피부를 보호하는 것이 중요하게 되었다. 그러나, UVA 파장영역의 자외선 흡수제는 UVB 흡수제에 비해 그 수가 극히 적어 사용에 제약이 많이 있었다. Therefore, in order to prevent skin aging, it is important to protect the skin from UVA as well as UVB. However, the number of ultraviolet absorbers in the UVA wavelength range is extremely small compared to the UVB absorbers, so that there are many restrictions.

따라서, 본 발명은 UVA 영역의 자외선에 대한 흡수력이 우수한 자외선 흡수제, 특히 화장품 등에 유효한 UVA 영역의 자외선 흡수제를 제공하는 데 그 목적이 있다.Accordingly, an object of the present invention is to provide an ultraviolet absorbent having excellent absorption of ultraviolet rays in the UVA region, particularly an ultraviolet absorbent in the UVA region, which is effective in cosmetics and the like.

상기와 같은 목적을 달성하기 위한 본 발명의 자외선 흡수제는 다음 화학식 1로 표시되는 치오펜 화합물인 것임을 그 특징으로 한다.Ultraviolet absorber of the present invention for achieving the above object is characterized in that the thiophene compound represented by the following formula (1).

화학식 1Formula 1

상기 식에서, R1은 수소원자, 하이드록시기 또는 탄소수 1 내지 10의 알킬기 또는 알콕시기이고, R2는 수소원자 또는 탄소수 1 내지 10의 알킬기이다.Wherein R 1 is a hydrogen atom, a hydroxy group or an alkyl group or alkoxy group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명자들은 다양한 화합물의 UV 흡수도와 각종 기질과의 상용성을 연구하여 다음 화학식 1로 표시되는 치오펜 유도체가 UVA 영역에서 우수한 흡수력을 갖는 것을 확인하고 본 발명에 이르게 된 것이다.The present inventors to a study by the compatibility of the UV absorption of various compounds to help various substrates and leads to the present invention confirmed that it has the following superior absorption in the UVA region value thiophene derivative represented by the general formula (1).

화학식 1로 표시되는 치오펜 화합물은 치오펜-2-카복스알데히드 및 그 유도체와 2-히드록시아세토페논 및 그 유도체를 공지의 알돌 반응으로 축합시켜 합성할 수 있는 바, 개략적으로는 다음 반응식 1에 나타낸 바와 같다.The thiophene compound represented by Chemical Formula 1 may be synthesized by condensing thiophen-2-carboxaldehyde and its derivatives with 2-hydroxyacetophenone and its derivatives in a known aldol reaction. As shown in.

상기 식에서, R1과 R2는 상기에서 정의한 바와 같다.Wherein R 1 and R 2 are as defined above.

치오펜-2-카복스알데히드 및 그 유도체로는 5-메틸치오펜-2-카복스알데히드가 바람직하다.As the thiopene-2-carboxaldehyde and derivatives thereof, 5-methylthiophene-2-carboxaldehyde is preferable.

그리고, 2-히드록시아세토페논의 유도체로는 2,4-디히드록시아세토페논, 2-히드록시-4-옥틸록시아세토페논, 2-히드록시-4-메틸아세토페논이 바람직하다. As the derivative of 2-hydroxyacetophenone, 2,4-dihydroxyacetophenone, 2-hydroxy-4-octyloxyacetophenone, and 2-hydroxy-4-methylacetophenone are preferable.

치오펜-2-카복스알데히드 및 그 유도체와 2-히드록시아세토페논 및 그 유도체는 1.0:1.0 ∼ 1.0:2.0 몰비 되도록 사용하는 것이 바람직하다. It is preferable to use thiopene-2-carboxaldehyde and its derivatives, and 2-hydroxyacetophenone and its derivatives in a molar ratio of 1.0: 1.0 to 1.0: 2.0.

반응시 용매로는 물, 탄소수 1 내지 4의 알코올류, 또는 물과 알코올류의 혼합물을 사용할 수 있고, 염기로는 알카리 또는 알카리토류 금속의 하이드록사이드 또는 알콕사이드를 사용하는 것이 가능하다. In the reaction, water, alcohols having 1 to 4 carbon atoms, or a mixture of water and alcohols can be used, and as the base, hydroxides or alkoxides of alkali or alkaline earth metals can be used.

반응온도는 0℃ 내지 용매 또는 혼합용매의 끓는 온도 사이에서 반응시키는 것이 바람직하다. The reaction temperature is preferably reacted between 0 ° C. and the boiling temperature of the solvent or mixed solvent.

이와같은 과정을 통해 얻어진 화학식 1로 표시되는 치오펜 화합물은 UVA 영역에서의 자외선 흡수가 우수한 특징을 갖는 바, 이 화합물을 특히 화장품 원료로 사용되는 각종 기제 및 각종 유기용제 등에 대한 용해성, 혼화성, 상용성 등에서 우수한 특징을 갖는다.The thiophene compound represented by Chemical Formula 1 obtained through such a process has excellent ultraviolet absorption in the UVA region, so that the compound has solubility, miscibility, and the like in various bases and various organic solvents, which are used as raw materials for cosmetics. It has excellent features in compatibility and the like.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

실시예 1: 화학식 1에 있어서 RExample 1 R in Formula 1 1One , R, R 22 가 수소원자인 치오펜 화합물의 제조Preparation of Thiophene Compounds That Are Hydrogen Atoms

2-히드록시아세토페논 1.36g(10mmol)과 수산화바륨 2g을 에탄올 20㎖에 녹인 후, 치오펜-2-카복스알데히드 2.2g(20mmol)을 가한 후 3시간 동안 끓였다. 1.36 g (10 mmol) of 2-hydroxyacetophenone and 2 g of barium hydroxide were dissolved in 20 ml of ethanol, and 2.2 g (20 mmol) of thiophen-2-carboxaldehyde was added thereto, followed by boiling for 3 hours.

반응물을 냉각시킨 후 2N 염산으로 중화시키고, 에틸아세테이트로 추출하였다. 에탄올과 물에서 재결정하여 화합물 1a(화학식 1에서 R1, R2가 수소원자인 치오펜 화합물)을 얻었다.The reaction was cooled, neutralized with 2N hydrochloric acid, and extracted with ethyl acetate. Recrystallization from ethanol and water to give compound 1a (Ciophene compound wherein R 1 , R 2 in the formula 1 is a hydrogen atom).

1H-NMR(CDCl3, δ) : 12.8 (S, 1H), 6.9 - 8 (m, 9H) 1 H-NMR (CDCl 3 , δ): 12.8 (S, 1H), 6.9-8 (m, 9H)

한편, 화합물 1a 7.2mg을 클로로포름 1L에 녹인후 UV 흡수스펙트럼을 측정한 결과 최대흡수파장은 364nm이며, 이때의 몰흡광계수는 21,675이었다.Meanwhile, after dissolving 7.2 mg of Compound 1a in 1 L of chloroform, the UV absorption spectrum was measured, and the maximum absorption wavelength was 364 nm. The molar absorption coefficient at this time was 21,675.

실시예 2: 화학식 1에 있어서 RExample 2: R in Formula 1 1One =옥틸록시이고, R= Octyloxy, R 22 =수소원자인 치오펜 화합물의 제조= Preparation of Thiophene Compounds as Hydrogen Atoms

2-히드록시-4-옥틸록시아세토페논 0.53g(2mmol)을 수산화칼륨 5M 수용액 10㎖에 녹인 후, 치오펜-2-카복스알데히드 0.44g(4mmol)을 가한 후 상온에서 24시간 동안 반응시켰다. 0.53 g (2 mmol) of 2-hydroxy-4-octyloxyacetophenone was dissolved in 10 ml of 5 M aqueous solution of potassium hydroxide, and then 0.44 g (4 mmol) of thiophen-2-carboxaldehyde was added and reacted at room temperature for 24 hours. .

2N 염산수용액으로 중화한 후 에틸아세테이트로 추출하였다. 에탄올과 물에서 재결정하여 화합물 1b(화학식 1에 있어서 R1=옥틸록시이고, R2=수소원자인 치오펜 화합물) 7.5mg을 얻었다.It was neutralized with 2N aqueous hydrochloric acid solution and extracted with ethyl acetate. Recrystallization from ethanol and water yielded 7.5 mg of compound 1b (a thiopen compound having R 1 = octyloxy and R 2 = hydrogen atom in Chemical Formula 1).

1H-NMR(CDCl3, δ) : 12.8 (S, 1H), 6.9 - 8 (m, 7H), 4.0 (t, 2H), 1.3 - 1.5 (m, 12H), 1.0 (t, 3H) 1 H-NMR (CDCl 3 , δ): 12.8 (S, 1H), 6.9-8 (m, 7H), 4.0 (t, 2H), 1.3-1.5 (m, 12H), 1.0 (t, 3H)

한편, 화합물 1b 7.5mg을 클로로포름 1L에 녹인 후 UV 흡수스펙트럼을 측정한 결과 최대흡수파장은 367nm이며, 이때의 몰흡광계수는 22,759이었다.On the other hand, after dissolving 7.5 mg of Compound 1b in 1 L of chloroform and measuring the UV absorption spectrum, the maximum absorption wavelength was 367 nm and the molar absorption coefficient at this time was 22,759.

실험예 : 자외선 차단 분산액의 제조Experimental Example: Preparation of UV Protection Dispersion

상기 실시예 1 및 2로부터 얻어진 화합물 1a와 1b와 화장품 원료의 기재 및 유기용제에 대한 용해성, 혼화성, 상용성이 우수함을 확인하기 위하여 다음과 같이 자외선 차단 분산액을 제조하였다. 구체 조성은 다음 표 1과 같다.In order to confirm the excellent solubility, miscibility, and compatibility of the compounds 1a and 1b obtained from Examples 1 and 2 with the base material of the cosmetic raw material and the organic solvent, a UV blocking dispersion was prepared as follows. Specific compositions are shown in Table 1 below.

AA 화합물 1a 혹은 1bUV-B 흡수제모노스테아린산 그리세린세타놀디메틸폴리실록산스테아린산유동 파라핀Compound 1a or 1b UV-B Absorbent Monostearic acid Griserincetanoldimethylpolysiloxanes Stearic Acid Fluid Paraffin 1.0%1.0%1.0%1.0%2.0%2.0%10.0%1.0% 1.0% 1.0% 1.0% 2.0% 2.0% 10.0% BB 정제수트리에타놀아민1,3-부틸렌글리콜산화티탄유색안료벤토나이트방부제Purified water triethanolamine 1,3-butylene glycol titanium oxide pigmented pigment bentonite preservative 나머지 양1.0%5.0%3.0%적당량0.5%적당량Remaining amount 1.0% 5.0% 3.0% appropriate amount 0.5% appropriate amount CC 향료Spices 적당량A reasonable amount

<제조방법><Production method>

혼합물 (A)를 80℃로 가열 교반하여 용해시켰다. 혼합물 (B)를 78℃로 가열하면서 교반하여 균일하게 분산시켰다. 이렇게 조제된 (A)를 (B)에 가하고, 교반하면서 냉각시켜 고르게 유화시켰다. 60℃에서 (C)를 가하여 30℃까지 냉각시켜, O/W 형의 자외선차단 분산액을 제조하였다.The mixture (A) was dissolved by heating and stirring to 80 ° C. The mixture (B) was stirred while heating to 78 ° C. to uniformly disperse. (A) thus prepared was added to (B), cooled with stirring to emulsify it evenly. (C) was added at 60 degreeC, it cooled to 30 degreeC, and the O / W type | mold sunscreen dispersion liquid was produced.

이상에서 상세히 설명한 바와 같이, 본 발명에 따른 신규한 자외선 흡수제인 치오펜 화합물은 UVA 영역에서 우수한 자외선흡수력을 가지면서 화장품 원료로 사용되는 각종 기제 및 각종 유기용제 등에 대한 용해성, 혼화성, 상용성 등에서 우수하므로 화장품용 자외선 흡수제로 유용하다. As described in detail above, the novel ultraviolet absorber, the thiophene compound according to the present invention has excellent ultraviolet absorbing ability in the UVA region, solubility, miscibility, compatibility with various bases and organic solvents, etc. As it is excellent, it is useful as a UV absorber for cosmetics.

Claims (2)

다음 화학식 1로 표시되는 자외선 흡수제용 치오펜 화합물.The following chemicals are used in the ultraviolet absorbent thiphene compound represented by the formula (1). 화학식 1Formula 1 상기 식에서, R1은 수소원자, 하이드록시기 또는 탄소수 1 내지 10의 알킬기 또는 알콕시기이고, R2는 수소원자 또는 탄소수 1 내지 10의 알킬기이다.Wherein R 1 is a hydrogen atom, a hydroxy group or an alkyl group or alkoxy group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 치오펜-2-카복스알데히드 및 그 유도체와 2-히드록시아세토페논 및 그 유도체를 알돌 반응으로 축합시켜 다음 화학식 1로 표시되는 자외선흡수제용 치오펜 화합물을 제조하는 방법.A method of preparing a thiefpene compound for ultraviolet absorbers represented by the following Chemical Formula 1 by condensing thiopene-2-carboxaldehyde and derivatives thereof with 2-hydroxyacetophenone and derivatives thereof by an Aldol reaction. 화학식 1Formula 1 상기 식에서, R1은 수소원자, 하이드록시기 또는 탄소수 1 내지 10의 알킬기 또는 알콕시기이고, R2는 수소원자 또는 탄소수 1 내지 10의 알킬기이다.Wherein R 1 is a hydrogen atom, a hydroxy group or an alkyl group or alkoxy group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
KR1020030062904A 2003-09-09 2003-09-09 A novel thiophene compound for ultraviolet absorbers KR20050026775A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020030062904A KR20050026775A (en) 2003-09-09 2003-09-09 A novel thiophene compound for ultraviolet absorbers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020030062904A KR20050026775A (en) 2003-09-09 2003-09-09 A novel thiophene compound for ultraviolet absorbers

Publications (1)

Publication Number Publication Date
KR20050026775A true KR20050026775A (en) 2005-03-16

Family

ID=37384424

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020030062904A KR20050026775A (en) 2003-09-09 2003-09-09 A novel thiophene compound for ultraviolet absorbers

Country Status (1)

Country Link
KR (1) KR20050026775A (en)

Similar Documents

Publication Publication Date Title
JP2000044452A (en) Use of 4,4-diarylbutadiene as uv filter, sunsreen- containing cosmetic and pharmaceutical preparation, 4,4-diarylbutadiene and pharmaceutical preparation
EP0833812A1 (en) Chemical compounds and methods of production thereof
KR20070113310A (en) Benzoic acid exter compounds, compositions, uses and methods related thereto
EP1904500A1 (en) New derivatives of heptaazaphenalene, methods for obtaining them, and their use as protecting agents against uv radiation
US5520906A (en) Triazine derivatives with UV filter properties
EP0714880A1 (en) Bis(methylidene)-phenylene-derivatives
EP2832727B1 (en) Novel benzylidene azolidine derivative or salt thereof
KR20060052830A (en) Dibenzoilmethane derivative compounds, the use thereof in the form of photoactivable solar filters and cosmetic compositions containing said compounds
JPS6396120A (en) Anti-suntan cosmetic
US4070450A (en) Sunscreening compound and method
JPH0812664A (en) Kojic acid derivative
KR20050026775A (en) A novel thiophene compound for ultraviolet absorbers
JPS61140543A (en) 4-methoxy-2&#39;-carboxydibenzoylmethane and salt thereof
EP0581954B1 (en) Use of alpha-hydroxyketoalkyl derivatives as protective light filters
US3065144A (en) Sun screening method using acetylated p-amino-cinnamates
US20100008874A1 (en) Substituted pyrimidines, process for their production and their use as effective absorbents of uv irradiation
Li et al. Functional Polymers. XXII. Ultraviolet Absorbers with 2 (2-Hydroxyphenyl) 2H-benzotriazole and 2-Hydroxybenzophenone (or Acetophenone) Chromophors in the Same Molecule
KR100449228B1 (en) EGCG derivatives, Preparation method thereof and cosmetic composition containing thereof
JP3534938B2 (en) Hydantoin derivatives, ultraviolet absorbers and skin external preparations
CA1069054A (en) 4-pyridoxinate derivatives as light screening agents
JP3976816B2 (en) Hydantoin derivatives, UV absorbers and skin external preparations
EP2046279A1 (en) Use of aminophenylbenzotriazole derivatives for protecting human and animal skin and hair from the harmful effects of uv radiation and cosmetic compositions thereof
JP3170389B2 (en) Silicone hydantoin derivatives, UV absorbers and skin external preparations
KR101298275B1 (en) Improved polyamide compound and its method of manufacture
JPS62158206A (en) Ultraviolet ray absorber

Legal Events

Date Code Title Description
WITN Withdrawal due to no request for examination