KR101614824B1 - Polydialkylsiloxane-bridged bi-photochromic molecules - Google Patents

Polydialkylsiloxane-bridged bi-photochromic molecules Download PDF

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KR101614824B1
KR101614824B1 KR1020117006235A KR20117006235A KR101614824B1 KR 101614824 B1 KR101614824 B1 KR 101614824B1 KR 1020117006235 A KR1020117006235 A KR 1020117006235A KR 20117006235 A KR20117006235 A KR 20117006235A KR 101614824 B1 KR101614824 B1 KR 101614824B1
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스티븐 마이클 파팅턴
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Abstract

이광변색성 분자는 폴리디알킬실록산 올리고머를 통해 연결된 2개의 광변색성 모이어티를 포함한다. 안과용 렌즈는 이광변색성 분자를 포함한다. 폴리머 호스트 물질은 상기 이광변색성 분자를 포함한다.The photochromic molecule comprises two photochromic moieties linked through a polydialkylsiloxane oligomer. The ophthalmic lens comprises a photochromic molecule. The polymer host material comprises the above photochromic molecules.

Description

폴리디알킬실록산-가교된 이광변색성 분자{Polydialkylsiloxane-bridged bi-photochromic molecules}Polydialkylsiloxane-bridged bi-photochromic molecules < RTI ID = 0.0 >

본 발명은 광변색성 분자에 관한 것이며, 특히 폴리디알킬실록산 올리고머 링커를 포함하는 이광변색성 분자(bi-photochromic molecules) 및 이들을 포함하는 제품에 관한 것이다.The present invention relates to photochromic molecules, and more particularly to bi-photochromic molecules comprising polydialkylsiloxane oligomeric linkers and products containing them.

광변색(Photochromism)은 잘 알려진 물리적 현상이고, “다른 구별가능한 흡수 스펙트럼을 가지는 두 상태 사이에서 전자기 방사에 의해 한 방향 또는 두 방향으로 유도된 단일 화학종의 가역 변환”으로서 정의된다. 이 현상의 자세한 논의는 “Photochromism : Molecules and Systems”, 개정판, H. Durr 와 H. Bouas-Laurent 편집, Elsevier, 2003.에서 볼 수 있다. 유기 광변색성 분자의 주요한 종류의 개관은 “Organic Photochromic and Thermochromic Compounds, Volume 1, Main Photochromic Families”, J. Crano와 R. Guglielmetti 편집, Plenum Press, 1999.에서 볼 수 있다. 광변색성 나프토피란의 구체적인 개관은“Functional Dyes”, Sung-Hoon Kim 편집, 85-137 페이지, Elsevier, Amsterdam, 2006에서 볼 수 있다.Photochromism is a well-known physical phenomenon and is defined as " reversible transformation of a single species induced in one or both directions by electromagnetic radiation between two states having different distinguishable absorption spectra ". A detailed discussion of this phenomenon can be found in "Photochromism: Molecules and Systems", ed., H. Durr and H. Bouas-Laurent, Elsevier, 2003. An overview of the major classes of organic photochromic molecules can be found in Organic Photochromic and Thermochromic Compounds, Volume 1, Main Photochromic Families, edited by J. Crano and R. Guglielmetti, Plenum Press, 1999. A specific overview of photochromic naphthopyran can be found in " Functional Dyes ", edited by Sung-Hoon Kim, pages 85-137, Elsevier, Amsterdam,

최근에 광변색성 분자에 대한 주요 사업 분야는 안과용 시장이며, 여기서 T-타입(열적으로 가역적인) 광변색성 재료(photochromics)가 사용된다. 안과용 시장용 유기 광변색성 분자의 가장 중요한 종류는 나프토피란(1,2-b 및 2,1-b 고리 시스템 둘다), 및 스피로-나트토옥사진(1,2-b 및 2,1-b 고리 시스템 둘다)이다. 이것은 상당히 특허 활동이 활발한 분야이여, 예를 들어 US 5,650,098 (1,2-b 나프토피란, Transitions), US 5,623,005 (2,1-b 나프토피란, Pilkington), US 5,446,151 (2,1-b 나프토옥사진, Pilkington), 및 US 6,303,673 (1,2-b 나프토옥사진, James Robinson)이다.Recently, the main business area for photochromic molecules is the ophthalmic market, where T-type (thermally reversible) photochromic materials are used. The most important classes of organic photochromic molecules for the ophthalmic market are naphthopyran (both 1,2-b and 2,1-b ring systems), and spiro-nattooks (1,2-b and 2,1 -b ring system). This is a field of considerable patent activity, for example US 5,650,098 (1,2-b naphthopyran, Transitions), US 5,623,005 (2,1-b naphthopyran, Pilkington), US 5,446,151 Pilkington), and US 6,303,673 (1,2-b naphthoque photograph, James Robinson).

특정 용도에 요구되는 특성으로 분자의 특성을 조율하기 위하여, 광변색성 분자의 광변색 특성과 물리적 특성을 변경시키기 위한 연구가 수행되고 있다. 한가지 접근방법은 다양한 장쇄 치환체를 부착하는 것이었다. Enichem (EP 0524692)는 장쇄 알콕시 치환체 및 장쇄 에스테르 치환체를 가진 옥사진을 청구한다.In order to adjust the characteristics of molecules with properties required for specific applications, research is being conducted to change photochromic properties and physical properties of photochromic molecules. One approach was to attach various long chain substituents. Enichem (EP 0524692) claims an oxazine with a long chain alkoxy substituent and a long chain ester substituent.

Polymers Australia의 특허(WO 04/41961)는 높은 유리 전이 온도(Tg)를 가진 강성 폴리머 매트릭스에서 단일 광변색성 분자의 퇴색 속도(fade speeds)에 대한 폴리디알킬실록산 사슬, 퍼플루오로알킬 사슬, 폴리에틸렌 글리콜 사슬 및 알킬 사슬의 효과를 밝힌다. 이 특허는 단일 광변색성 분자의 광변색 퇴색 속도에서 가장 큰 증가가 폴리디메틸실록산 사슬에 의해 야기되었다고 밝히고 있다. Polymers Australia의 후속 특허는 “리빙 중합(living polymerisation)”에 의해 생성된 폴리메틸(메타크릴레이트) 및 폴리부타크릴레이트 사슬(WO 05/105875, WO 06/24099) 및 폴리에테르 사슬(WO 05/105874)의 효과를 밝힌다. 상기 Polymers Australia 특허의 저자로부터의 논문(R. Evans et al, Nature 2005, VoI 4, p249)은 폴리디알킬실록산 사슬의 사용이 안과용 렌즈 매트릭스에서 단일 광변색성 화합물의 퇴색율(rate of fade)을 증가시키는데 가장 큰 향상을 준다는 것을 나타낸다. 상업적으로 수용가능한 색강도를 달성하면서도 증가된 퇴색율은, 안과용 렌즈에 바람직한 특성이다. Polymers Australia's patent (WO 04/41961) discloses a polydialkylsiloxane chain, a perfluoroalkyl chain, and a perfluoroalkyl chain with respect to the fade speeds of a single photochromic molecule in a rigid polymer matrix having a high glass transition temperature (Tg) The effect of polyethylene glycol chain and alkyl chain is revealed. This patent discloses that the greatest increase in photochromic fade rate of a single photochromic molecule is caused by a polydimethylsiloxane chain. Subsequent patents of Polymers Australia include poly (methyl methacrylate) and poly (butyrate) chains (WO 05/105875, WO 06/24099) and polyether chains (WO 05 / 105874). A paper from the author of the Polymers Australia patent (R. Evans et al, Nature 2005, VoI 4, p249) showed that the use of polydialkylsiloxane chains reduced the rate of fade of single photochromic compounds in ophthalmic lens matrices ), Which is the most significant increase in the number of patients. The increased discoloration rate, while achieving commercially acceptable color strength, is a desirable characteristic for ophthalmic lenses.

중합가능한 기들이 옥사진에 부착되어 있다(US 5821287, National Science Council Taiwan). 중합가능한 폴리알콕실화 피란은 PPG (WO 00/15629) 및 Transitions (WO 03/56390)에 의해 청구되어 있다.Polymerizable groups are attached to the ox photos (US 5821287, National Science Council Taiwan). Polymerizable polyalkoxylated pyran is claimed by PPG (WO 00/15629) and Transitions (WO 03/56390).

가교(bridge) 수단에 의해 두개의 광변색성 유닛을 연결하는 연구가 또한 수행되고 있다. Guglielmetti et al은 에탄, 에틸렌계, 아세틸렌계, 에스테르, 모노-, 바이- 및 터-티오펜 가교에 의해 옥사진과 피란을 연결했다(참조 F. Ortica et al, J. Photochem. Photobiol A, (2001), 139, 2-3; M. Frigoli et al, HeIv. Chim. Acta, Vol 83, (2000), P3043-3052; A. Yassar et al, Applied Physics Letters, (2002), Vol 80, 23, P4297-4299). Rodenstock (EP 0686685)은 피란들을 -CH2CH2- 가교에 의해 연결했고, 상기 가교는 광변색성 모이어티의 광변색 특성에 영향을 미치지 않는다는 것이 교시되어 있고: 상기 가교가 퇴색율 또는 색 강도와 같은 특성의 향상의 관점에서는 어떠한 잇점을 제공하지 않는다는 것은 명확하다. Zhao 및 Carreira(JACS 2002, 124, 8, p1582)는 비스-티오펜에 의해, 페닐기에 의해(Organic Letters, 2006, VoI 8 No. 1, p99), 및 올리코티오펜(Chenn. Eur. J. 2007, 13, 2671-2685)에 의해 연결된 비스-나프토피란을 제조했고, Coelho et al (Tetrahedron, 2005, 61, p11730)은 페닐, 페닐-O-페닐, 및 페닐-CH2CH2-페닐 가교 결합에 의해 피란들을 연결했다. Great Lakes (WO 00/39245)은 세개의 옥사진이 중앙의 트리아진에 부착된 삼량체 종(trimeric species)을 청구하였다. 또한, Great Lakes (WO 00/05325 및 WO 00/21968)은 두개, 세개 또는 네개의 옥사진이 중앙의 테트라메틸시클로테트라실록산 고리에 연결된 화합물을 청구한다. Research is also being carried out to link two photochromic units by means of bridging. Guglielmetti et al linked the oxazine and pyran with ethane, ethylenic, acetylenic, ester, mono-, bi- and terthiophene bridges (see F. Ortica et al, J. Photochem. Photobiol A, 2001, 139, 2-3; M. Frigoli et al, HeIv. Chim. Acta, Vol. 83, (2000), P3043-3052; A. Yassar et al., Applied Physics Letters, , P4297-4299). Rodenstock (EP 0686685) teaches that piranes are linked by -CH 2 CH 2 -crosslinking and that the crosslinking does not affect the photochromic properties of the photochromic moiety: the crosslinking has a discoloration rate or color strength It is clear that it does not provide any advantage in terms of the improvement of characteristics such as < Desc / Clms Page number 2 > Zhao and Carreira (JACS 2002, 124, 8, p1582) were synthesized by bis-thiophene, by phenyl groups (Organic Letters, 2006, VoI 8 No. 1, p99), and by olcotiophene. Phenyl-O-phenyl, and phenyl-CH 2 CH 2 -phenyl (phenyl) -phenyl-O-phenyl, The piranha was connected by crosslinking. The Great Lakes (WO 00/39245) claimed that the three jade photographs were trimeric species attached to the central triazine. Also, Great Lakes (WO 00/05325 and WO 00/21968) claim compounds in which two, three or four ox pictures are attached to the central tetramethylcyclotetrasiloxane ring.

그러나, 이들 공지된 많은 분자들은 느린 퇴색율, 불량 색강도, 및 불량 열적 안정성을 포함하는 단점들을 겪는다. 그 결과, 이들 많은 분자들은 예를 들어 안과용 렌즈에 병합과 같은 특정 용도에 잘 부합되지 않는다. 따라서, 향상된 특성을 나타내는 광변색성 분자에 대한 필요성이 존재한다.However, many of these known molecules suffer from drawbacks including slow fading rate, poor color strength, and poor thermal stability. As a result, many of these molecules are not well suited for particular applications, such as, for example, merging into ophthalmic lenses. Thus, there is a need for photochromic molecules that exhibit improved properties.

본 발명의 가장 넓은 측면에 의하면, 폴리디알킬실록산 올리고머를 통해 연결된 두개의 광변색성 모이어티를 포함하는 이광변색성 분자가 제공된다. According to a broadest aspect of the present invention there is provided a photochromic molecule comprising two photochromic moieties linked through a polydialkylsiloxane oligomer.

추가적인 일 측면에 따르면, 청구항 4항에 기재된 구조를 가지는 이광변색성 분자가 제공된다.According to a further aspect, there is provided a photochromic molecule having the structure as set forth in claim 4.

또한, 본 발명에 따른 이광변색성 분자를 포함하는 안과용 렌즈가 제공된다.Also provided is an ophthalmic lens comprising a photochromic molecule according to the present invention.

추가적인 일 측면에 따르면, 본 발명은 본 발명에 따른 이광변색성 분자를 포함하는 폴리머 호스트 재료(polymeric host material)를 제공한다. According to a further aspect, the present invention provides a polymeric host material comprising a photochromic molecule according to the present invention.

상기 분자들은 모체 광변색성 분자(parent photochromic molecules)에 비해 중합체 매트릭스에서의 퇴색율 면에서 상당한 향상을 나타낸다는 것이 발견되었다. 분자량과 존재하는 광변색성 유닛의 수 때문에, 본 발명의 화합물은 종종 모체 광변색성 분자에 비해 증가된 광변색성 컬러의 강도를 나타낸다. 본 발명의 화합물은 광변색성 안과용 렌즈용으로 특히 유용하다.It has been found that the molecules show a significant improvement in the discoloration rate in the polymer matrix as compared to the parent photochromic molecules. Due to the molecular weight and the number of photochromic units present, the compounds of the present invention often exhibit increased photochromic color strength compared to the parent photochromic molecules. The compounds of the present invention are particularly useful for photochromic ophthalmic lenses.

폴리머에 통합될 때, 이들 분자들은, 가교기에 의해 연결되지 않은 개개의 광변색성 분자에 비해, 열 안정성이 향상된다는 것을 뜻하지 않게 발견하였다. 이것은 본 발명의 분자들이 연결되지 않은 광변색성 분자들에 비해 더 높은 가공 온도를 요구하는 중합체에 통합될 수 있게 한다.When incorporated into polymers, these molecules have unexpectedly been found to improve thermal stability compared to individual photochromic molecules that are not linked by a crosslinking group. This allows the molecules of the present invention to be incorporated into polymers that require higher processing temperatures compared to unconnected photochromic molecules.

또한, 본 발명의 분자는 동일한 온도에서 동일한 폴리머에서 가공될 때 폴리디알킬실록산 올리고머를 통해 연결되지 않는 개개의 광변색성 분자에 비해 더 낮은 황변화 지수(yellowness index)의 유리한 특성을 가진다.In addition, the molecules of the present invention have advantageous properties of a lower yellowness index compared to individual photochromic molecules that are not linked through polydialkylsiloxane oligomers when processed in the same polymer at the same temperature.

유사하게, 본 발명의 화합물은 가교기를 포함하는 공지의 이광변색성 화합물에 비해 향상된 퇴색율, 향상된 광변색 색 강도, 증가된 열 안정성 및 감소된 황변화 지수의 잇점을 가진다.Similarly, the compounds of the present invention have the advantages of improved fade rate, improved photochromic color strength, increased thermal stability, and reduced sulfur change index compared to known photochromic compounds comprising crosslinking groups.

본 발명의 바람직한 일 구현예에서, 두개의 광변색성 분자가 중앙의 폴리디알킬실록산(PDAS) 사슬의 각각의 말단에 연결기를 포함하는 가교 수단에 의해 연결되어 신규한 폴리디알킬실록산 가교된 이광변색성 분자를 제공한다. 바람직하게는, 상기 가교는 중앙의 PDAS 사슬의 각각의 말단에서의 연결기로 이루어진다.In one preferred embodiment of the present invention, the two photochromic molecules are connected by a crosslinking means comprising a linking group to each end of a central polydialkylsiloxane (PDAS) chain to form a new polydialkylsiloxane crosslinked < RTI ID = 0.0 & Providing a discolorable molecule. Preferably, said bridging consists of a connector at each end of the central PDAS chain.

광변색성 유닛은 동일하거나 다를 수 있으며, 이는 다른 퇴색율을 가진 다른 발색단(chromophores)이 동일한 분자 내에 존재할 가능성을 허용한다. The photochromic units may be the same or different, allowing the possibility that different chromophores with different fade rates are present in the same molecule.

본 발명이 분자는 폴리디알킬실록산 사슬에 의해 연결된 두개의 광변색성 모이어티 또는 분자를 포함한다. 폴리디알킬실록산 가교, 또는 링커가 각각의 말단에 연결기를 포함하는 것이 매우 바람직하다. 바람직하게는, 가교 또는 링커는 중앙의 폴리디알킬실록산 사슬의 각각의 말단에서의 연결기로 이루어진다. 임의의 적합한 폴리디알킬실록산 사슬 및 연결기가 사용될 수 있다.The molecule of the present invention comprises two photochromic moieties or molecules linked by a polydialkylsiloxane chain. It is highly preferred that the polydialkylsiloxane bridges, or linkers, contain a linking group at each end. Preferably, the bridging or linker consists of a linking group at each end of the central polydialkylsiloxane chain. Any suitable polydialkylsiloxane chain and linking group may be used.

바람직하게는, 상기 화합물은 하기 일반식을 갖는다: Preferably, the compound has the general formula:

Figure 112011019688345-pct00001
Figure 112011019688345-pct00001

여기서, PC 및 PC’는 광변색성 모이어티를 나타내고; PDAS는 폴리디알킬실록산 사슬을 나타내고; 및 L 및 L’는 연결기를 나타낸다.Where PC and PC 'represent photochromic moieties; The PDAS represents a polydialkylsiloxane chain; And L and L 'represent a linking group.

PC 및 PC’는 동일하거나 다를 수 있다. PC 및 PC’가 독립적으로 일반 구조 Ⅰ 내지 Ⅳ의 광변색성 모이어티를 나타내는 것이 특히 바람직하다:PC and PC 'may be the same or different. It is particularly preferred that PC and PC 'independently represent photochromic moieties of general structure I to IV:

Figure 112011019688345-pct00002
Figure 112011019688345-pct00002

여기서 R1 및 R2는 독립적으로 수소, 선형 또는 분지형 C1 -10 알킬, 선형 또는 분지형 C1 -10 알콕시, C1 -10 하이드록시알콕시, C1 -10 알콕시(C1-10)알콕시, 페닐, C1 -10 알콕시페닐, 할로겐, C1 -5 할로알킬, C1 -5 알킬아미노, C1 -5 디알킬아미노, 아릴아미노, 디아릴아미노, 아릴 C1 -5 알킬아미노, 또는 시클릭 아미노기를 나타내고; Wherein R1 and R2 are independently hydrogen, linear or branched C 1 -10 alkyl, linear or branched C 1 -10 alkyl, C 1 -10-hydroxy-alkoxy, C 1 -10 alkoxy (C 1-10) alkoxy, phenyl, C 1 -10 alkoxy, phenyl, halogen, C 1 -5 alkyl, halo, C 1 -5 alkyl, C 1 -5 dialkylamino, arylamino, diarylamino, aryl C 1 -5 alkyl, or when Represents a click amino group;

R3는 수소, 선형 또는 분지형 C1 -10 알킬 C3-C20 시클로알킬, C6-C2O 바이시클로알킬, 선형 또는 분지형 C2 -10 알케닐, 선형 또는 분지형 C1 -10 알콕시, C1 -10 하이드록시알킬, C1 -10 아미노알킬, 선형 또는 분지형 C1 -20 알콕시카르보닐, 카르복실, 할로겐, 아릴옥시카르보닐, 포밀, 아세틸 또는 아로일을 나타내고; R3 is hydrogen, a linear or branched C 1 -10 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 2O alkyl, bicycloalkyl, linear or branched C 2 -10 alkenyl, linear or branched C 1 -10 alkoxy , C 1 -10 alkyl, hydroxy, C 1 -10 alkyl, amino, C 1 -20 linear or branched alkoxycarbonyl, carboxyl, halogen, aryloxy-carbonyl, formyl, represents acetyl or aroyl;

R4는 R3에 상술한 기외에, 페닐, C1 -10 알콕시페닐, C1 -10 디알콕시페닐, C1 -10 알킬페닐, C1 -10 디알킬페닐을 나타내고;R4 is a gioe described in R3, phenyl, C 1 -10 alkoxyphenyl, C 1 -10-dialkoxy phenyl, C 1 -10 alkyl, phenyl, C 1 -10 alkyl di represents phenyl;

또는 R3 및 R4는 함께 하기 타입의 고리형 구조를 형성하며 Or R3 and R4 together form a cyclic structure of the following type

Figure 112011019688345-pct00003
Figure 112011019688345-pct00003

R5, R6, R7, R8, R9, R10, R14, R15, R16는 R1 및 R2에 대해 상술한 바와 같고;R5, R6, R7, R8, R9, R10, R14, R15, R16 are as defined above for R1 and R2;

R11는 선형 또는 분지형 C1 -20 알킬, C3-C20 시클로알킬, C6-C20 바이시클로알킬, (C1-5 알킬)아릴, (C1 -5 알킬)시클로알킬, (C1 -5 알킬) 바이시클로알킬, C1 -5 할로알킬, C1-5 디할로알킬 또는 C1 -5 트리할로알킬을 나타내고; R11 is a linear or branched C 1 -20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 bicycloalkyl alkyl, (C 1-5 alkyl) aryl, cycloalkyl, (C (C 1 -5 alkyl) 1-5 alkyl) bicyclo alkyl, C 1-5 haloalkyl, alkyl, or C 1-5 alkyl denotes a trihaloalkyl with 1-5 C-dihalo;

R12 및 R13은 C1 -10 알킬, C1 -5 알킬 알콕시카르보닐을 나타내거나, 또는 C5 -7 고리를 함께 형성하고; 및R12 and R13 are C 1 -10 alkyl, C 1 -5 alkyl, or represent alkoxycarbonyl, or form a C 5 -7 ring together; And

R17 및 R18은 선형 또는 분지형 C1 -10 알킬, C1 -10 하이드록시알킬을 나타내거나 또는 함께 C5 -7 고리를 형성한다. R17 and R18 form a linear or branched C 1 -10 alkyl, C 1 -10-hydroxy-C 5 -7 ring represent alkyl or together.

L 및 L'는 동일하거나 다를 수 있고, 연결기를 나타낸다. 임의의 적합한 연결기가 사용될 수 있다. L 및 L'는 하기 형태의 연결기를 나타내는 것이 바람직하고L and L 'may be the same or different and represent a linking group. Any suitable linker may be used. L and L 'preferably represent a linking group of the form

Figure 112011019688345-pct00004
Figure 112011019688345-pct00004

여기서 Y는 독립적으로 산소 또는 황이며, R19는 수소 또는 C1 -10 선형 또는 분지형 알킬이고, R20은 C1 -10 선형 또는 분지형 알킬이고, p는 1 내지 15의 정수이고, 및 r은 0 내지 10의 정수이고, 및 여기서 Q는 선형 또는 분지형 C1 -10 알킬, C1 -10 알케닐 또는 1,2-, 1,3, 또는 1,4-치환된 아릴, 또는 치환된 헤테로아릴이다. Wherein Y is independently oxygen or sulfur, R19 is hydrogen or C 1 -10 linear or branched alkyl, and, R20 is C 1 -10 linear or a branched alkyl, p is an integer from 1 to 15, and r is an integer from 0 to 10, and wherein Q is a linear or branched C 1 -10 alkyl, C 1 -10 alkenyl, or 1,2, 1,3, or 1,4-substituted aryl, or substituted heteroaryl / RTI >

Y는 산소가 바람직하다.Y is preferably oxygen.

특히 바람직한 링커기(linker group) L 및 L' 는:Particularly preferred linker groups L and L 'are:

Figure 112011019688345-pct00005
이다.
Figure 112011019688345-pct00005
to be.

PDAS는 폴리디알킬실록산 사슬을 나타낸다. 바람직하게는, PDAS는 하기 형태의 올리고머를 나타내고PDAS represents a polydialkylsiloxane chain. Preferably, the PDAS represents an oligomer of the form

Figure 112011019688345-pct00006
Figure 112011019688345-pct00006

여기서 R19는 C1 -10 알킬이고, n은 4 내지 75의 정수이다. Wherein R19 is a C 1 -10 alkyl, n is an integer from 4 to 75.

폴리디알킬실록산 올리고머는 예를 들어 Gelest Inc, Shin-Etsu Chemical Co. Ltd; Chisso Corp; Toshiba Silicone Co. Ltd; 및 Toray-Dow Corning Co. Ltd로부터 상업적으로 입수가능하다. Polydialkylsiloxane oligomers are commercially available from, for example, Gelest Inc, Shin-Etsu Chemical Co. Ltd; Chisso Corp; Toshiba Silicone Co. Ltd; And Toray-Dow Corning Co. Lt; / RTI >

적합한 폴리디알킬실록산 올리고머는 이에 한정되는 것은 아니지만, 폴리디메틸실록산 올리고머를 포함하며, 따라서 R19는 바람직하게는 메틸이다.Suitable polydialkylsiloxane oligomers include, but are not limited to, polydimethylsiloxane oligomers, and thus R19 is preferably methyl.

n은 1 내지 30(경계 포함)인 것이 바람직하다. 특히 바람직하게는, R19는 메틸이고 n은 6 내지 30의 정수이다.
바람직한 폴리디메틸실록산 올리고머는 Gelest Inc.로부터 입수가능한 올리고머 DMS-B12(α, w-비스 카르복시-종결된 폴리디메틸실록산), DMS-C15, DMS-C16 또는, DMS-C21(α, w-비스 하이드록시-종결된 폴리디메틸실록산들), DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A211 및 DMS-A214(α, w-비스 아미노-종결된 폴리디메틸실록산들); Shin-Etsu로부터 입수가능한 KF-6001, KF-6002, KF-6003, KF-8010, X-22-160AS, X-22-162A, X-22-161A, X-22-161B 및 X-22-162C; 및 Chisso로부터 입수가능한 Silaplane FM-44를 포함한다. Gelest로부터의 상기 올리고머 DMS-B 12, DMS-C15, DMS-C16, DMS-C21, DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A211 및 DMS-A214가 특히 바람직하다. 이들은 하기의 구조 및 대략적인 분자량 또는 분자량 범위를 가지는 것으로 인용된다. 편의상, 복잡한 시스템적인 명칭(또한 올리고머는 혼합물이므로, 엄격하게 정확하지는 않음)보다, Gelest 명명법이 하기의 폴리디알킬실록산 올리고머를 명명하는데 사용된다.n is preferably 1 to 30 (inclusive). Particularly preferably, R19 is methyl and n is an integer of 6 to 30.
Preferred polydimethylsiloxane oligomers include the oligomers DMS-B12 (a, w-biscarboxy-terminated polydimethylsiloxane), DMS-C15, DMS-C16 or DMS-C21 (a, w- DMS-A11, DMS-A21, DMS-A211 and DMS-A214 (a, w-bisamino-terminated polydimethylsiloxanes); X-22-161A, X-22-161B, and X-22-161B available from Shin-Etsu, KF-6001, KF-6002, KF-6003, KF- 162C; And Silaplane FM-44, available from Chisso. The oligomers DMS-B12, DMS-C15, DMS-C16, DMS-C21, DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A211 and DMS-A214 from Gelest are particularly preferred. They are cited as having the following structures and approximate molecular weight or molecular weight ranges. For convenience, the Gelest nomenclature is used to designate the polydialkylsiloxane oligomers described below, rather than the complex systematic designations (and because oligomers are mixtures, not strictly precise).

삭제delete

Figure 112011019688345-pct00007
Figure 112011019688345-pct00007

Figure 112011019688345-pct00008
Figure 112011019688345-pct00008

당업자가 알고 있는 바와 같이, 상업적으로 입수가능한 폴리디메틸실록산 올리고머는 일반적으로 평균 분자량 또는 분자량 범위를 가지고 공급되고, 디메틸실록산의 반복 단위의 수로서 인용된 모든 수치는 평균값으로 해석된다.As known to those skilled in the art, commercially available polydimethylsiloxane oligomers are generally supplied in a range of average molecular weights or molecular weights, and all numbers recited as the number of repeating units of dimethylsiloxane are interpreted as mean values.

모체 광변색성 화합물은 US 5,650,098 (1,2-b 나프토피란), US 5,623,005 (2,1-b 나프토피란), US 5,446,151 (2,1-b 나프토옥사진), 및 US 6,303,673 (1,2-b 나프토옥사진)에 개시된 바와 같이 제조될 수 있다. The host photochromic compounds are disclosed in US 5,650,098 (1,2-b naphthopyran), US 5,623,005 (2,1-b naphthopyran), US 5,446,151 (2,1-b naphthoquinone), and US 6,303,673 , 2-bnaphthoquinone).

필요하다면, 전형적으로 연결기는 상업적으로 입수가능한 올리고머에 부착되고, 이 시약(reagent)은 이후 모체 광변색성 화합물과 반응하여 폴리디알킬실록산-가교된 이광변색성 분자를 낳는다. 연결기는 모체 광변색성 화합물에 부착될 수 있고, 이것은 이후 상업적으로 입수가능한 올리고머와 반응하여 폴리디알킬실록산-가교된 이광변색성 분자를 생성한다. 적합한 반응 조건은 당업자에게 자명할 것이다.  If necessary, the linker is typically attached to a commercially available oligomer, which reacts with the parent photochromic compound to yield a polydialkylsiloxane-crosslinked photochromic molecule. The linker can be attached to the parent photochromic compound, which in turn reacts with commercially available oligomers to yield polydialkylsiloxane-bridged, photochromic molecules. Appropriate reaction conditions will be apparent to those skilled in the art.

하기의 실시예들이 발명을 설명하기 위한 것이고, 발명의 범위를 제한하는 것은 아니다.The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

실시예Example

상업적으로 입수가능한 폴리디메틸실록산 올리고머는 평균 분자량 또는 분자량 범위를 가지고 공급되고, 디메틸실록산의 반복 단위의 수로서 언급된 모든 수치는 평균값으로 해석된다. 따라서, 하기 실시예에서 언급된 모든 수율은 필연적으로 개략적인 값이다. 올리고머 DMS-B12, DMS-C15, DMS-C16 및 DMS-A214가 Gelest Inc로부터 입수가능하며, 하기의 구조와 개략적인 분자량 또는 분자량 범위를 갖는 것으로 인용된다. 복잡한 시스템적인 명칭(또한, 올리고머는 혼합물이므로, 매우 정확하지는 않음) 보다, Gelest 명명법이 폴리디알킬실록산-가교된 이광변색성 분자의 폴리디메틸실록산 올리고머 부분을 명명하는데 사용될 것이다. DMS-C16 및 DMS-A214를 사용한 경우의 수율 계산을 위해, 분자량 범위의 중간값을 사용하였다.Commercially available polydimethylsiloxane oligomers are supplied with an average molecular weight or molecular weight range and all numbers mentioned as the number of repeating units of dimethylsiloxane are interpreted as mean values. Thus, all yields mentioned in the following examples are necessarily approximate values. The oligomers DMS-B12, DMS-C15, DMS-C16 and DMS-A214 are available from Gelest Inc. and are cited as having the following structures and approximate molecular weight or molecular weight ranges. Rather than a complex systematic designation (and oligomers are mixtures, not very precise), the Gelest nomenclature will be used to designate the polydimethylsiloxane oligomeric portion of the polydialkylsiloxane-bridged photochromic molecule. For yield calculations when DMS-C16 and DMS-A214 were used, a median of the molecular weight range was used.

Figure 112011019688345-pct00009
Figure 112011019688345-pct00009

실시예Example 1: One: 비스Bis -- 숙시닐Succino -- DMSDMS -- C15C15

Figure 112011019688345-pct00010
Figure 112011019688345-pct00010

비스-하이드록시-종결된 실록산 DMS-C15 (9.1 g, 분자량 = 1000)을 숙신산 무수물(2.8 g) 및 톨루엔(120 ml)과 2분 동안 혼합하였다. 트리에틸아민(5.0 ml = 3.5 g)을 첨가하였고 상기 혼합물을 70-75℃까지 1.5시간 동안 가열하였다. 상기 용액을 25℃로 냉각하였고, 이후 PEG 모노메틸에테르(2.6 g)를 첨가하였고 상기 혼합물을 20분 동안 교반하였다.The bis-hydroxy-terminated siloxane DMS-C15 (9.1 g, molecular weight = 1000) was mixed with succinic anhydride (2.8 g) and toluene (120 ml) for 2 minutes. Triethylamine (5.0 ml = 3.5 g) was added and the mixture was heated to 70-75 [deg.] C for 1.5 hours. The solution was cooled to 25 < 0 > C, then PEG monomethyl ether (2.6 g) was added and the mixture was stirred for 20 minutes.

상기 용액을 HCI (5 ml) 및 물(100 ml)의 혼합물로 두번 세척하였고, 이후 포화된 염수(3 x 100 ml)로 세척하였다. 유기층을 소듐 설페이트로 건조하였고, 여과하여 110.2 g을 얻었다. 이론적인 수율은 10.9 g 이었고, 최대 강도 9.9%이었다.The solution was washed twice with a mixture of HCl (5 ml) and water (100 ml), then with saturated brine (3 x 100 ml). The organic layer was dried over sodium sulfate and filtered to give 110.2 g. The theoretical yield was 10.9 g and the maximum strength was 9.9%.

실시예Example 2:  2: 비스Bis -- 프탈로일Phthaloyl DMSDMS -- C15C15

Figure 112011019688345-pct00011
Figure 112011019688345-pct00011

숙신산 무수물 대신에 등가량의 프탈산 무수물을 사용하여, 실시예 1의 비스-숙시닐-DMS-C15와 유사한 방식으로 시약 비스-프탈로일-DMS-C15를 제조하였다. DMS-C15 was prepared in a manner similar to that of bis-succinyl-DMS-C15 of Example 1, using an equivalent amount of phthalic anhydride instead of succinic anhydride.

실시예Example 3:  3: 비스Bis -- 숙시닐Succino -- DMSDMS -- C16C16

Figure 112011019688345-pct00012
Figure 112011019688345-pct00012

비스-하이드록시-종결된 폴리디메틸실록산 DMS-C16 (분자량 범위 = 600-850)을 사용하여, 비스-숙시닐-DMS-C15와 유사한 방식(실시예 1)으로 시약 비스-숙시닐-DMS-C16을 제조하였다.Succinyl-DMS-C15 in a similar manner to bis-succinyl-DMS-C15 (Example 1) using bis-hydroxy-terminated polydimethylsiloxane DMS-C16 (molecular weight range = 600-850) C16.

실시예Example 4:  4: 비스Bis -- 숙신아미도Succinamido -- DMSDMS -A214-A214

Figure 112011019688345-pct00013
Figure 112011019688345-pct00013

비스-2급 아미노-종결된 폴리디메틸실록산 DMS-A214 (분자량 = 2500-3000)을 사용하여, 비스-숙시닐-DMS-C15와 유사한 방식으로 시약 비스-숙신아미도-DMS-A214를 제조하였다. The reagent bis-succinimido-DMS-A214 was prepared in a similar manner to bis-succinyl-DMS-C15 using bis-secondary amino-terminated polydimethylsiloxane DMS-A214 (molecular weight = 2500-3000) .

실시예Example 5: (1,3- 5: (1,3- 디하이드로Dihydro -3,3-디메틸-1--3,3-dimethyl-1- 네오펜틸Neopentyl -6'-(4"-N-에틸,N-(-6 '- (4 "-N-ethyl, N- ( 숙시닐에틸Succinyl ethyl )) 아닐리노Anilino )) 스피로Spiro [2H-인돌-2,3'-3H-[2H-Indole-2,3'-3H- 나프토[1,2-b][1,4]옥사진Naphtho [1,2-b] [1,4] oxazine ]] 22 -- DMSDMS -- C15C15

Figure 112011019688345-pct00014
Figure 112011019688345-pct00014

1,3-디하이드로-3,3-디메틸-1-네오펜틸-6'-(4"-N-에틸,N-하이드록시에틸아닐리노)스피로[2H-인돌-2,3'-3H-나프토[1,2-b][1,4]옥사진] (1.00 g)을 비스-숙시닐-DMS-C15의 톨루엔 용액(실시예 1에 따라 제조됨, 톨루엔 6.4% 용액 18.5 g = 100% 환산 1.18 g), 디메틸아미노피리딘(0.05 g) 및 톨루엔(20 ml)과 혼합하였다. 디시클로헥실 카보디이미드(0.75 g)를 첨가하기 전에, 상기 혼합물을 실온에서 10 분 동안 교반하였다. 이후 이것을 실온에서 45분 동안 교반하였다.Dihydro-3,3-dimethyl-1-neopentyl-6 '- (4'-N-ethyl, N-hydroxyethylanilino) spiro [2H- (1.00 g) was dissolved in a toluene solution of bis-succinyl-DMS-C15 (prepared according to Example 1, 18.5 g of toluene 6.4% solution = 100 The mixture was stirred for 10 minutes at room temperature, before addition of dicyclohexylcarbodiimide (0.75 g), followed by stirring at room temperature for 2 hours. This was stirred at room temperature for 45 minutes.

더 많은 비스-숙시닐-DMS-C15 (톨루엔 6.4% 용액 6.0 g = 0.38 g)을 첨가하였고 상기 혼합물을 40분 더 교반하였다. TLC는 미반응 출발 물질에 대해 희미한 흔적만 보였다. More bis-succinyl-DMS-C15 (6.0 g of a 6.4% solution of toluene = 0.38 g) was added and the mixture was stirred for an additional 40 minutes. TLC showed only a faint trace of unreacted starting material.

상기 혼합물은 아이스 배스에서 15분 동안 냉각하였고, 이후 여과하고, 고형물을 톨루엔(5 ml)으로 세척하였다. 상기 용액을 플래쉬 크로마토그래피에 사용하였다. 최적 분획들(best fractions)을 혼합하고 증발시켰다. 그 결과인 그린 검(green gum)을 아세톤(15ml)에 용해하였고, 여과하고, 이후 증발시켜 1.6g의 녹색 오일(green oil)를 얻었고, 상기 녹색 오일을 방치에 의해 옅은 녹색 불투명한 부드러운 고체로 전환되었다. 대략적인 수율 = 77%. The mixture was cooled in an ice bath for 15 minutes, then filtered and the solids were washed with toluene (5 ml). The solution was used for flash chromatography. The best fractions were mixed and evaporated. The resulting green gum was dissolved in acetone (15 ml), filtered and then evaporated to give 1.6 g of green oil. The green oil was allowed to settle to a pale green opaque smooth solid Respectively. Approximate yield = 77%.

실시예Example 6: (3-(4'- 6: (3- (4'- 메톡시페닐Methoxyphenyl ),3-(4"-(), 3- (4 "- ( 숙시닐에톡시Succinylethoxy )) 페닐Phenyl )-6-) -6- 모폴리노Morpolino -3H-나프토[2,1-b]피란)-3H-naphtho [2,1-b] pyran) 22 -- DMSDMS -- C16C16

Figure 112011019688345-pct00015
Figure 112011019688345-pct00015

3-(4'-메톡시페닐),3-(4"-하이드록시에톡시페닐)-6-모폴리노-3H-나프토[2,1-b]피란(1.50 g)을 비스-숙시닐-DMS-C16의 톨루엔 용액(실시예 3에 따라 제조됨, 11.6% 용액 14.7g = 100% 환산 1.71g), 톨루엔 (20 ml) 및 디메틸아미노피리딘 (0.07 g)과 혼합하였다. 이것을 2분 동안 교반하였고, 이후 디시클로헥실 카르보디이미드(0.67 g)를 첨가하였고 상기 혼합물을 실온에서 교반하였다. 상기 혼합물은 1-2분 교반한 후 불투명해졌다. 3-naphtho [2,1-b] pyran (1.50 g) was added to a solution of bis-succinic anhydride Was mixed with toluene (20 ml) and dimethylaminopyridine (0.07 g) in toluene (prepared according to Example 3, 14.7 g of 11.6% solution = 1.71 g in terms of 100%), , Then dicyclohexylcarbodiimide (0.67 g) was added and the mixture was stirred at room temperature. The mixture became opaque after stirring for 1-2 minutes.

45분 후, 박층크로마토그래피(TLC)(3:1 페트롤:아세톤)가 일부 미반응 출발물질이 남았다는 것을 나타내었다. 비스-숙시닐-DMS-C16의 톨루엔 용액(11.6% 용액 6.1g = 100% 환산 0.71g)을 더 첨가하였고, 상기 혼합물을 1 시간 동안 교반하였다. 이 점에서 TLC는 출발 물질이 거의 남아있지 않다는 것을 나타냈다.After 45 min, thin layer chromatography (TLC) (3: 1 petrol: acetone) indicated that some unreacted starting material remained. A toluene solution of bis-succinyl-DMS-C16 (6.1 g of an 11.6% solution = 0.71 g in terms of 100%) was further added and the mixture was stirred for 1 hour. At this point TLC indicated that there was little starting material left.

상기 혼합물을 4℃까지 45분 동안 냉각하였고, 이후 여과하고 고형물을 톨루엔(5 ml)으로 세척하였다. 용액을 플래쉬 크로마토크래피에 사용하였고, 석유 에테르(petroleum ether) 및 에틸 아세테이트의 혼합물로 용리하였다. 이것은 오렌지 오일 2.7 g을 주었으며 이것은 불투명한 오렌지 고형물로 경화되었다. 수율 = 약 96% .The mixture was cooled to 4 < 0 > C for 45 min, then filtered and the solids were washed with toluene (5 ml). The solution was used for flash chromatography and was eluted with a mixture of petroleum ether and ethyl acetate. This gave 2.7 g of orange oil which hardened to an opaque orange solid. Yield = about 96%.

실시예Example 7: (1,3- 7: (1,3- 디하이드로Dihydro -3,3-디메틸-1-이소부틸-9'--3,3-dimethyl-1-isobutyl-9'- 숙시닐Succino -스피로[2H-인돌-2,3'-3H-나프토[2,1-b][1,4]옥사진)-Spiro [2H-indole-2,3'-3H-naphtho [2,1-b] [1,4] oxazine) 22 -- DMSDMS -- C16C16

Figure 112011019688345-pct00016
Figure 112011019688345-pct00016

1,3-디하이드로-3,3-디메틸-1-이소부틸-9'하이드록시-스피로[2H-인돌-2,3'-3H-나프토[2,1-b][1,4]옥사진](1.50g)을 비스-숙시닐-DMS-C16의 톨루엔 용액(실시예 3에 따라 제조됨, 9.7% 톨루엔 용액 29.8g = 100% 환산 2.90g), 톨루엔 (20 ml) 및 디메틸아미노 피리딘(0.07 g)과 혼합하였다. 이것을 고형물 전부가 용해될 때까지 2분 동안 교반하였다. 디시클로헥실 카르보디이미드(0.90 g)을 첨가하였고 혼합물을 실온에서 45분 동안 교반하였다. 10분 후, 이 용액은 디시클로헥실 우레아의 흰색 침전물로 흐려졌다.1,3-dihydro-3,3-dimethyl-1-isobutyl-9'hydroxy-spiro [2H-indole-2,3'-3H-naphtho [ (1.50 g) was dissolved in a toluene solution of bis-succinyl-DMS-C16 (prepared according to Example 3, 29.8 g of 9.7% toluene solution = 2.90 g in terms of 100%), toluene (20 ml) Pyridine (0.07 g). This was stirred for 2 minutes until all of the solids dissolved. Dicyclohexylcarbodiimide (0.90 g) was added and the mixture was stirred at room temperature for 45 minutes. After 10 minutes, the solution became clouded with a white precipitate of dicyclohexylurea.

45분 후, TLC (3:1 페트롤:아세톤)은 출발 물질의 거의 대부분이 보다 약한 극성의 광변색성 생성물로 전환되었다는 것을 나타냈다. 상기 혼합물을 4℃까지 45분 동안 냉각하였고, 이후 여과하였고 고형물을 톨루엔(5 ml)으로 세척하였다. 용액을 석유 에테르와 에틸 아세테이트의 혼합물로 용리하여 플래쉬 크로마토그래피에 사용하였다. 최적 분획들을 혼합하고 증발시켰다. 그 결과물인 청색 오일(blue oil)을 아세톤(30 ml)에 다시 용해하였고, 여과하고 다시 증발시켰다. 이것은 옅은 청색-녹색 오일:2.3g을 생성하였다. 수율 = 약 68%.After 45 minutes, TLC (3: 1 petrol: acetone) indicated that almost all of the starting material was converted to a photochromic product with a weaker polarity. The mixture was cooled to 4 < 0 > C for 45 min, then filtered and the solids were washed with toluene (5 ml). The solution was used for flash chromatography eluting with a mixture of petroleum ether and ethyl acetate. Optimal fractions were combined and evaporated. The resulting blue oil was redissolved in acetone (30 ml), filtered and evaporated again. This yielded 2.3 g of a pale blue-green oil. Yield = about 68%.

실시예Example 8: 2-(4'- 8: 2- (4'- 피롤리디노페닐Pyrrolidinophenyl )-2-)-2- 페닐Phenyl -5--5- 프탈로일메틸Phthaloylmethyl -6-아니실-9--6-anilyl-9- 메톡시Methoxy -2H-나프토[1,2-b]피란)-2H-naphtho [l, 2-b] pyran) 22 -- DMSDMS -- C15C15

Figure 112011019688345-pct00017
Figure 112011019688345-pct00017

2-(4'-피롤리디노페닐)-2-페닐-5-하이드록시메틸-6-아니실-9-메톡시-2H-나프토[1,2-b]피란 (1.50 g)을 비스-프탈로일-DMS-C15의 톨루엔 용액(실시예 2에 따라 제조됨, 9.2% 용액 22.8 g = 100% 환산 2.10 g), 톨루엔(20 ml), 및 디메틸아미노피리딘 (0.05 g)과 혼합하였다. 이것을 2분 동안 교반하였고, 이후 DCCI(0.60 g = 1.10 몰/몰)을 첨가하였다. 이것을 45분 동안 교반하였고, 이 시점에서 TLC가 일부 미반응 출발 물질이 남았다는 것을 나타냈다. 비스-프탈로일 DMS-C15 의 톨루엔 용액(용액 1.9 g = 100% 환산 0.17g)을 더 첨가하였고 상기 혼합물을 40분 동안 더 교반하였다. TLC는 출발물질이 거의 남아있지 않다는 것을 나타냈고, 따라서 상기 혼합물을 4℃까지 45분 동안 냉각하였다. 이것을 여과하고 고형물을 톨루엔(5 ml)으로 세척하였다.6-anisyl-9-methoxy-2H-naphtho [l, 2-b] pyran (1.50 g) was added to a solution of bis (4-pyrrolidinophenyl) (Prepared according to example 2, 22.8 g of 9.2% solution = 2.10 g in terms of 100%), toluene (20 ml), and dimethylaminopyridine (0.05 g) in toluene-DMS- . This was stirred for 2 min, after which DCCI (0.60 g = 1.10 mol / mol) was added. This was stirred for 45 min, at which time TLC indicated that some unreacted starting material remained. Further, a toluene solution of bis-phthaloyl DMS-C15 (1.9 g of the solution = 0.17 g in terms of 100%) was further added and the mixture was further stirred for 40 minutes. TLC indicated that there was little starting material left, so the mixture was cooled to 4 < 0 > C for 45 minutes. It was filtered and the solids were washed with toluene (5 ml).

상기 용액은 플래쉬 크로마토그래피에 사용하였고, 에틸 아세테이트 및 톨루엔의 혼합물로 용리하였다. 최적 분획들을 혼합하고 증발시켰다. 청색 타르를 아세톤(20 ml)에 용해하였고, 여과하고 증발시켜 2.3g의 어두운 청색 타르를 얻었다. 약 69% 수율.The solution was used for flash chromatography and eluted with a mixture of ethyl acetate and toluene. Optimal fractions were combined and evaporated. The blue tar was dissolved in acetone (20 ml), filtered and evaporated to give 2.3 g of dark blue tar. About 69% yield.

실시예Example 9:2,2- 9: 2,2- 비스Bis (4'-(4'- 메톡시페닐Methoxyphenyl )-5-) -5- 하이드록시메틸Hydroxymethyl -6--6- 메틸methyl -2H-나프토[1,2-b]피란)-2H-naphtho [l, 2-b] pyran) 22 -- DMSDMS -B12-B12

Figure 112011019688345-pct00018
Figure 112011019688345-pct00018

2,2-비스(4'-메톡시페닐)-5-하이드록시메틸-6-메틸-2H-나프토[1,2-b]피란(1.50 g)을 비스-카르복시-종결된 실록산 DMS-B12 (2.10 g), 디메틸아미노피리딘 (0.07 g) 및 톨루엔 (35 ml)과 실온에서 혼합하였다. 이것을 2분 동안 교반한 후, 이후 디시클로헥실 카르보디이미드(0.80 g)을 첨가하였고 상기 혼합물을 45 분 동안 교반하였다. TLC는 모든 출발물질이 소모되었다는 것을 나타냈다. 상기 혼합물을 4℃까지 45분 동안 냉각하였다. 이것을 여과하고 이후 고형물을 톨루엔(5 ml)으로 세척하였다.Methyl-2H-naphtho [l, 2-b] pyran (1.50 g) was added to a bis-carboxy-terminated siloxane DMS- B12 (2.10 g), dimethylaminopyridine (0.07 g) and toluene (35 ml) at room temperature. After stirring for 2 minutes, dicyclohexylcarbodiimide (0.80 g) was then added and the mixture was stirred for 45 minutes. TLC indicated that all starting material was consumed. The mixture was cooled to 4 DEG C for 45 minutes. This was filtered off and the solids were then washed with toluene (5 ml).

상기 용액을 석유 에테르와 에틸 아세테이트의 혼합물로 용리하여 크로마토그래피에 사용하였다. 최적 분획들을 혼합하고 증발시켜 오렌지-레드 오일:1.3g을 얻었다. 수율 = 약 41%The solution was used for chromatography eluting with a mixture of petroleum ether and ethyl acetate. The optimum fractions were mixed and evaporated to obtain 1.3 g of orange-red oil. Yield = about 41%

실시예Example 10 : (2-(4'- 10: (2- (4'- 피롤리디노페닐Pyrrolidinophenyl )-2-)-2- 페닐Phenyl -5--5- 숙시닐메틸Succinylmethyl -6-아니실-9--6-anilyl-9- 메톡Meth 시-2H-나프토[1,2-b]피란)-Yl-2H-naphtho [l, 2-b] pyran) - DMSDMS -- C15C15 -(3-- (3- 페닐Phenyl -3-(4'--3- (4'- 숙시닐에톡시Succinylethoxy )) 페닐Phenyl )-6-) -6- 모폴리노Morpolino -3H-나프토[2,1-b]피란)-3H-naphtho [2,1-b] pyran)

Figure 112011019688345-pct00019
Figure 112011019688345-pct00019

2-(4'-피롤리디노페닐)-2-페닐-5-하이드록시메틸-6-아니실-9-메톡시-2H-나프토[1,2-b]피란 (0.57 g = 0.001몰, 청색 피란)을 3-페닐-3-(4'-하이드록시에톡시페닐)-6-모폴리노-3H-나프토[2,1-b]피란(0.48 g = 0.001몰, 황색 피란), 비스-숙시닐-DMS-C15의 톨루엔 용액(실시예 1에 따라 제조됨, 6.8% 용액 30.0 g = 100% 환산 1.92 g) 및 디메틸아미노피리딘(0.05 g)을 혼합하였고, 고형물이 용해될 때까지 실온에서 10분 동안 교반하였다. 디시클로헥실 카르보디이미드(0.90 g)을 첨가하였고, 상기 혼합물을 실온에서 2시간 동안 교반하였다. TLC (5:1 톨루엔:EtOAc)는 두개의 광변색성 출발 물질이 소모되었음을 나타내었다. 상기 혼합물을 여과하여 디시클로헥실 우레아를 제거하였고, 톨루엔(5 ml)으로 세척하였다.Phenylmethyl-6-anilyl-9-methoxy-2H-naphtho [l, 2-b] pyran (0.57 g = 0.001 mol , 2,1-b] pyran (0.48 g = 0.001 moles, yellow piranha) was added to a solution of 3-phenyl-3- (4'-hydroxyethoxyphenyl) (Prepared according to Example 1, 30.0 g of 6.8% solution = 1.92 g in terms of 100%) and dimethylaminopyridine (0.05 g) were mixed and the solids dissolved At room temperature for 10 minutes. Dicyclohexylcarbodiimide (0.90 g) was added and the mixture was stirred at room temperature for 2 hours. TLC (5: 1 toluene: EtOAc) indicated that two photochromic starting materials were consumed. The mixture was filtered to remove dicyclohexylurea and washed with toluene (5 ml).

상기 용액을 톨루엔 및 에틸 아세테이트의 혼합물로 용리하여, 크로마토그래피에 사용하였다. 첫번째 크로마토그래피 컬럼은 사슬의 각 말단에 청색 피란을 가진 생성물의 대부분과, 사슬의 말단에서 황색 피란을 가진 생성물의 대부분을 제거하였고, 남아있는 분획들은 대부분 목적한“혼합(mixed)”생성물을 함유하였다. 이들 분획들을 혼합하고, 증발하고 다시 크로마토그래피하였다. 최적 분획들을 결합하였고, 증발시켰고, 아세톤(20 ml)에서 용해하고, 여과하고, 다시 증발시켜 점성이 있는 엘로우-브라운 오일:1.15 g을 얻었다. 대략적인 수율 = 52%The solution was used for chromatography, eluting with a mixture of toluene and ethyl acetate. The first chromatographic column removed most of the product with blue turbidity at each end of the chain and most of the product with yellow turbidity at the end of the chain, and the remaining fractions mostly contained the desired " mixed & Respectively. These fractions were combined, evaporated and again chromatographed. Optimal fractions were combined, evaporated, dissolved in acetone (20 ml), filtered and evaporated again to give 1.15 g of viscous yellow-brown oil. Approximate yield = 52%

실시예Example 11:(1,3- 11: (1,3- 디하이드로Dihydro -3,3-디메틸-1--3,3-dimethyl-1- 네오펜틸Neopentyl -9'--9'- 숙시닐Succino -스피로[2H-인돌-2,3'-3H--Spiro [2H-indole-2,3 ' - < 나프토[2,1-b][1,4]옥사진Naphtho [2,1-b] [1,4] oxazine ])]) 22 -- DMSDMS -A214-A214

Figure 112011019688345-pct00020
Figure 112011019688345-pct00020

1,3-디하이드로-3,3-디메틸-1-네오펜틸-9'-하이드록시-스피로[2H-인돌-2,3'-3H-나프토[2,1-b][1,4]옥사진](0.47 g)을 비스-숙신아미도-DMS-A214 (17.1% 톨루엔 용액 12.5 g = 100% 환산 2.14 g)와 혼합하였다. 디메틸아미노피리딘 (0.03 g)을 첨가하였고 상기 혼합물을 디시클로헥실 카르보디이미드(0.29 g)를 첨가하기 전에 1 분 동안 교반하였다. 상기 혼합물을 45분 동안 교반하였고 TLC는 비극성 생성물얼룩(swear)을 나타냈고, 및 미반응된 출발물질에 대한 흔적을 나타내지 않았다. 3-dimethyl-1-neopentyl-9'-hydroxy-spiro [2H-indole-2,3'-3H-naphtho [2,1- b] [1,4 ] Oxazine] (0.47 g) was mixed with bis-succinamido-DMS-A214 (12.1 g of a 17.1% toluene solution = 2.14 g in terms of 100%). Dimethylaminopyridine (0.03 g) was added and the mixture was stirred for 1 minute before adding dicyclohexylcarbodiimide (0.29 g). The mixture was stirred for 45 min and TLC showed a non-polar product sweat and no trace of unreacted starting material.

상기 혼합물은 아이스 배스에서 45분 동안 냉각하였고, 이후 여과하여 디시클로헥실 우레아를 제거하였다. 상기 용액을 에틸 아세테이트와 석유 에테르로 용리하여 크로마토그래피에 사용하였다. 최적 분획들을 혼합하고 증발시켰다. 그 결과의 그린-브라운 오일을 아세톤(30 ml)에 용해하고, 여과하고 이후 다시 증발시켜 1.8 g = 82%을 얻었다.The mixture was cooled in an ice bath for 45 minutes and then filtered to remove dicyclohexylurea. The solution was used for chromatography eluting with ethyl acetate and petroleum ether. Optimal fractions were combined and evaporated. The resulting green-brown oil was dissolved in acetone (30 ml), filtered and then evaporated again to give 1.8 g = 82%.

실시예Example 12: (2,2- 12: (2,2- 비스Bis (4'-(4'- 메톡시페닐Methoxyphenyl )-5-) -5- 숙시닐메틸Succinylmethyl -6--6- 메틸methyl -2H-나프토[1,2-b]피란)-2H-naphtho [l, 2-b] pyran) 22 -- DMSDMS -- C15C15

Figure 112011019688345-pct00021
Figure 112011019688345-pct00021

2,2-비스(4'-메톡시페닐)-5-하이드록시메틸-6-메틸-2H-나프토[1,2-b]피란을 비스-숙시닐-DMS-C15 (2.0 g), 톨루엔 (20 ml) 및 디메틸아미노피리딘 (0.05 g)과 혼합하였다. 이것을 2분 동안 교반하였고, 이후 디시클로헥실 카르보디이미드(0.51 g)을 첨가하였다. 상기 혼합물을 45분 동안 교반하였고 TLC (3:1 톨루엔: EtOAc)는 폴리디알킬실록산-가교된 이광변색성 생성물에 대한 메인 스팟(main spot)을 나타내었고, 실질적으로 출발 물질이 남아 있지 않았다. 상기 혼합물을 아이스 배스에서 1시간 동안 냉각하였고, 이후 여과하고 디시클로헥실 우레아를 톨루엔(5 ml)으로 세척하였다.Bis-4-methoxyphenyl) -5-hydroxymethyl-6-methyl-2H-naphtho [1,2-b] pyran was reacted with bis- succinyl-DMS- Was mixed with toluene (20 ml) and dimethylaminopyridine (0.05 g). This was stirred for 2 minutes, after which dicyclohexylcarbodiimide (0.51 g) was added. The mixture was stirred for 45 minutes and TLC (3: 1 toluene: EtOAc) showed the main spot for the polydialkylsiloxane-crosslinked photochromic product and virtually no starting material remained. The mixture was cooled in an ice bath for 1 hour, then filtered and dicyclohexylurea was washed with toluene (5 ml).

상기 용액을, 에틸 아세테이트와 석유 에테르로 용리하여 크로마토그래피에 사용하였다. 최적 분획들을 혼합하고 증발시켜 어두운 오렌지 오일을 얻었다. 이것을 아세톤(약 40 ml)에 용해하고 여과하였다. 상기 용액을 증발시켜 2.1 g을 얻었다. 약 90% 수율.The solution was used for chromatography eluting with ethyl acetate and petroleum ether. Optimal fractions were combined and evaporated to give a dark orange oil. This was dissolved in acetone (ca. 40 ml) and filtered. The solution was evaporated to yield 2.1 g. Approximately 90% yield.

비교 화합물Comparative compound

Figure 112011019688345-pct00022

Figure 112011019688345-pct00022

퇴색 속도 및 Fading rate and 아크릴레이트게Acrylate crab 렌즈에서 강도 측정 Strength measurement in the lens

실시예 5 내지 11의 샘플 및 비교 화합물 C1 내지 C6을 에톡시레이티드(4)비스페놀 A 디메타아크릴레이트 모노머에 250 중량 ppm으로 용해하였고, 이후 200℃에서 렌즈 몰드에서 경화하였다. 그 결과물인 렌즈를 냉각하고 테스트 전 24시간 이상 방치하였다. 상기 렌즈는 23℃의 일정한 온도의 워터 배스에서 10분 동안 활성화하였고, 50 Klux 광원을 Air Mass 2 standard로 필터링하였다. 그 결과 야기된 흡수(Delta Abs)는 화합물의 람다 맥스(lambda max)에서 측정하였다. 광원을 끄고 퇴색 결과를 모니터하였고, 최초 흡수의 절반(T1 /2) 및 최초 흡수의 4분의 1(T3 /4)까지의 퇴색 시간을 얻었다. Samples of Examples 5 to 11 and Comparative Compounds C1 to C6 were dissolved in 250 ppm by weight of ethoxylated (4) bisphenol A dimethacrylate monomer and then cured at 200 ° C in a lens mold. The resultant lens was cooled and allowed to stand for 24 hours or more before the test. The lens was activated for 10 minutes in a water bath at a constant temperature of 23 ° C and the 50 Klux light source was filtered with an Air Mass 2 standard. The resulting absorption (Delta Abs) was measured in the lambda max of the compound. Monitoring the result was washed off the light source, a half of the initial absorption (T 1/2) and to obtain a fade time of up to 4 minutes 1 (T 3/4) of the first absorbent.

파라미터 “조정된 델타 Abs(Adjusted Delta Abs)”는 폴리디알킬실록산-가교된 이광변색성 화합물의 분자량, 비가교된 비교 화합물의 분자량 및 존재하는 광변색성 유닛의 수를 고려하였다. 이것은 하기와 같이 계산되었다:The parameter " Adjusted Delta Abs " takes into account the molecular weight of the polydialkylsiloxane-crosslinked photochromic compound, the molecular weight of the uncrosslinked comparison compound and the number of photochromic units present. This was calculated as follows:

조정된 델타 Abs = (실시예 화합물의 Delta Abs x (실시예 화합물의 몰 Wt)/(비교예 화합물의 몰 Wt))/실시예 화합물 중에 존재하는 광변색성 유닛의 수 Adjusted Delta Abs = (Delta Abs x of Example Compound (moles Wt of Example Compound) / (moles Wt of Comparative Example Compound) / number of photochromic units present in the Example Compound

사슬의 각각의 말단에 다른 광변색성 유닛을 가지는, 실시예 10의 경우, 각각의 광변색성 유닛으로부터 흡수는 분리하여 처리하였다.In the case of Example 10 having different photochromic units at each end of the chain, the absorption from each photochromic unit was treated separately.

Figure 112011019688345-pct00023
Figure 112011019688345-pct00023

Figure 112011019688345-pct00024
Figure 112011019688345-pct00024

상기 표에서 볼 수 있는 바와 같이, 꼬리 달린 이량체(tailed dimers)의 T1 /2 값은 대응되는 비교 화합물의 T1 /2 값의 29.4% 내지 65.4%이다. 꼬리 달린 이량체의 T3/4 값은 더 큰 향상을 보여주는데, 해당 비교 화합물의 T3 /4 값의 13.9% 내지 40.0% 사이에 있다.As can be seen in the Table, T 1/2 value of the tailed dimers (tailed dimers) is 29.4% to 65.4% of T 1/2 values of the corresponding comparative compounds. T 3/4 value of the tailed dimer to show a further improvement, it is between 13.9% to 40.0% of T 3/4 values of the comparative compound.

조정된 델타 Abs(Delta Abs)값은 폴리디알킬실록산-가교된 이광변색성 화합물의 색강도가 비교예 화합물(실시예 11) 보다 조금 약한 값에서 상당히 높은 범위(실시예 6,8,9 및 10)에 있다는 것을 나타낸다.The adjusted Delta Abs values show that the color strength of the polydialkylsiloxane-crosslinked photochromic compound was significantly higher than the comparative compound (Example 11) to a significantly higher value (Examples 6, 8, 9, 10).

열 안정성 테스트Thermal stability test

실시예 7 및 실시예 12의 화합물 및 대응되는 비교예 화합물 C4 및 C2의 샘플을 250 ppm으로 다른 가공 온도에서 Boy 35M 사출 성형기를 사용하여 폴리카보네이트, 및 폴리스티렌에 병합하였고, 직사각형 칩(rectangular chips)을 얻었다. 상기 칩들은 렌즈를 측정하기 위해 사용된 것과 동일한 기계를 사용하여 흡수를 측정하였다. 상기 칩들은 Datacolor Spectraflash SF450 colour spectrometer를 사용하여 황변화 지수(yellowness index ASTM D1925에 따름)를 측정하였다.Samples of the compounds of Examples 7 and 12 and the corresponding comparative compounds C4 and C2 were incorporated into polycarbonate and polystyrene using a Boy 35M injection molding machine at 250 ppm at different processing temperatures and rectangular chips, ≪ / RTI > The chips were measured for absorption using the same machine used to measure the lens. The chips were measured using a Datacolor Spectraflash SF450 color spectrometer to measure the yellowness index (according to ASTM D1925).

(i) 폴리카보네이트 중에 250 ppm으로 혼합되고 315℃ 및 330℃에서 가공된 실시예 12 및 C2.(i) Example 12 and C2 mixed at 250 ppm in polycarbonate and processed at 315 캜 and 330 캜.

Figure 112011019688345-pct00025
Figure 112011019688345-pct00025

(ii) 폴리스티렌 중에 250 ppm으로 혼합된 실시예 7 및 C4.(ii) Example 7 and C4 mixed at 250 ppm in polystyrene.

Figure 112011019688345-pct00026
Figure 112011019688345-pct00026

Claims (25)

폴리디알킬실록산(PDAS) 올리고머를 통해 연결된 두개의 광변색성 모이어티를 포함하고, 하기 일반식을 갖는 이광변색성 분자(bi-photochromic molecule):
PC-L-PDAS-L'-PC'
여기서, PC 및 PC'는 동일하거나 다를 수 있으며, 하기 일반구조 Ⅰ 내지 Ⅳ의 모이어티를 나타내고,
Figure 112015101451282-pct00027

Figure 112015101451282-pct00028

여기서, R1 및 R2는 독립적으로 수소, 선형 또는 분지형 C1-10 알킬, 선형 또는 분지형 C1-10 알콕시, C1-10 하이드록시알콕시, C1-10 알콕시(C1-10)알콕시, 페닐, C1-10 알콕시페닐, 할로겐, C1-5 할로알킬, C1-5 알킬아미노, C1-5 디알킬아미노, 아릴아미노, 디아릴아미노, 아릴 C1-5 알킬아미노, 또는 고리형 아미노기를 나타내며;
R3는 수소, 선형 또는 분지형 C1-10 알킬, C3-20 시클로알킬, C6-20 바이시클로알킬, 선형 또는 분지형 C2-10 알케닐, 선형 또는 분지형 C1-10 알콕시, C1-10 하이드록시알킬, C1-10 알콕시(C1-10)알킬, C1-10 아미노알킬, 선형 또는 분지형 C1-20 알콕시카르보닐, 카르보닐, 할로겐, 아릴옥시카보닐, 포르밀, 아세틸 또는 아로일(aroyl)을 나타내고;
R4는 페닐, C1-10 알콕시페닐, C1-10 디알콕시페닐, C1-10 알킬페닐, C1-10 디알킬페닐 또는 상기 R3에 대해 특정한 기 중의 하나를 나타내고;
또는 R3 및 R4는 함께 하기 타입의 고리형 구조를 형성하고
Figure 112015101451282-pct00029

R5, R6, R7, R8, R9, R10, R14, R15, R16는 R1 및 R2에 대해 정의된 바와 같고;
R11은 선형 또는 분지형 C1-20 알킬, C3-20 시클로알킬, C6-20 바이시클로알킬, (C1-5 알킬)아릴, (C1-5 알킬)시클로알킬, (C1-5 알킬)바이시클로알킬, C1-5 할로알킬, C1-5 디할로알킬, 또는 C1-5 트리할로알킬을 나타내고;
R12 및 R13은 C1-10 알킬, C1-5 알킬 알콕시카르보닐을 나타내거나, 또는 함께 C5-7 고리를 형성하고;
R17 및 R18은 선형 또는 분지형 C1-10 알킬, C1-10 하이드록시알킬을 나타내거나, 또는 함께 C5-7 고리를 형성하고;
L 및 L'는 동일하거나 다를 수 있으며, 연결기를 나타낸다.A bi-photochromic molecule comprising two photochromic moieties connected through a polydialkylsiloxane (PDAS) oligomer and having the general formula:
PC-L-PDAS-L'-PC '
Here, PC and PC 'may be the same or different and represent a moiety of the following general structures I to IV,
Figure 112015101451282-pct00027

Figure 112015101451282-pct00028

Wherein R 1 and R 2 are independently selected from the group consisting of hydrogen, linear or branched C 1-10 alkyl, linear or branched C 1-10 alkoxy, C 1-10 hydroxyalkoxy, C 1-10 alkoxy (C 1-10 ) alkoxy , phenyl, C 1-10 alkoxy, phenyl, halogen, C 1-5 haloalkyl, C 1-5 alkylamino, C 1-5 dialkylamino, arylamino, diarylamino, aryl C 1-5 alkylamino, or A cyclic amino group;
R 3 is selected from the group consisting of hydrogen, linear or branched C 1-10 alkyl, C 3-20 cycloalkyl, C 6-20 bicycloalkyl, linear or branched C 2-10 alkenyl, linear or branched C 1-10 alkoxy, C 1-10 hydroxyalkyl, C 1-10 alkoxy (C 1-10) alkyl, C 1-10 aminoalkyl, linear or branched C 1-20 alkoxycarbonyl, carbonyl, halogen, aryloxy-carbonyl, Formyl, acetyl or aroyl;
R4 is phenyl, C 1-10 alkoxyphenyl, di-C 1-10 alkoxyphenyl, C 1-10 alkyl phenyl, C 1-10 dialkyl phenyl or represents one of the specific groups for the above R3;
Or R3 and R4 together form a cyclic structure of the following type
Figure 112015101451282-pct00029

R5, R6, R7, R8, R9, R10, R14, R15, R16 are as defined for R1 and R2;
R11 is a linear or branched C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 bicycloalkyl alkyl, (C 1-5 alkyl) aryl, (C 1-5 alkyl) cycloalkyl, (C 1- 5 alkyl, bicycloalkyl, C 1-5 haloalkyl, C 1-5 dihaloalkyl, or C 1-5 trihaloalkyl;
R 12 and R 13 represent C 1-10 alkyl, C 1-5 alkylalkoxycarbonyl, or together form a C 5-7 ring;
R 17 and R 18 represent linear or branched C 1-10 alkyl, C 1-10 hydroxyalkyl, or together form a C 5-7 ring;
L and L 'may be the same or different and represent a linking group. 제 1항에 있어서, 상기 폴리디알킬실록산(PDAS) 올리고머는 하기식으로 표시되는 이광변색성 분자:
Figure 112011019690180-pct00030

여기서, R19는 C1-10 알킬이고, n은 4 내지 75의 정수(경계 포함)이다.2. The polymer of claim 1, wherein the polydialkylsiloxane (PDAS) oligomer is a dichroic dye molecule represented by the formula:
Figure 112011019690180-pct00030

Here, R19 is a C 1-10 alkyl, n is an integer inclusive of from 4 to 75. 제 1항에 있어서, 상기 폴리디알킬실록산 올리고머는 폴리디메틸실록산 올리고머인 이광변색성 분자.The photochromic molecule of claim 1, wherein the polydialkylsiloxane oligomer is a polydimethylsiloxane oligomer. 제 1항에 있어서, 상기 L 및 L'가 하기 형태의 연결기를 나타내는 폴리디메틸실록산 올리고머인 이광변색성 분자:
Figure 112015101451282-pct00031

여기서 Y는 독립적으로 산소 또는 황이며, R19는 수소 또는 C1-10 선형 또는 분지형 알킬이고, R20은 C1-10 선형 또는 분지형 알킬이고, p는 1 내지 15의 정수이며, 및 r은 0 내지 10의 정수이고, 여기서 Q는 선형 또는 분지형 C1-10 알킬, C2-10 알케닐 또는 1,2-, 1,3-, 또는 1,4- 위치에 C=Y의 탄소 원자가 연결된 아릴, 또는 헤테로아릴이다.The photochromic molecule of claim 1, wherein L and L 'are polydimethylsiloxane oligomers that represent linking groups of the form:
Figure 112015101451282-pct00031

Wherein Y is independently oxygen or sulfur, R19 is hydrogen or C 1-10 linear or branched alkyl, R20 is a C 1-10 linear or branched alkyl, p represents an integer from 1 to 15, and r Wherein Q is a linear or branched C 1-10 alkyl, C 2-10 alkenyl or a C- Y carbon atom in the 1,2-, 1,3-, or 1,4-position Aryl, or heteroaryl. 제 1항에 있어서, 상기 폴리디알킬실록산 올리고머는 DMS-B12, DMS-C15, DMS-C16, DMS-C21, DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A211, DMS-A214, KF-6001, KF-6002, KF-6003, KF-8010, X-22-160AS, X-22-162A, X-22-161A, X-22-161B, X-22-162C, 및 Silaplane FM-44로부터 선택되고, 상기 폴리디알킬실록산 올리고머의 구조는 하기와 같은 이광변색성 분자:
Figure 112015101451282-pct00032

Figure 112015101451282-pct00033
The polymeric siloxane oligomer of claim 1, wherein the polydialkylsiloxane oligomer is selected from the group consisting of DMS-B12, DMS-C15, DMS-C16, DMS-C21, DMS-A11, DMS-A12, DMS- -214, KF-6001, KF-6002, KF-6003, KF-8010, X-22-160AS, X-22-162A, X-22-161A, X-22-161B, X- Silaplane FM-44, and the structure of the polydialkylsiloxane oligomer is selected from the following photochromic molecules:
Figure 112015101451282-pct00032

Figure 112015101451282-pct00033
 제 4항에 있어서, 상기 PC와 PC' 각각은 일반 구조 1의 나프토[1,2-b]피란 또는 일반 구조 2의 나프토[2,1-b]피란인 이광변색성 분자.5. The photochromic molecule of claim 4, wherein PC and PC 'are each naphtho [1,2-b] pyran of general structure 1 or naphtho [2,1-b] 제 6항에 있어서, 상기 PC와 PC'는 둘다 일반 구조 1의 나프토[1,2-b]피란인 이광변색성 분자.7. The photochromic molecule of claim 6, wherein PC and PC 'are both naphtho [1,2-b] pyran of general structure 1. 제 6항에 있어서, 상기 PC와 PC'는 둘다 일반 구조 2의 나프토[2,1-b]피란인 이광변색성 분자.7. The photochromic molecule of claim 6, wherein PC and PC 'are both naphtho [2,1-b] pyran of general structure 2. 제 6항에 있어서, 상기 PC 및 PC' 중 하나는 일반 구조 1의 나프토[1,2-b]피란이고, 다른 하나는 일반 구조 2의 나프토[2,1-b]피란인 이광변색성 분자.7. The composition of claim 6 wherein one of the PC and PC 'is naphtho [1,2-b] pyran of general structure 1 and the other is naphtho [2,1- b] Sex Molecules. 제 4항에 있어서, Y는 산소를 나타내고, Q는 -(CH2CH2)-를 나타내고, R19는 메틸인 이광변색성 분자.The photochromic molecule according to claim 4, wherein Y represents oxygen, Q represents - (CH 2 CH 2 ) - and R 19 represents methyl. 제 4항에 있어서, Y는 산소를 나타내고, Q는
Figure 112015101451282-pct00034
을 나타내고 R19는 메틸인 이광변색성 분자.5. The compound according to claim 4, wherein Y represents oxygen, Q represents
Figure 112015101451282-pct00034
And R19 is methyl. 제 4항에 있어서, 상기 이광변색성 분자가 (1,3-디하이드로-3,3-디메틸-1-네오펜틸-6'-(4"-N-에틸, N-(숙시닐에틸)아닐리노)스피로[2H-인돌-2,3'-3H-나프토[1,2-b][1,4]옥사진)2-DMS-C15이고, 여기서 상기 DMS-C15는 제 5항에 정의된 바와 같은 것인 이광변색성 분자.5. The composition of claim 4 wherein said photochromic molecule is selected from the group consisting of (1,3-dihydro-3,3-dimethyl-1-neopentyl-6 '- (4 " Dino-spiro [2H-indole-2,3'-3H-naphtho [1,2- b] [1,4] oxazine) 2- DMS-C15, Lt; / RTI > 제 4항에 있어서, 상기 이광변색성 분자는 (3-(4'-메톡시페닐),3-(4"-(숙시닐에톡시)페닐)-6-모폴리노-3H-나프토[2,1-b]피란)2-DMS-C16이고, 여기서 상기 DMS-C16는 제 5항에 정의된 바와 같은 것인 이광변색성 분자.5. The composition of claim 4, wherein the photochromic molecule is selected from the group consisting of (3- (4'-methoxyphenyl), 3- (4 "-( succinylethoxy) 2,1-b] pyran) 2- DMS-C16, wherein said DMS-C16 is as defined in claim 5. 제 4항에 있어서, 상기 이광변색성 분자는 (3-(4'-메톡시페닐),3-(4"-(숙시닐에톡시)페닐)-6-모폴리노-3H-나프토[2,1-b]피란)2-DMS-C15이고, 여기서 상기 DMS-C15는 제 5항에 정의된 바와 같은 것인 이광변색성 분자.5. The composition of claim 4, wherein the photochromic molecule is selected from the group consisting of (3- (4'-methoxyphenyl), 3- (4 "-( succinylethoxy) 2,1-b] pyran) 2- DMS-C15, wherein said DMS-C15 is as defined in claim 5. 제 4항에 있어서, 상기 이광변색성 분자는 (1,3-디하이드로-3,3-디메틸-1-이소부틸-9'-숙시닐-스피로[2H-인돌-2,3'-3H-나프토[2,1-b][1,4]옥사진)2-DMS-C16이고, 여기서 상기 DMS-C16는 제 5항에 정의된 바와 같은 것인 이광변색성 분자.The method of claim 4, wherein the photochromic molecule is (1,3-dihydro-3,3-dimethyl-1-isobutyl-9'-succinyl- spiro [2H- indole- Naphtho [2,1-b] [1,4] oxazine) 2- DMS-C16, wherein said DMS-C16 is as defined in claim 5. 제 4항에 있어서, 상기 이광변색성 분자는 (2-(4'-피롤리디노페닐)-2-페닐-5-프탈로일메틸-6-아니실-9-메톡시-2H-나프토[1,2-b]피란)2-DMS-C15이고, 여기서 상기 DMS-C15는 제 5항에 정의된 바와 같은 것인 이광변색성 분자.5. The composition of claim 4, wherein the photochromic molecule is selected from the group consisting of (2- (4'-pyrrolidinophenyl) -2-phenyl-5-phthaloylmethyl-6-anilyl-9-methoxy- [1,2-b] pyran) 2- DMS-C15, wherein DMS-C15 is as defined in claim 5. 제 4항에 있어서, 상기 이광변색성 분자는 (2,2-비스(4'-메톡시페닐)-5-하이드록시메틸-6-메틸-2H-나프토[1,2-b]피란)2-DMS-B12이고, 여기서 상기 DMS-B12는 제 5항에 정의된 바와 같은 것인 이광변색성 분자.5. The composition of claim 4, wherein the photochromic molecule is selected from the group consisting of (2,2-bis (4'-methoxyphenyl) -5-hydroxymethyl-6-methyl-2H- 2- DMS-B12, wherein said DMS-B12 is as defined in claim 5. 제 4항에 있어서, 상기 이광변색성 분자는 (2-(4'-피롤리디노페닐)-2-페닐-5-숙시닐메틸-6-아니실-9-메톡시-2H-나프토[1,2-b]피란)-DMS-C15-(3-페닐-3-(4'-(숙시닐에톡시)페닐)-6-모폴리노-3H-나프토[2,1-b]피란)이고, 여기서 상기 DMS-C15는 제 5항에 정의된 바와 같은 것인 이광변색성 분자.5. The method of claim 4, wherein the photochromic molecule is selected from the group consisting of (2- (4'-pyrrolidinophenyl) -2-phenyl-5-succinylmethyl- 1,2-b] pyran) -DMS-C15- (3-phenyl-3- (4 '-( succinylethoxy) Pyran), wherein said DMS-C15 is as defined in claim 5. 제 4항에 있어서, 상기 이광변색성 분자는 (1,3-디하이드로-3,3-디메틸-1-네오펜틸-9'-숙시닐-스피로[2H-인돌-2,3'-3H-나프토[2,1-b][1,4]옥사진])2-DMS-A214이고, 여기서 상기 DMS-A214는 제 5항에 정의된 바와 같은 것인 이광변색성 분자.5. The method of claim 4, wherein the photochromic molecule is selected from the group consisting of (1,3-dihydro-3,3-dimethyl-1-neopentyl-9'-succinyl- spiro [2H- indole- Naphtho [2,1-b] [1,4] oxazine]) 2- DMS-A214, wherein said DMS-A214 is as defined in claim 5. 제 4항에 있어서, 상기 이광변색성 분자는 (2,2-비스(4'-메톡시페닐)-5-숙시닐메틸-6-메틸-2H-나프토[1,2-b]피란)2-DMS-C15이고, 여기서 상기 DMS-C15는 제 5항에 정의된 바와 같은 것인 이광변색성 분자.5. The composition of claim 4, wherein the photochromic molecule is selected from the group consisting of (2,2-bis (4'-methoxyphenyl) -5-succinylmethyl-6-methyl-2H-naphtho [ 2- DMS-C15, wherein said DMS-C15 is as defined in claim 5. 제 1항 내지 제 20항 중 어느 한 항에 따른 이광변색성 분자를 포함하는 안과용 렌즈An ophthalmic lens comprising a photochromic molecule according to any one of claims 1 to 20 제 1항 내지 제 20항 중 어느 한 항에 따른 이광변색성 분자를 포함하는 폴리머 호스트 재료.20. A polymer host material comprising a photochromic molecule according to any one of claims 1 to 20. 제 1항 내지 제 20 항 중 어느 한 항에 따른 이광변색성 분자의 제조방법으로서, 폴리디알킬실록산 올리고머, 연결기 및 하나 이상의 광변색성 화합물을 반응시켜서 상기 이광변색성 분자를 형성하는 단계를 포함하는 이광변색성 분자의 제조방법. A process for producing a photochromic molecule according to any one of claims 1 to 20, comprising the step of reacting a polydialkylsiloxane oligomer, a linking group and at least one photochromic compound to form the photochromic molecule Lt; RTI ID = 0.0 > 2, < / RTI > 제 23항에 있어서, 상기 연결기가 상기 하나 이상의 광변색성 화합물과 반응하기 전에 상기 폴리디알킬실록산 올리고머에 부착되는 제조방법.24. The process of claim 23, wherein the linker is attached to the polydialkylsiloxane oligomer prior to reacting with the at least one photochromic compound. 제 23항에 있어서, 상기 연결기가 상기 폴리디알킬실록산 올리고머와 반응하기 전에 상기 하나 이상의 광변색성 화합물에 부착되는 제조방법.24. The process of claim 23, wherein the linker is attached to the at least one photochromic compound before reacting with the polydialkylsiloxane oligomer.
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