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KR101824443B1 - Novel fluorenyl oxime ester compounds, photopolymerization initiator and photoresist composition containing the same - Google Patents

Novel fluorenyl oxime ester compounds, photopolymerization initiator and photoresist composition containing the same Download PDF

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KR101824443B1
KR101824443B1 KR1020150050017A KR20150050017A KR101824443B1 KR 101824443 B1 KR101824443 B1 KR 101824443B1 KR 1020150050017 A KR1020150050017 A KR 1020150050017A KR 20150050017 A KR20150050017 A KR 20150050017A KR 101824443 B1 KR101824443 B1 KR 101824443B1
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bis
diethyl
diyl
oxime
fluorene
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KR20160121623A (en
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오천림
이득락
이민선
이원중
이재훈
조용일
신승림
신종일
안경룡
전근
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주식회사 삼양사
한국화학연구원
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Priority to PCT/KR2016/001103 priority patent/WO2016126070A1/en
Priority to JP2017541678A priority patent/JP6408715B2/en
Priority to CN201680008616.0A priority patent/CN107250105B/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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Abstract

본 발명은 신규한 플루오렌일 옥심 에스테르 화합물, 이를 포함하는 광중합 개시제 및 포토레지스트 조성물에 관한 것으로, 상세하게는 본 발명에 따른 플루오렌일 옥심 에스테르 화합물은 하기 화학식 1로 표시되는 것을 특징으로 한다.
[화학식 1]

Figure 112015034569412-pat00064

상기 화학식 1에서 A, L1, 및 R1 내지 R4 은 각각 발명의 상세한 설명에서 정의한 바와 같다. The present invention relates to a novel fluorenyl oxime ester compound, a photopolymerization initiator containing the same, and a photoresist composition. More particularly, the fluorenyl oxime ester compound according to the present invention is represented by the following general formula (1).
[Chemical Formula 1]
Figure 112015034569412-pat00064

In formula (1), A, L 1 , and R 1 to R 4 are each as defined in the description of the invention.

Description

신규한 플루오렌일 옥심 에스테르 화합물, 이를 포함하는 광중합 개시제 및 포토레지스트 조성물{Novel fluorenyl oxime ester compounds, photopolymerization initiator and photoresist composition containing the same}[0001] The present invention relates to novel fluorenyl oxime ester compounds, photopolymerization initiators containing the same, and photoresist compositions containing the same.

본 발명은 신규한 플루오렌일 옥심 에스테르 화합물, 이를 포함하는 광중합 개시제 및 포토레지스트 조성물에 관한 것이다.The present invention relates to a novel fluorenyl oxime ester compound, a photopolymerization initiator containing the same, and a photoresist composition.

포토레지스트 조성물에 사용되는 광중합 개시제의 일반적인 예는 아세토페논 유도체, 벤조페논 유도체, 트리아진 유도체, 비이미다졸 유도체, 아실포스핀 옥사이드 유도체 및 옥심에스테르 유도체 등 여러 종류가 알려져 있으며, 이중 옥심에스테르 유도체는 자외선을 흡수하여 색을 거의 나타내지 않고, 라디칼 발생 효율이 높으며, 포토레지스트 조성물 재료들과의 상용성 및 안정성이 우수한 장점을 갖고 있다. 그러나 초기에 개발된 옥심 유도체 화합물은 광개시 효율이 낮으며, 특히 패턴 노광 공정시 감도가 낮아 노광량을 늘려야 하고 이로 인해 생산량이 줄어드는 문제가 있다.As typical examples of the photopolymerization initiator used in the photoresist composition, various kinds of acetophenone derivatives, benzophenone derivatives, triazine derivatives, nonimidazole derivatives, acylphosphine oxide derivatives and oxime ester derivatives are known, Absorbs ultraviolet light to hardly show color, has a high radical generation efficiency, and is excellent in compatibility and stability with photoresist composition materials. However, the oxime derivative compounds initially developed have a low photoinitiator efficiency, and in particular, there is a problem that the sensitivity is low in the pattern exposure process to increase the exposure dose, thereby decreasing the yield.

그러므로 광 감도가 우수한 광중합 개시제의 개발은 적은 양으로 충분한 감도를 구현 할 수 있어 원가 절감 효과 및 우수한 감도로 인해 노광량을 낮출 수 있어 생산량을 높일 수 있다. Therefore, the development of a photopolymerization initiator having excellent photosensitivity can realize a sufficient sensitivity with a small amount, and the amount of exposure can be lowered due to the cost reduction effect and the excellent sensitivity, thereby increasing the production amount.

포토레지스트 조성물에 광중합 개시제로 사용 가능한 하기 화학식 A로 표시되는 다양한 옥심에스테르 화합물 유도체는 이미 공지되어 있다.Various oxime ester compound derivatives represented by the following formula (A), which can be used as a photopolymerization initiator in a photoresist composition, are already known.

[화학식 A] (A)

Figure 112015034569412-pat00001
Figure 112015034569412-pat00001

상기 화학식 A로 표시되는 옥심에스테르 화합물의 경우, R, R' 및 R" 각각에 적절한 치환기를 도입함으로써, 이를 포함하는 광중합 개시제의 광 흡수영역이 조절 가능할 수 있다.In the case of the oxime ester compound represented by the above formula (A), the light absorption region of the photopolymerization initiator containing the oxime ester compound can be adjusted by introducing an appropriate substituent to each of R, R 'and R ".

옥심에스테르 화합물은 포토레지스트 조성물에 365 내지 435 nm의 빛을 조사함으로서 불포화 결합을 갖는 중합성 화합물을 중합 및 경화시킬 수 있어서 블랙매트릭스, 컬러필터, 컬럼스페이서, 유연절연막, 오버코트용 포토레지스트 조성물 등에 이용되고 있다.The oxime ester compound can polymerize and cure a polymerizable compound having an unsaturated bond by irradiating the photoresist composition with light of 365 to 435 nm, and is useful for a black matrix, a color filter, a column spacer, a flexible insulating film, .

따라서, 광개시제는 365 내지 435 nm 등 장파장 광원에 높은 감도를 가지며, 광중합 반응성이 좋고, 제조가 용이하며, 열안정성 및 저장안정성이 높아 취급이 용이하며 용제(PGMEA; 프로필렌 글리콜 모노메틸 에테르 아세테이트)에 대한 만족할 만한 용해도 등 산업 현장의 요구를 충족시킬 수 있는 다양한 용도에 적합한 새로운 광개시제가 지속적으로 요구되고 있다.Therefore, the photoinitiator has high sensitivity to a long wavelength light source such as 365 to 435 nm, has good photopolymerization reactivity, is easy to manufacture, has high thermal stability and storage stability and is easy to handle, and has a high solubility in solvents (PGMEA; propylene glycol monomethyl ether acetate) There is a continuing need for new photoinitiators suitable for a variety of uses that can meet the needs of industrial sites such as satisfactory solubility in water.

이에, 최근에는 액정표시소자 및 OLED 등 박막 디스플레이 등에 사용되는 포토레지스트 조성물에 있어서, 보다 상세하게는 알칼리 현상액으로 현상되어 TFT-LCD와 같은 액정표시소자의 유기 절연막, 컬럼스페이서, UV 오버코트, R.G.B. 컬러 레지스트 및 Black Matrix 등으로 패턴 형성이 가능한 고감도 광중합 개시제를 함유하는 포토레지스트 조성물에 관한 연구가 많이 진행되고 있다.In recent years, in a photoresist composition used for a liquid crystal display device and a thin film display such as an OLED, more specifically, an organic insulating film of a liquid crystal display device such as a TFT-LCD, a column spacer, a UV overcoat, Studies on a photoresist composition containing a color-resist and a high-sensitivity photopolymerization initiator capable of forming a pattern by a Black Matrix or the like have been conducted.

종래 패턴을 형성하기 위해서 이용되는 포토레지스트 조성물로는 바인더 수지, 에틸렌 불포화 결합을 갖는 다관능성 모노머 및 광중합 개시제 등을 함유하는 포토레지스트 조성물이 선호되고 있으나, 이러한 종래 포토레지스트 조성물을 이용하여 패턴을 형성하는 경우 패턴 형성을 위한 노광 공정 시 감도가 낮아 광중합 개시제의 사용량을 늘리거나 노광량을 늘려야 하고, 이로 인해 노광 공정에서 마스크를 오염시키고, 고온 가교 시에 광중합 개시제가 분해한 후 발생하는 부산물로 수율이 저하되는 단점이 있고, 노광량 증가에 따른 노광공정 시간이 늘어나 생산량이 줄어드는 등의 문제점을 가진다.As a photoresist composition used for forming a conventional pattern, a photoresist composition containing a binder resin, a polyfunctional monomer having an ethylenically unsaturated bond, and a photopolymerization initiator is preferred, but a conventional photoresist composition is used to form a pattern It is necessary to increase the amount of photopolymerization initiator used or to increase the amount of exposure, thereby contaminating the photoresist in the exposure process, and as a by-product after decomposition of the photopolymerization initiator at high temperature crosslinking, yield There is a disadvantage in that the time required for the exposure process increases with an increase in the exposure dose and the production amount is reduced.

이에, 본 출원인은 상기와 같은 종래 포토레지시트 조성물의 문제점을 개선하기 위해 광에 대한 감도가 우수하여 반응 전환율이 높으며, 열 안정성 및 광 안정성이 뛰어나 광개시 후 분해되지 않아 높은 패턴 안정성 및 잔막율을 구현할 수 있는 신규한 플루오렌일 옥심 에스테르 화합물, 이를 포함하는 광중합 개시제 및 포토레지스트 조성물을 제공하고자 본 발명을 완성하였다.In order to solve the problems of the conventional photoresist composition as described above, the applicant of the present invention has found that the photoresist composition of the present invention is excellent in sensitivity to light and has high reaction conversion rate, excellent thermal stability and light stability, Lt; RTI ID = 0.0 > fluorenyloxime < / RTI > ester A photopolymerization initiator comprising the same, and a photoresist composition.

[특허문헌 1] 일본 공개특허공보 JP 2001-302871 (2001.10.31)[Patent Document 1] JP-A-2001-302871 (Oct. 31, 2001) [특허문헌 2] 국제 공개특허공보 WO 2002-100903 (2002.12.19)[Patent Document 2] International Patent Publication No. WO 2002-100903 (Dec. 19, 2002) [특허문헌 3] 일본 공개특허공보 JP 2006-160634 (2006.06.22)[Patent Document 3] JP-A-2006-160634 (Jun. 22, 2006) [특허문헌 4] 일본 공개특허공보 JP 2005-025169 (2005.01.27)[Patent Document 4] JP-A-2005-025169 (2005.01.27) [특허문헌 5] 일본 공개특허공보 JP 2005-242279 (2005.09.08)[Patent Document 5] JP-A-2005-242279 (2005.09.08) [특허문헌 6] 국제 공개특허공보 WO 2007-071497 (2007.06.28)[Patent Document 6] International Patent Publication No. WO 2007-071497 (Jun. 28, 2007) [특허문헌 7] 국제 공개특허공보 WO 2008-138733 (2008.11.20)[Patent Document 7] International Patent Publication No. WO 2008-138733 (2008.11.20) [특허문헌 8] 국제 공개특허공보 WO 2008-078686 (2008.07.03)[Patent Document 8] International Patent Publication No. WO 2008-078686 (Jul. 3, 2008) [특허문헌 9] 국제 공개특허공보 WO 2009-081483 (2009.07.02)[Patent Document 9] International Patent Publication No. WO 2009-081483 (2009.07.02) [특허문헌 10] 한국 공개특허공보 KR 2013-0049811 (2013.11.13)[Patent Document 10] Korean Published Patent Application No. 2013-0049811 (Nov. 13, 2013) [특허문헌 11] 한국 공개특허공보 KR 2013-0115272 (2013.10.21)[Patent Document 11] Korean Patent Laid-Open Publication No. 2013-0115272 (Oct. 31, 2013) [특허문헌 12] 유럽 공개특허공보 EP 2128132 (2009.12.02)[Patent Document 12] European Patent Publication No. EP 2128132 (2009.12.02)

본 발명의 목적은 감도, 내열성, 내광성, 내화학석 및 내현상성이 우수한 신규의 플루오렌일 옥심 에스테르 화합물, 이를 함유하는 광중합 개시제 및 포토레지스트 조성물을 제공하는 것이다.An object of the present invention is to provide a novel fluorenyl oxime ester compound excellent in sensitivity, heat resistance, light resistance, chemical resistance and resistance to development, a photopolymerization initiator containing the same, and a photoresist composition.

상기의 목적을 달성하기 위하여 본 발명은 하기 화학식 1로 표시되는 플루오렌일 옥심 에스테르 화합물, 이를 포함하는 광중합 개시제 및 포토레지스트 조성물을 제공한다.In order to accomplish the above object, the present invention provides a fluorenyl oxime ester compound represented by the following general formula (I), a photopolymerization initiator containing the same, and a photoresist composition.

[화학식 1][Chemical Formula 1]

Figure 112015034569412-pat00002
Figure 112015034569412-pat00002

[상기 화학식 1에서, [In the above formula (1)

R1 내지 R4는 각각 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C1-C20)알콕시, (C6-C20)아릴(C1-C20)알킬, 히드록시(C1-C20)알킬, 히드록시(C1-C20)알콕시(C1-C20)알킬, (C3-C20)사이클로알킬 또는 (C3-C20)사이클로알킬(C1-C20)알킬이고; R 1 to R 4 are independently hydrogen, halogen, (C 1 -C 20) alkyl, respectively, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C 1 -C 20) alkyl, hydroxy (C 1 -C 20) alkyl, hydroxy (C 1 -C 20) alkoxy (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl or (C 3 -C 20) cycloalkyl (C 1 -C 20) alkyl;

A는 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C6-C20)아릴(C1-C20)알킬, 니트로 또는 시아노이고;A is hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, nitro or cyano;

L1은 단일결합, -CO- 또는

Figure 112015034569412-pat00003
이다.]L 1 is a single bond, -CO- or
Figure 112015034569412-pat00003
to be.]

상기 화학식 1에서, 각각의 R2와 R4는 서로 동일하거나 상이할 수 있다.In Formula 1, each of R 2 and R 4 may be the same or different from each other.

본 발명의 용어 “할로겐”은 불소, 염소, 브롬 또는 요오드 원자를 의미한다. The term " halogen " of the present invention means a fluorine, chlorine, bromine or iodine atom.

본 발명의 용어 “알킬”은 탄소 및 수소 원자만으로 구성된 1가의 직쇄 또는 분쇄 포화 탄화수소 라디칼을 의미하는 것으로, 구체적인 예로 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸, s-부틸, t-부틸, n-펜틸, i-펜틸, s-펜틸, n-헥실, i-헥실, s-헥실, n-헵틸, n-옥틸, n-노닐, n-데실, i-데실, n-운데실, n-도데실, n-트리데실, n-테트라데실, n-펜타데실 및 n-헥사데실 등을 포함하지만 이에 한정되지는 않는다.The term "alkyl" of the present invention to mean a monovalent linear or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms, and specific examples of methyl, ethyl, n - propyl, i - propyl, n - butyl, i - butyl, s - butyl, t - butyl, n - pentyl, i-pentyl, s-pentyl, n-hexyl, i-hexyl, s-hexyl, n- heptyl, n- octyl, n- nonyl, n- decyl, i-decyl , n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl, and the like.

본 발명의 용어 “아릴”은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포함한다. 구체적인 예로 페닐, 나프틸, 바이페닐, 터페닐, 안트릴, 인데닐(indenyl), 플루오레닐, 페난트릴 등을 포함하지만, 이에 한정되지는 않는다. The term " aryl " of the present invention refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, with a single or fused ring containing, suitably, 4 to 7, preferably 5 or 6, ring atoms in each ring And includes a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl and the like.

본 발명의 용어 “알콕시”는 -O-알킬 라디칼을 의미하는 것으로, 구체적인 예로 메톡시, 에톡시, 이소프로폭시, 부톡시, 이소부톡시, t-부톡시 등으로 예시될 수 있다.The term " alkoxy " of the present invention means a -O -alkyl radical, and specific examples thereof include methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t -butoxy and the like.

본 발명의 용어 “아릴알킬”는 상기 정의한 아릴이 치환된 알킬기로, 구체적인 예로 벤질 등으로 예시될 수 있다.The term " arylalkyl " of the present invention is an aryl-substituted alkyl group as defined above, and specific examples thereof include benzyl and the like.

본 발명의 용어 “히드록시알킬”은 히드록시가 치환된 알킬기로, 구체적인 예로 히드록시메틸, 히드록시에틸, 히드록시프로필, 히드록시부틸, 히드록시펜틸, 히드록시헥실 등으로 예시될 수 있다.The term " hydroxyalkyl " of the present invention is an alkyl group substituted with hydroxy, and specific examples thereof include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl and the like.

본 발명의 용어 “히드록시알콕시알킬”은 히드록시알콕시로 치환된 알킬기로, 구체적인 예로 히드록시메톡시메틸, 히드록시메톡시에틸, 히드록시메톡시프로필, 히드록시메톡시부틸, 히드록시에톡시메틸, 히드록시에톡시에틸, 히드록시에톡시프로필, 히드록시에톡시부틸, 히드록시에톡시펜틸, 히드록시에톡시헥실 등으로 예시될 수 있다.The term " hydroxyalkoxyalkyl " of the present invention is an alkyl group substituted by hydroxyalkoxy, and specific examples thereof include hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxy Methyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl, and the like.

본 발명의 용어 “사이클로알킬”은 탄소 고리원수 3 내지 7의 단환상 알킬 기 뿐만 아니라 두 개 이상의 단환상 알킬이 융합된 다환상 알킬기를 의미한다. 구체적인 예로 시클로프로필, 시클로부틸, 시클로펜틸, 시클로헥실 등을 들 수 있으나, 이에 한정되지는 않는다.The term " cycloalkyl " in the present invention means a monocyclic alkyl group having 3 to 7 carbon ring atoms as well as a polycyclic alkyl group fused with two or more monocyclic alkyls. Specific examples thereof include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

본 발명의 용어 “사이클로알킬알킬”은 상기 정의한 사이클로알킬이 치환된 알킬기를 의미하는 것으로, 구체적인 예로 시클로프로필메틸, 시클로부틸메틸, 시클로펜틸메틸, 시클로프로필에틸 등으로 예시될 수 있다.The term " cycloalkylalkyl " in the present invention means an alkyl group substituted with the above-defined cycloalkyl, and specific examples thereof include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl, and the like.

본 발명의 일 실시예에 따른 상기 플루오렌일 옥심 에스테르 화합물은 365 내지 435 nm 파장의 빛에 대한 뛰어난 감도를 가지는 측면에서 하기 화학식 2 또는 3으로 표시되는 플루오렌일 옥심 에스테르 화합물일 수 있다. The fluorenyl oxime ester compound according to an embodiment of the present invention may be a fluorenyl oxime ester compound represented by the following formula 2 or 3 in view of excellent sensitivity to light having a wavelength of 365 to 435 nm.

[화학식 2](2)

Figure 112015034569412-pat00004
Figure 112015034569412-pat00004

[화학식 3](3)

Figure 112015034569412-pat00005
Figure 112015034569412-pat00005

[상기 화학식 2 및 화학식 3에서, [In the formulas (2) and (3)

R1 내지 R4는 각각 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C1-C20)알콕시, (C6-C20)아릴(C1-C20)알킬, 히드록시(C1-C20)알킬, 히드록시(C1-C20)알콕시(C1-C20)알킬, (C3-C20)사이클로알킬 또는 (C3-C20)사이클로알킬(C1-C20)알킬이고; R 1 to R 4 are independently hydrogen, halogen, (C 1 -C 20) alkyl, respectively, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C 1 -C 20) alkyl, hydroxy (C 1 -C 20) alkyl, hydroxy (C 1 -C 20) alkoxy (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl or (C 3 -C 20) cycloalkyl (C 1 -C 20) alkyl;

A는 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, 니트로 또는 시아노이고;A is hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, nitro or cyano;

수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, 니트로 또는 시아노Hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, nitro or cyano

n은 0 또는 1 이다.]n is 0 or 1.]

바람직하게, 상기 화학식 1에서 R1 내지 R4는 각각 독립적으로 수소, 할로겐, (C1-C10)알킬, (C6-C18)아릴, (C6-C18)아릴(C1-C10)알킬, 히드록시(C1-C10)알킬, 히드록시(C1-C10)알콕시(C1-C10)알킬, (C3-C10)사이클로알킬 또는 (C3-C10)사이클로알킬(C1-C10)알킬이고; R4는 수소, (C1-C10)알킬, (C6-C18)아릴(C1-C10)알킬, 히드록시(C1-C10)알킬, 히드록시(C1-C10)알콕시(C1-C10)알킬, (C3-C10)사이클로알킬 또는 (C3-C10)사이클로알킬(C1-C10)알킬이고; A는 수소, 할로겐, 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸, t-부틸, n-펜틸, i-펜틸, n-헥실, i-헥실, 페닐, 나프틸, 바이페닐, 터페닐, 안트릴, 인데닐, 페난트릴, 니트로 또는 시아노 일 수 있으며, 이에 한정되지는 않는다.Preferably, in the formula 1 R 1 to R 4 are independently hydrogen, halogen, (C 1 -C 10) alkyl, (C 6 -C 18) aryl, (C 6 -C 18) aryl, each (C 1 - C 10) alkyl, hydroxy (C 1 -C 10) alkyl, hydroxy (C 1 -C 10) alkoxy (C 1 -C 10) alkyl, (C 3 -C 10) cycloalkyl or (C 3 -C 10) cycloalkyl (C 1 -C 10) alkyl; R 4 is hydrogen, (C 1 -C 10) alkyl, (C 6 -C 18) aryl (C 1 -C 10) alkyl, hydroxy (C 1 -C 10) alkyl, hydroxy (C 1 -C 10 ) alkoxy (C 1 -C 10) alkyl, (C 3 -C 10) cycloalkyl or (C 3 -C 10) cycloalkyl (C 1 -C 10) alkyl; A is hydrogen, halogen, methyl, ethyl, n - propyl, i - propyl, n - butyl, i - butyl, t - butyl, n - pentyl, i - pentyl, n - hexyl, i - cyclohexyl, phenyl, naphthyl , Biphenyl, terphenyl, anthryl, indenyl, phenanthryl, nitro, or cyano.

보다 바람직하게, 상기 R1 내지 R4는 각각 독립적으로 수소, 브로모, 클로로, 아이오도, 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸, t-부틸, n-펜틸, i-펜틸, n-헥실, i-헥실, 페닐, 나프틸, 바이페닐, 터페닐, 안트릴, 인데닐, 페난트릴, 메톡시, 에톡시, n-프로필옥시, i-프로필옥시, n-부톡시, i-부톡시, t-부톡시, 벤질, 히드록시메틸, 히드록시에틸, 히드록시n-프로필, 히드록시n-부틸, 히드록시i-부틸, 히드록시n-펜틸, 히드록시i-펜틸, 히드록시n-헥실, 히드록시i-헥실, 히드록시메톡시메틸, 히드록시메톡시에틸, 히드록시메톡시프로필, 히드록시메톡시부틸, 히드록시에톡시메틸, 히드록시에톡시에틸, 히드록시에톡시프로필, 히드록시에톡시부틸, 히드록시에톡시펜틸, 히드록시에톡시헥실, 사이클로프로필, 사이클로펜틸, 사이클로헥실, 사이클로프로필메틸, 사이클로펜틸메틸 또는 사이클로헥실메틸이고;More preferably, the R 1 to R 4 are each independently hydrogen, bromo, chloro, iodo, methyl, ethyl, n - propyl, i - propyl, n - butyl, i - butyl, t - butyl, n - pentyl, i - pentyl, n - hexyl, i - cyclohexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n - propyloxy, i - propyloxy, n -butoxy, i -butoxy, t -butoxy, benzyl, hydroxymethyl, hydroxyethyl, hydroxy n -propyl, hydroxy n -butyl, hydroxy i -butyl, hydroxy n -pentyl, I -pentyl, hydroxy n -hexyl, hydroxy i -hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxy Methoxyethyl, ethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl, cyclopropyl, cyclopentyl, cyclohexyl, Cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl;

A는 수소, 할로겐, 니트로 또는 시아노일 수 있다.A can be hydrogen, halogen, nitro or cyano.

본 발명의 일 실시예에 따른 상기 플루오렌일 옥심 에스테르 화합물로는 대표적으로 하기의 화합물을 들 수 있으나, 하기 화합물이 본 발명을 한정하는 것은 아니다.

Figure 112015034569412-pat00006
Examples of the fluorenyl oxime ester compound according to an embodiment of the present invention include the following compounds, but the following compounds are not intended to limit the present invention.
Figure 112015034569412-pat00006

Figure 112015034569412-pat00007
Figure 112015034569412-pat00007

Figure 112015034569412-pat00008
Figure 112015034569412-pat00008

Figure 112015034569412-pat00009
Figure 112015034569412-pat00009

Figure 112015034569412-pat00010
Figure 112015034569412-pat00010

Figure 112015034569412-pat00011
Figure 112015034569412-pat00011

Figure 112015034569412-pat00012
Figure 112015034569412-pat00012

Figure 112015034569412-pat00013
Figure 112015034569412-pat00013

Figure 112015034569412-pat00014
Figure 112015034569412-pat00014

Figure 112015034569412-pat00015
Figure 112015034569412-pat00015

본 발명에 따른 상기 화학식 2 또는 화학식 3으로 표시되는 플루오렌일 옥심 에스테르 화합물은 하기 반응식 1에 나타난 바와 같이 제조될 수 있으나 이에 한정되는 것은 아니다.The fluorenyl oxime ester compound represented by Formula 2 or Formula 3 according to the present invention can be prepared as shown in the following Reaction Scheme 1, but is not limited thereto.

[반응식 1] [Reaction Scheme 1]

Figure 112015034569412-pat00016
Figure 112015034569412-pat00016

[상기 반응식 1에서 A와 R1 내지 R4 및 n은 화학식 2 및 3에서의 정의와 동일하고, X1 내지 X4는 각각 독립적으로는 할로겐이다.]Wherein A, R 1 to R 4 and n are the same as defined in formulas (2) and (3), and X 1 to X 4 are each independently halogen.

또한, 본 발명은 상기 화학식 1로 표시되는 플루오렌일 옥심 에스테르 화합물을 포함하는 광중합 개시제를 제공한다.The present invention also provides a photopolymerization initiator comprising the fluorenyl oxime ester compound represented by the above formula (1).

또한, 본 발명은 상기 화학식 1로 표시되는 플루오렌일 옥심 에스테르 화합물을 포함하는 포토레지스트 조성물을 제공한다. 이때, 상기 포토레지스트 조성물은 상기 화학식 1로 표시되는 플루오렌일 옥심 에스테르 화합물 이외 바인더 수지 , 광반응성 화합물 및 용매 등을 더 포함할 수 있으며, 이들의 적절한 조합으로 패턴의 특성 조절과 내열성 및 내화학성 등의 우수한 박막 물성을 구현할 수 있다.The present invention also provides a photoresist composition comprising the fluorenyl oxime ester compound represented by the above formula (1). The photoresist composition may further contain a binder resin, a photoreactive compound, a solvent, and the like in addition to the fluorenyl oxime ester compound represented by the formula (1). By appropriately combining them, And the like can be realized.

본 발명에서 상기 화학식 1로 표시되는 플루오렌일 옥심 에스테르 화합물은 광중합 개시제로서 포토레지스트 조성물에 포함될 수 있으며, 상기 플루오렌일 옥심 에스테르 화합물의 첨가량은 투명성을 높이며 노광량을 최소화하기 위한 함량으로서 전체 포토레지스트 조성물 100 중량%에 대하여 0.01 내지 15 중량%로 포함될 수 있으며, 바람직하게는 0.01 내지 10 중량%, 보다 바람직하게는 0.01 내지 5 중량%로 포함되는 것이 광 개시 후 분해되는 부산물에 의한 오염을 최소화 할 수 있어 좋다.In the present invention, the fluorenyl oxime ester compound represented by the general formula (1) may be included in the photoresist composition as a photopolymerization initiator. The amount of the fluorenyl oxime ester compound added is to increase the transparency and minimize the exposure dose. May be contained in an amount of 0.01 to 15% by weight, preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight, based on 100% by weight of the composition, to minimize contamination with by- Can be good.

또한 본 발명의 일 실시예에 따른 상기 포토레지스트 조성물에 있어서, 상기 바인더 수지는 패턴 특성 조절을 위해 점도를 조절하는 효과 또는 알칼리 현상액을 이용한 패터닝을 가능하게 하는 효과가 있는 것이라면 한정되는 것은 아니며, 바람직하게는 아크릴 중합체, 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체, 에틸렌성 불포화결합을 갖는 중합성 화합물 등일 수 있다. 이때, 상기 바인더 수지는 상기 포토레지스트 조성물 100 중량%에 대하여 3 내지 50 중량%를 사용될 수 있다.Further, in the photoresist composition according to an embodiment of the present invention, the binder resin is not limited as long as it has an effect of controlling the viscosity for controlling the pattern characteristics or an effect of enabling patterning using an alkaline developer, May be an acrylic polymer, an acrylic polymer having an acrylic unsaturated bond in the side chain, a polymerizable compound having an ethylenic unsaturated bond, and the like. In this case, the binder resin may be used in an amount of 3 to 50% by weight based on 100% by weight of the photoresist composition.

본 발명의 일 실시예에 따른 상기 바인더 수지의 구체적인 일예로는 평균 분자량 2,000 내지 30O,O00, 분산도는 1.0 내지 10.0 인 아크릴 중합체일 수 있으며, 보다 바람직하게는 평균 분자량 4,000 내지 10O,O00 인 것이 좋다. 상기 아크릴 중합체는 하기 단량체들을 포함하는 단량체들의 공중합체로서, 단량체의 예로는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 시클로헥실(메타)아크릴 레이트, 헵틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 노닐(메타)아크릴 레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 도데실(메타) 아크릴레이트, 테트라데실(메타)아크릴레이트, 헥사데실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 아다만틸(메타)아크릴레이트, 디시클로펜타닐(메타) 아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 아크릴산, 메타아크릴산, 이타코닉산, 말레익산, 말레익산무수물, 말레익산모노알킬 에스터, 모노알킬 이타코네이트, 모노알킬 퓨말레이트, 글리시딜아크릴레이트, 글리시딜 메타아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 2,3-에폭시시클로헥실 (메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트, 3-메틸 옥세탄-3-메틸(메타)아크릴레이트, 3-에틸옥세탄-3-메틸(메타)아크릴레이트, 스틸렌, α-메틸스틸렌, 아세톡시스틸렌, N-메틸말레이미드, N-에틸말레이미드, N-프로필말레이미드, N-부틸말레이미드, N-시클로헥실말레이미드, (메타)아크릴 아미드, N-메틸(메타)아크릴아미드 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상 일 수 있다.The binder resin according to one embodiment of the present invention may be an acrylic polymer having an average molecular weight of 2,000 to 300 and a dispersity of 1.0 to 10.0, more preferably an average molecular weight of 4,000 to 10O, good. (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate and the like. The acrylic polymer is a copolymer of monomers comprising the following monomers: Acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (Meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, isobonyl (Meth) acrylate, 2-methoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl Maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, 3-methyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl oxetan-3-methyl (meth) acrylate, styrene, α- methyl styrene, acetoxy-styrene, N - methyl maleimide, N - ethyl maleimide, N - propyl maleimide, N - butyl maleimide, N - cyclo (Meth) acrylamide, N -methyl (meth) acrylamide, and the like, each of which may be used alone or in combination of two or more.

상기 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체는 카르복실 산을 함유한 아크릴 공중합체에 에폭시 수지를 부가반응한 공중합체로서, 단량체의 예로는 아크릴산, 메타아크릴산, 이타코닉산, 말레익산, 말레익산모노알킬 에스터 등의 카르복실산을 함유한 아크릴 모노머와 메틸(메타)아크릴레이트, 헥실(메타) 아크릴레이트 등의 알킬(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 아다만틸(메타)아크릴레이트, 디시클로펜타닐 (메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 스틸렌, α-메틸스틸렌, 아세톡시스틸렌, N-메틸말레이미드, N-에틸말레이미드, N-프로필말레이미드, N-부틸말레이미드, N-시클로헥실말레이미드, (메타)아크릴 아미드, N-메틸(메타)아크릴아미드 등의 모노머 2종 이상을 공중합 하여 얻은 카르복실산을 함유한 아크릴 공중합체에 글리시딜아크릴레이트, 글리시딜메타 아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 2,3-에폭시시클로헥실(메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상 일 수 있다. The acrylic polymer having an acryl unsaturated bond in the side chain is a copolymer obtained by addition reaction of an epoxy resin to an acrylic copolymer containing a carboxylic acid. Examples of the monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, Alkyl (meth) acrylates such as methyl (meth) acrylate and hexyl (meth) acrylate, alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, isobonyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl ethoxyethyl (meth) acrylate, styrene, α- methyl styrene, acetoxy-styrene, N - methyl maleimide, N - ethyl maleimide, N - propyl maleimide, N - butyl maleimide, N - cyclo Room maleimide, (meth) acrylamide, N - methyl (meth) when the acrylic copolymer glycidyl methacrylate, glycidyl acrylate to copolymers containing a carboxylic acid obtained by copolymerizing monomers of two or more thereof, such as acrylamide, glycidyl methacrylate , 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate. Or more.

상기 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체의 또 다른 예로는 에폭시기를 함유한 아크릴 공중합체에 카르복실 산을 부가반응한 공중합체로, 단량체의 예로는 글리시딜아크릴레이트, 글리시딜 메타아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 2,3-에폭시시클로헥실(메타)아크릴레이트, 3,4-에폭시시클로헥실 메틸(메타)아크릴레이트 등의 에폭시기를 함유한 아크릴 모노머와 메틸(메타) 아크릴레이트, 헥실(메타)아크릴레이트 등의 알킬(메타)아크릴레이트, 시클로 헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 아다만틸(메타)아크릴 레이트, 디시클로펜타닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타) 아크릴레이트, 스틸렌, α-메틸스틸렌, 아세톡시스틸렌, N-메틸말레이미드, N-에틸말레이미드, N-프로필말레이미드, N-부틸말레이미드, N-시클로헥실 말레이미드, (메타)아크릴아미드, N-메틸(메타)아크릴아미드 등의 모노머 1종 또는 2종 이상을 공중합 하여 얻은 에폭시기를 함유한 아크릴 공중합체에 아크릴산, 메타아크릴산, 이타코닉산, 말레익산, 말레익산모노알킬 에스터 등의 카르복실산을 함유한 아크릴 모노머와 40 내지 180 ℃의 온도에서 부가 반응하여 얻어진 바인더 수지일 수 있다.Another example of the acrylic polymer having an acryl unsaturated bond in the side chain is a copolymer obtained by addition reaction of a carboxylic acid to an acrylic copolymer containing an epoxy group. Examples of the monomer include glycidyl acrylate, glycidyl methacrylate , An acrylic monomer containing an epoxy group such as 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) (Meth) acrylates such as cyclohexyl (meth) acrylate, hexyl (meth) acrylate, and the like; alkyl (meth) acrylates such as cyclohexyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl Alkylene, acetoxy-styrene, N - methyl maleimide, N - ethyl maleimide, N - propyl maleimide, N - butyl maleimide, N - cyclohexyl maleimide, (meth) acrylamide, N - methyl (meth) acrylate Acrylic acid, acrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, etc., to an acrylic copolymer containing an epoxy group obtained by copolymerizing one or more kinds of monomers such as acrylic acid, And may be a binder resin obtained by an addition reaction at a temperature of 40 to 180 ° C.

또한 본 발명의 일 실시예에 따른 상기 포토레지스트 조성물에 있어서, 상기 에틸렌성 불포화결합을 갖는 중합성 화합물은 패턴 형성시 광반응에 의하여 가교되어 패턴을 형성하는 역할을 하며 고온 가열시 가교되면서 우수한 내화학성 및 내열성을 부여할 수 있다. 이때, 상기 에틸렌성 불포화결합을 갖는 중합성 화합물은 포토레지스트 조성물 100 중량%에 대하여 0.001 내지 40 중량%를 사용하는 것이 바람직하며, 상기 범위로 사용될 경우 우수한 패턴의 연성을 구현할 수 있어 좋다.In the photoresist composition according to an embodiment of the present invention, the polymerizable compound having an ethylenically unsaturated bond is crosslinked by a photoreaction at the time of pattern formation to form a pattern, Chemical resistance and heat resistance. At this time, the polymerizable compound having an ethylenically unsaturated bond is preferably used in an amount of 0.001 to 40 wt% based on 100 wt% of the photoresist composition, and when used in the above range, a good pattern can be obtained.

상기 에틸렌성 불포화결합을 갖는 중합성 화합물은 구체적으로 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 라우릴(메타)아크릴레이트 등의 (메타)아크릴산의 알킬에스테르, 글리시딜(메타)아크릴레이트, 에틸렌옥사이드기의 수가 2 내지 14인 폴리에틸렌 글리콜모노(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 에틸렌 옥사이드기의 수가 2 내지 14인 폴리에틸렌 글리콜디(메타)아크릴레이트, 프로필렌옥사이드기의 수가 2 내지 14인 프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 비스페놀 A 디글리시딜에테르아크릴산 부가물, β-히드록시 에틸(메타)아크릴레이트의 프탈산디에스테르, β-히드록시에틸(메타)아크릴레이트의 톨루엔 디이소시아네이트 부가물, 트리메틸올프로판트리(메타) 아크릴레이트, 펜타에리스리톨트리(메타) 아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 디펜타에리스리톨 트리(메타)아크릴레이트와 같이 다가 알콜과 α,β-불포화 카르복시산을 에스테르화하여 얻어지는 화합물, 트리메틸올프로판트리글리시딜에테르아크릴산 부가물과 같이 다가 글리시딜 화합물의 아크릴산 부가물 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상 함께 사용할 수 있다. The polymerizable compound having an ethylenically unsaturated bond is specifically exemplified by methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) (Meth) acrylate, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate having a number of ethylene oxide groups of 2 to 14, ethylene glycol di (meth) acrylate, ethylene oxide Propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate having 2 to 14 carbon atoms, Acrylic acid adducts, phthalic acid diesters of? -Hydroxyethyl (meth) acrylate, toluene diisocyanates of? -Hydroxyethyl (meth) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, A compound obtained by esterifying a polyhydric alcohol and an alpha, beta -unsaturated carboxylic acid such as dipentaerythritol tri (meth) acrylate, an acrylic acid adduct of a polyglycidyl compound such as trimethylolpropane triglycidyl ether acrylic acid adduct These may be used alone or in combination of two or more.

또한, 본 발명의 일 실시예에 따른 상기 포토레지스트 조성물은 필요에 따라 추가적으로 접착보조제인 에폭시기 또는 아민기를 갖는 실리콘계 화합물을 더 포함할 수 있다.In addition, the photoresist composition according to an embodiment of the present invention may further include a silicone compound having an epoxy group or an amine group, which is an adhesion aid, if necessary.

본 발명의 포토레지스트 조성물에서 실리콘계 화합물은 ITO 전극과 포토레지스트 조성물과의 접착력을 향상시키기 위함이며, 경화 후 내열 특성을 증대시킬 수 있다. 상기 에폭시기 또는 아민기를 갖는 실리콘계 화합물의 구체적인 일예로는 (3-글리시드옥시프로필)트리메톡시실레인, (3-글리시드옥시프로필)트리에톡시실레인, (3-글리시드옥시프로필)메틸디메톡시실레인, (3-글리시드옥시프로필)메틸디에톡시실레인, (3-글리시드옥시프로필)디메틸메톡시실레인, (3-글리시드옥시프로필)디메틸에톡시실레인, 3,4-에폭시부틸트리메톡시실레인, 3,4-에폭시부틸트리에톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실레인 및 아미노프로필트리메톡시 실레인 등이 있으며, 이들을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 상기 에폭시기 또는 아민기를 갖는 실리콘계 화합물은 포토레지스트 조성물 100 중량%에 대하여 0.0001 내지 3 중량%로 사용되는 것이 좋다.In the photoresist composition of the present invention, the silicone compound is used to improve the adhesion between the ITO electrode and the photoresist composition, and can increase the heat resistance after curing. Specific examples of the silicone compound having an epoxy group or an amine group include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) Dimethoxysilane, (3-glycidoxypropyl) dimethyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4 (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -butyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- Ethyl triethoxysilane, and aminopropyltrimethoxysilane. These may be used alone or in combination of two or more. The silicone compound having an epoxy group or an amine group is preferably used in an amount of 0.0001 to 3% by weight based on 100% by weight of the photoresist composition.

또한, 본 발명의 포토레지스트 조성물은 필요에 따라 광증감제, 열중합 금지제, 소포제, 레벨링제 등의 상용성이 있는 첨가제를 더 포함할 수 있다.
In addition, the photoresist composition of the present invention may further contain a compatibilizing additive such as a photosensitizer, a thermal polymerization inhibitor, a defoaming agent, and a leveling agent, if necessary.

본 발명의 포토레지스트 조성물은 용매를 가하여 기판 위에 스핀코팅한 후 마스크를 이용하여 자외선을 조사하여 알칼리 현상액으로 현상하는 방법을 통하여 패턴을 형성하게 되는데, 상기 포토레지스트 조성물 100 중량%에 대하여 15 내지 95 중량%의 용매를 첨가하여 점도를 1 내지 50 cps 범위가 되도록 조절하는 것이 바람직하다. The photoresist composition of the present invention forms a pattern by spin coating a substrate with a solvent and then developing it with an alkali developer by irradiating ultraviolet rays using a mask. It is preferable to add a solvent by weight to adjust the viscosity to be in the range of 1 to 50 cps.

본 발명의 일 실시예에 따른 상기 광반응성 화합물은 당업계에서 상용으로 사용되는 광반응성을 가지는 화합물이라면 한정되는 것은 아니나 구체적일 일예로 디펜타에리스리톨헥사아크릴산, 펜타에리스리톨트리아크릴산, 트리메틸올프로판트리아크릴산, 에틸렌글리콜디아크릴산, 비스페놀-A 디글리시딜에테르아크릴산 부가물, 트리메틸올프로판트리글리시딜에테르아크릴산 부가물, 펜타에리스리톨트리메타아크릴산, 디펜타에리스리톨헥사아크릴산, 트리메틸올프로판트리메타크릴산, 펜타에리스리톨테트라아크릴산, 네오펜틸글리콜디메타크릴산, 트리에틸렌글리콜디아크릴산, 트리에틸렌글리콜디메타크릴산, 비스페놀A의 비스(아크릴로이록시(iroxi)에틸)에테르, 3-메틸펜탄디올디아크릴산 및 3-메틸펜탄디올디메타크릴산 등에서 선택되는 하나 또는 하나 이상일 수 있다. 이때, 상기 광반응성 화합물은 상기 포토레지스트 조성물 100 중량%에 대하여 1 내지 25 중량%로 포함되는 것이 바람직하다.The photoreactive compound according to an embodiment of the present invention is not limited as long as it is a photoreactive compound commonly used in the art, and specific examples thereof include dipentaerythritol hexaacrylic acid, pentaerythritol triacrylic acid, trimethylolpropane triacrylic acid , Ethylene glycol diacrylic acid, bisphenol-A diglycidyl ether acrylic acid adduct, trimethylol propane triglycidyl ether acrylic acid adduct, pentaerythritol trimethacrylic acid, dipentaerythritol hexaacrylic acid, trimethylolpropane trimethacrylic acid, penta (3-methylpentanediol diacrylic acid, 3-methylpentanediol diacrylic acid, and 3-methylpentanediol diacrylic acid) of bisphenol A, triethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, erythritol tetraacrylic acid, neopentyl glycol dimethacrylic acid, -Methylpentanediol dimethacrylic acid, and the like. Or more than one. At this time, it is preferable that the photoreactive compound is contained in an amount of 1 to 25% by weight based on 100% by weight of the photoresist composition.

상기 용매로는 바인더 수지, 광개시제 및 기타 화합물과의 상용성을 고려하여 에틸아세테이트, 부틸아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜 디메틸에틸에테르, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트(EEP), 에틸락테이트, 프로필렌글리콜모노메틸에테르아세테이트(PGMEA), 프로필렌글리콜메틸에테르프로피오네이트(PGMEP), 프로필렌글리콜메틸에테르, 프로필렌글리콜프로필에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜메틸아세테이트, 디에틸렌글리콜에틸아세테이트, 아세톤, 메틸이소부틸케톤, 시클로헥사논, 디메틸포름아미드(DMF), N,N-디메틸아세트아미드(DMAc), N-메틸-2-피롤리돈(NMP), γ-부틸로락톤, 디에틸에테르, 에틸렌글리콜 디메틸 에테르, 다이글라임(Diglyme), 테트라하이드로퓨란(THF), 메탄올, 에탄올, 프로판올, 이소-프로판올, 메틸셀로솔브, 에틸셀로솔브, 디에틸렌글리콜메틸 에테르, 디에틸렌글리콜에틸에테르, 디프로필렌글리콜메틸에테르, 톨루엔, 크실렌, 헥산, 헵탄, 옥탄 등의 용매를 각각 단독 또는 2종 이상 혼합하여 사용할 수 있다.In view of compatibility with a binder resin, a photoinitiator and other compounds, the solvent may be ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, , diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N - dimethylacetamide (DMAc), N - methyl-2-pyrrolidone (NMP),? -Butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, , Octane, etc. may be used alone or in combination of two or more.

본 발명의 일 실시예에 따른 상기 첨가제에 있어, 상기 레벨링제는 상기 포토레지스트 조성물의 도포시 얼룩이나 반점을 방지하고 레벨링 성능을 개선하기 위한 것으로, 구체적인 일예로 BM Chemie사의 BM-1000, BM-1100 등; 다이 닛폰 잉키 가가꾸 고교(주)사의 메카 팩 F 142D, 동 F 172, 동 F 173, 동 F 183 등; 스미토모 스리엠(주)사의 프로라드 FC-135, 동 FC-170C, 동 FC-430, 동 FC-431 등; 아사히 그라스(주)사의 사프론 동 S-112, 동 S-113, 동 S-131, 동 S-141, 동S-145 등; 도레이 실리콘(주)사의 SH-28PA, 동-190, 동-193, SZ-6032, SF-8428 등; 의 시판품일 수 있으나 이에 한정되는 것은 아니다. 이때, 상기 첨가제는 상기 포토레지스트 조성물 100 중량%에 대하여 0.1 내지 2.0 중량%로 포함되는 것이 바람직하다.In the additive according to an embodiment of the present invention, the leveling agent is used to prevent spots or spots during application of the photoresist composition and to improve leveling performance. For example, a BM-1000 BM- 1100 Etc; Mechac-packs F 142D, F 172, F 173, and F 183 manufactured by Dainippon Ink & Chemicals Incorporated. Etc; Prorad FC-135, FC-170C, FC-430 and FC-431 of Sumitomo 3M Ltd. Etc; S-112, S-113, S-131, S-141, and S-145 of Saffron copper of Asahi Glass Co., Etc; SH-28PA, -190, -193, SZ-6032 and SF-8428 of Toray Silicone Co., Etc; But is not limited thereto. In this case, the additive is preferably contained in an amount of 0.1 to 2.0% by weight based on 100% by weight of the photoresist composition.

또한, 본 발명은 상기 화학식 1로 표시되는 플루오렌일 옥심 에스테르 화합물 및 색재를 포함하는 착색 포토레지스트 조성물을 제공한다.
The present invention also provides a colored photoresist composition comprising a fluorenyl oxime ester compound represented by the above formula (1) and a coloring material.

컬러 필터나 블랙 매트릭스 형성용 레지스트로 적용하기 위해 포함되는 상기 색재의 구체적인 일예로는 레드, 그린, 블루와 감색 혼합계의 시안, 마젠다, 옐로우, 블랙 안료를 들 수 있으며, 안료의 구체적인 일예로는 C.I.피그먼트 옐로우 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168, C.I. 피그먼트 오렌지 36, 43, 51, 55, 59, 61, C.I.피그먼트 레드 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. 피그먼트바이올렛 19, 23, 29, 30, 37, 40, 50, C.I.피그먼트 블루 15, 15:1, 15:4, 15:6, 22, 60, 64, C.I.피그먼트 그린 7, 36, C.I.피그먼트 브라운 23, 25, 26, C.I.피그먼트 블랙 7, 카본블랙 및 티탄 블랙 등일 수 있다.Specific examples of the coloring material to be applied as a resist for forming a color filter or a black matrix include cyan, magenta, yellow and black pigments of red, green, blue and a mixture of nacreous colors. Specific examples of the pigment include CI Pigment Yellow 12,13,14,17,20,24,55,83,86,93,109,110,117,125,137,147,148,153,154,166,168, CI Pigment Orange 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240, CI CI Pigment Blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, CI Pigment Green 7, 36, CI Pigment Brown 23, 25, 26, CI Pigment Black 7, carbon black and titanium black.

본 발명은 상기 착색 포토레지스트 조성물로 제조되는 블랙 매트릭스 또는 컬러 필터를 제공한다.The present invention provides a black matrix or color filter made of the colored photoresist composition.

본 발명의 일 실시예에 따른 상기 착색 포토레지스트 조성물을 이용한 구현예 중 하나인 컬러 필터는 하기와 같은 제조방법으로 제조될 수 있으나 이에 한정되는 것은 아니다.The color filter, which is one embodiment using the colored photoresist composition according to an embodiment of the present invention, may be manufactured by the following manufacturing method, but is not limited thereto.

유리기판 위에 스핀 도포, 롤러 도포, 스프레이 도포 등의 적당한 방법을 사용하여, 예를 들면, 0.5 내지 10 ㎛의 두께로 전술한 착색 포토레지스트 조성물을 도포한 후 상기 기판에 컬러 필터에 필요한 패턴을 형성하도록 광을 조사한다. 조사에 사용되는 광원으로는 UV, 전자선 또는 X선을 사용할 수 있고, 예를 들면, 190 내지　450 nm, 구체적으로는 200 nm 내지 400 nm 영역의 UV를 조사할 수 있다. 　또한 상기 조사하는 공정에서 포토레지스트 마스크를 사용하여 실시할 수도 있다. 　이와 같이 조사하는 공정을 실시한 후, 상기 광원이 조사되어 패턴화된　착색 포토레지스트 조성물 층을 현상액으로 처리한다. 이때, 상기 착색 포토레지스트 조성물 층에서 비노광 부분은 용해됨으로써 컬러 필터에 필요한 패턴이 형성되는 것일 수 있다. 이러한 공정을 필요한 색의 수에 따라 반복함으로써 원하는 패턴을 갖는 컬러필터를 수득할 수 있다. 또한 상기 공정에서 현상에 의해 수득된 화상 패턴을 다시 가열하거나 활성선 조사 등에 의해 경화시키면 내크랙성, 내용제성 등이 향상된 컬러 필터를 구현할 수 있다.After applying the above-mentioned colored photoresist composition to a glass substrate in a thickness of, for example, 0.5 to 10 탆 using a suitable method such as spin coating, roller coating or spray coating, a pattern necessary for a color filter is formed on the substrate . As the light source used for the irradiation, UV, electron beam or X-ray can be used. For example, UV of 190 to 450 nm, specifically 200 nm to 400 nm can be irradiated. Further, a photoresist mask may be used in the above irradiation step. After the step of irradiating in this manner, the light source is irradiated to treat the patterned colored photoresist composition layer with a developing solution. At this time, the non-exposed portion in the colored photoresist composition layer may be dissolved to form a necessary pattern in the color filter. By repeating such a process according to the number of necessary colors, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above step is heated again or cured by actinic radiation or the like, a color filter having improved crack resistance, solvent resistance and the like can be realized.

본 발명의 옥심에스테르 화합물은 포토레지스트 조성물의 광중합 개시제로 사용될 때 소량을 사용하여도 감도가 월등히 우수하며, 잔막율, 패턴안정성, 내화학성 및 연성 등의 물성이 뛰어나 TFT-LCD 제조 공정 중의 노광 및 포스트베이크 공정에서 광중합 개시제로부터 발생하는 아웃개싱을 최소화할 수 있어 오염을 줄일 수 있고 이로 인해 발생할 수 있는 불량을 최소화할 수 있는 장점이 있다.When the oxime ester compound of the present invention is used as a photopolymerization initiator of a photoresist composition, the sensitivity is remarkably excellent even when a small amount is used, and excellent properties such as residual film ratio, pattern stability, chemical resistance and ductility, The outgassing generated from the photopolymerization initiator in the postbake process can be minimized, so that contamination can be reduced and defects that may occur due to this can be minimized.

이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 실시예 및 비교예를 들어 상세하게 설명하겠는바, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석 되어져서는 안 된다. 본 발명의 실시예들은 당 업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.
For a better understanding of the present invention, representative compounds of the present invention will be described in detail with reference to Examples and Comparative Examples. However, the embodiments according to the present invention can be modified into various other forms, Should not be construed as being limited to the embodiments described below. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

(실시예 1) 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-아세틸 옥심)(5)의 제조(Example 1) 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-acetyl oxime) (5) Manufacturing

Figure 112015034569412-pat00017
Figure 112015034569412-pat00017

반응 1. 9,9-디에틸-9H-플루오렌(2)합성 Reaction 1. 9,9-diethyl -9 H - fluorene (2) Synthesis

플루오렌(1) 200.0 g (1.20 mol), 수산화칼륨 268.8 g (4.80 mol)과 요오드화칼륨 19.9 g (0.12 mol)을 질소 분위기 하에서 무수 디메틸설폭사이드 1 L에 용해시키고 반응물을 15 ℃로 유지한 다음, 브로모에탄 283.3 g (2.60 mol)를 2 시간에 걸쳐서 천천히 가해주고 반응물을 15 ℃에서 1시간 동안 교반하였다. 그런 다음 반응물에 증류수 2 L를 가해주고 30분 동안 교반 후, 디클로로메탄으로 생성물을 추출하고, 추출한 유기층을 증류수로 씻어준 다음, 회수한 유기 층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 에틸아세테이트 : n-헥산 = 1 : 4)로 정제하여 9,9-디에틸-9H-플루오렌(2) 248.6 g (93.3 %)을 얻었다.200.0 g (1.20 mol) of fluorene (1), 268.8 g (4.80 mol) of potassium hydroxide and 19.9 g (0.12 mol) of potassium iodide were dissolved in 1 L of anhydrous dimethylsulfoxide under nitrogen atmosphere and the reaction was maintained at 15 , 283.3 g (2.60 mol) of bromoethane was slowly added over 2 hours, and the reaction was stirred at 15 ° C for 1 hour. Then, 2 L of distilled water was added to the reaction mixture, and the mixture was stirred for 30 minutes. The product was extracted with dichloromethane. The extracted organic layer was washed with distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate. the product was purified by silica gel column chromatography (developing solvent; ethyl acetate: n - hexane = 1: 4) to give 9,9-diethyl -9 H - fluorene (2) was obtained 248.6 g (93.3%).

1H-NMR(δ ppm; CDCl3) : 0.31(6H, t), 2.0(4H, q), 7.26-7.31(6H, m), 7.68(2H, d) 1 H-NMR (δ ppm; CDCl 3): 0.31 (6H, t), 2.0 (4H, q), 7.26-7.31 (6H, m), 7.68 (2H, d)

MS(m/e): 222
MS ( m / e ): 222

반응 2. 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온(3)의 합성Synthesis of ethanone 3-1,1`- reaction 2. (9,9-diethyl -9 H-fluorene-2,7-diyl) bis

9,9-디에틸-9H-플루오렌(2) 100.5 g (0.45 mol)을 디클로로메탄 1 L에 용해시키고 반응물을 -5 ℃로 냉각한 후, 염화알루미늄 151.8 g (1.14 mol)을 천천히 가해준 다음 반응물의 온도가 승온되지 않도록 주의 하면서 디클로로메탄 100 mL에 희석시킨 염화아세틸 88.8 g (1.14 mol)을 2시간에 걸쳐서 천천히 가해주고 -5 ℃에서 1시간 동안 반응물을 교반하였다. 그런 다음 반응물을 얼음물에 천천히 붓고 30분 동안 교반하여 유기층을 분리한 후, 증류수로 씻어주고 회수한 유기 층을 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 에틸아세테이트 : n-헥산 = 1 : 4)로 정제하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온(3) 81.6 g (59.2 %)을 얻었다. 9,9-diethyl -9 H - fluorene (2) After dissolving 100.5 g (0.45 mol) in 1 L of dichloromethane and cooling the reaction to -5 ° C, 151.8 g (1.14 mol) of aluminum chloride was slowly added, and 100 mL of dichloromethane 88.8 g (1.14 mol) of acetyl chloride diluted in toluene was added slowly over 2 hours and the reaction was stirred at -5 ° C for 1 hour. The reaction mixture was poured slowly into ice water and stirred for 30 minutes to separate the organic layer. The organic layer was washed with distilled water and the recovered organic layer was distilled under reduced pressure. The resulting product was purified by silica gel column chromatography (developing solvent; ethyl acetate: n -hexane = 1 : purification 4) to 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone (3) was obtained 81.6 g (59.2%).

1H-NMR(δ ppm; CDCl3) : 0.82(6H, t), 1.91(4H, q), 2.53 (6H, s), 7.35-7.36(2H, m), 7.75 (2H, t), 7.97(2H, d) 1 H-NMR (δ ppm; CDCl 3): 0.82 (6H, t), 1.91 (4H, q), 2.53 (6H, s), 7.35-7.36 (2H, m), 7.75 (2H, t), 7.97 (2H, d)

MS(m/e):306
MS ( m / e ): 306

반응 3. 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(4)의 합성Synthesis of -ethanone -1,1`- bis (oxime) (4) - 3. The reaction 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis

1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온(3) 10.0 g (0.033 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 5.77 g (0.083 mol)과 초산나트륨 6.81 g (0.083 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 에틸아세테이트 200 mL를 가해준 다음, 30분 정도 교반한 후 하여 유기층을 분리한 후 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 에틸아세테이트 : n-헥산 = 1 : 4)로 정제하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(4) 7.58 g (68.3 %)을 얻었다. 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone (3) 10.0 g (0.033 mol ) of was dispersed in 100 mL ethanol, hydroxylamine hydrochloride 5.77 g (0.083 mol) and sodium acetate (6.81 g, 0.083 mol) were added to the reaction mixture, and the reaction solution was slowly heated to reflux for 1 hour. The reaction mixture was cooled to room temperature, and 100 mL of distilled water and 200 mL of ethyl acetate were added. After stirring for 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained product was purified by silica gel column chromatography developing solvent; ethyl acetate: n-hexane = 1: 4) to give 1,1`- (9,9-diethyl -9 H in --2,7-diyl) bis-ethanone -1,1 7.58 g (68.3%) of bis (oxime) (4) were obtained.

1H-NMR(δ ppm; DMSO-d 6 ) : 0.98(6H, t), 1.86 (6H, s) 1.91(4H, m), 2.89 (2H, s), 7.34-7.38(2H, m), 7.80-7.86 (2H, m), 8.01-8.12 (2H, m), 11.05 (2H, s) 1 H-NMR (δ ppm; DMSO- d 6): 0.98 (6H, t), 1.86 (6H, s) 1.91 (4H, m), 2.89 (2H, s), 7.34-7.38 (2H, m), 7.80-7.86 (2H, m), 8.01-8.12 (2H, m), 11.05 (2H, s)

MS(m/e):336
MS ( m / e ): 336

반응 4. 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-아세틸 옥심)(5)의 합성Synthesis of (acetyl oxime-O), (5) reaction 1,1`- 4. (9,9-diethyl -9 H - --2,7-diyl) bis ethanone -1,1`- bis

1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(4) 5.0 g (0.015 mol)을 질소 분위기 하에서 에틸아세테이트 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.84 g (0.038 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 3.01 g (0.038 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 에틸아세테이트 : n-헥산 = 1 : 4)로 정제하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-아세틸옥심) (5) 4.87 g (77.2 %)을 얻었다.1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (oxime) (4) 5.0 g (0.015 mol) of N (3.38 g, 0.038 mol) was added to the reaction solution, and the reaction solution was stirred for 30 minutes. Then, 3.01 g (0.038 mol) of acetyl chloride was slowly added thereto And stirred for 30 minutes while careful not to raise the temperature of the reaction product. Distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (developing solvent; ethyl acetate: n - hexane = 1: 4) to give a 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-acetyl Oxime) (5) (4.87 g, 77.2%).

1H-NMR(δ ppm; CDCl3) : 0.96(6H, t), 1.88 (6H, s) 1.91 (4H, m), 2.08 (6H, s), 2.11(6H, s), 2.89 (2H, s), 7.34-7.38 (2H, m), 7.80-7.86 (2H, m), 8.01-8.12 (2H, m) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.88 (6H, s) 1.91 (4H, m), 2.08 (6H, s), 2.11 (6H, s), 2.89 (2H, s), 7.34-7.38 (2H, m), 7.80-7.86 (2H, m), 8.01-8.12

MS(m/e):421
MS ( m / e ): 421

(실시예 2) 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-아세틸 옥심)(8)의 제조(Example 2) 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (O - acetyl oxime ) Preparation of (8)

Figure 112015034569412-pat00018
Figure 112015034569412-pat00018

반응 1. 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1-프로판온(6)의 합성 Synthesis of - (9,9-diyl-2,7-diethyl -9 H) bis-1-propanone (6) reaction 1. 1,1`-

실시예 1의 반응 1 조건으로 제조된 9,9-디에틸-9H-플루오렌(2)과 염화프로피오닐을 반응하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1-프로판온(6) (58.6 %)을 얻었다. Embodiment 1 is manufactured by the reaction conditions of Example 1, 9,9-diethyl -9 H - fluorene (2) and By reacting a chloride propionyl 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1-propanone to give 6 (58.6%).

1H-NMR(δ ppm; CDCl3) : 0.96(6H, t), 1.28 (6H, s) 1.91 (4H, m), 3.06 (4H, q), 7.35-7.36(2H, m), 7.76 (2H, t), 7.98(2H, d) 1 H-NMR (? Ppm; CDCl 3 ): 0.96 (6H, t), 1.28 (6H, s) 1.91 (4H, m), 3.06 (4H, q), 7.35-7.36 2H, t), 7.98 (2H, d)

MS(m/e):334
MS ( m / e ): 334

반응 2. 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(7)의 합성Of - (9,9-diyl-2,7-diethyl -9 H) bis-1,2-propanedione--2,2`- bis (oxime) (7) reaction 2. 1,1`- synthesis

1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1-프로판온(6) 15.0 g (0.045 mol)을 테트라히드로푸란(THF) 200 ml에 용해시키고 1,4-디옥산에 용해된 4N HCl 50 ml과 이소부틸아질산 13.9 g (0.135 mol)를 차례로 가해주고 반응물을 25 ℃에서 6시간 동안 교반하였다. 그런 다음 반응 용액에 에틸아세테이트를 가해주고 30분 동안 교반하여 유기층을 분리한 후 증류수로 씻어준 다음, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻어진 생성물을 실리카겔 칼럼 그로마토그래피(전개용매 ; 에틸아세테이트 : n-헥산 = 1 : 4)로 정제하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(7) 8.67 g (49.1 %)을 얻었다. 1,1`- - a (9,9-diethyl -9 H-2,7-diyl) bis-1-propanone (6) 15.0 g (0.045 mol ) in tetrahydrofuran (THF) in 200 ml 50 ml of 4 N HCl dissolved in 1,4-dioxane and 13.9 g (0.135 mol) of isobutyl nitrite were added in this order, and the reaction was stirred at 25 ° C for 6 hours. Ethyl acetate was then added to the reaction solution and stirred for 30 minutes. The organic layer was separated and washed with distilled water. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained product was purified by silica gel column chromatography developing solvent; ethyl acetate: n-hexane = 1: 4) to 1,1`- (9,9-diethyl -9 H purification --2,7-diyl) bis-1,2-propanedione -2,2'-bis (oxime) (7) (8.67 g, 49.1%).

1H-NMR(δ ppm; DMSO-d 6 ) : 0.92(6H, t), 1.26 (6H, s) 1.88 (4H, m), 7.34-7.36(2H, m), 7.75 (2H, t), 7.98(2H, d), 10.91 (2H, s) 1 H-NMR (δ ppm; DMSO- d 6): 0.92 (6H, t), 1.26 (6H, s) 1.88 (4H, m), 7.34-7.36 (2H, m), 7.75 (2H, t), 7.98 (2 H, d), 10.91 (2 H, s)

MS(m/e) : 392
MS ( m / e ): 392

반응 3. 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-아세틸 옥심) (8)의 합성3. reaction 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (O - acetyl oxime) ( 8) Synthesis of

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(7)과 염화아세틸을 반응하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-아세틸 옥심) (8) (75.2 %)을 얻었다.Example 1 reaction conditions with 4 1,1`- of (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (oxime ) (7) and by reacting the acetyl chloride 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione-bis -2,2`- ( O -acetyloxime) (8) (75.2%).

1H-NMR(δ ppm; CDCl3) : 0.92(6H, t), 1.26 (6H, s) 1.88 (4H, m), 2.05 (6H, s), 7.35 (2H, m), 7.79 (2H, t), 8.00(2H, d) 1 H-NMR (δ ppm; CDCl 3): 0.92 (6H, t), 1.26 (6H, s) 1.88 (4H, m), 2.05 (6H, s), 7.35 (2H, m), 7.79 (2H, t), 8.00 (2H, d)

MS(m/e):477
MS ( m / e ): 477

(실시예 3) 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-벤조일 옥심)(9)의 제조(Example 3) 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-benzoyl oxime) (9) Manufacturing

Figure 112015034569412-pat00019
Figure 112015034569412-pat00019

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(4)과 염화벤조일을 반응하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-벤조일 옥심)(9) (76.2 %)을 얻었다.Carried out in reaction conditions of Example 1, 4 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (oxime) (4) and the reaction of benzoyl chloride 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-benzoyl oxime) (9 ) (76.2%).

1H-NMR(δ ppm; CDCl3) :0.92(6H, t), 1.26 (6H, s) 1.88 (4H, m), 2.05 (6H, s), 7.35 (2H, m), 7.45(4H, t), 7.66 (2H, t), 7.79 (2H, t), 8.00(2H, d), 8.11 (4H, d) 1 H-NMR (δ ppm; CDCl 3): 0.92 (6H, t), 1.26 (6H, s) 1.88 (4H, m), 2.05 (6H, s), 7.35 (2H, m), 7.45 (4H, t), 7.66 (2H, t), 7.79 (2H, t), 8.00

MS(m/e):544
MS ( m / e ): 544

(실시예 4) 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-시클로헥산카보닐 옥심)(10)의 제조(Example 4) 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-cyclohexane-carbonyl-oxime) (10)

Figure 112015034569412-pat00020
Figure 112015034569412-pat00020

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(4)과 염화시클로헥산카보닐을 사용하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-시클로헥산카보닐 옥심)(10) (70.2 %)을 얻었다.Carried out in reaction conditions of Example 1, 4 1,1`- (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (oxime) (4) and cyclohexane carbonyl chloride 1,1`- using carbonyl (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-cyclohexane Carbonyloxime) (10) (70.2%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.21 (6H, s) 1.50-1.80 (10H, m), 1.7 (5H, m), 1.89-2.20 (11H, m), 8.01-8.12 (4H, m), 8.20 (2H, s) 1 H-NMR (? Ppm; CDCl 3 ): 0.96 (6H, t), 1.21 (6H, s) 1.50-1.80 (10H, m), 1.7 (5H, m), 1.89-2.20 8.01-8.12 (4 H, m), 8.20 (2 H, s)

MS(m/e):557
MS ( m / e ): 557

(실시예 5) 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-벤조일 옥심)(11)의 제조(Example 5) 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (O - benzoyl oxime ) Production of (11)

Figure 112015034569412-pat00021
Figure 112015034569412-pat00021

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`비스(옥심)(7)과 염화벤조일을 반응하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-벤조일 옥심)(11) (65.2 %)을 얻었다.Example 4 1,1`- the reaction conditions of the 1 (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2` bis (oxime) 7 and the reaction of benzoyl chloride 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis ( O -benzoyloxime) (11) (65.2%).

1H-NMR(δ ppm; CDCl3) : 0.96(6H, t), 1.88 (6H, s) 1.92 (4H, m), 7.65-7.7 (4H, m), 7.90-7.93 (2H, m), 8.10-8.15 (6H, m) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.88 (6H, s) 1.92 (4H, m), 7.65-7.7 (4H, m), 7.90-7.93 (2H, m), 8.10-8.15 (6 H, m)

MS(m/e):601
MS ( m / e ): 601

(실시예 6) 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-시클로헥산카보닐 옥심)(12)의 제조(Example 6) 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (O - cyclohexane Carbonyloxime) < / RTI > (12)

Figure 112015034569412-pat00022
Figure 112015034569412-pat00022

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`비스(옥심)(7)과 염화시클로헥산카보닐을 반응하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-시클로헥산카보닐 옥심) (12) (61.3 %)을 얻었다.Example 4 1,1`- the reaction conditions of the 1 (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2` bis (oxime) 7 and cyclohexane carbonyl chloride to react a carbonyl 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2` -Bis ( O -cyclohexanecarbonyloxime) (12) (61.3%).

1H-NMR(δ ppm; CDCl3) : 0.96(6H, t), 1.2 (6H, s) 1.52-1.82 (10H, m), 1.60-1.93 (5H, m), 1.89-2.31 (11H, m), 7.90-7.94 (2H, m), 8.01-8.04 (2H, m), 8.12 (2H, s) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.2 (6H, s) 1.52-1.82 (10H, m), 1.60-1.93 (5H, m), 1.89-2.31 (11H, m ), 7.90-7.94 (2H, m), 8.01-8.04 (2H, m), 8.12 (2H, s)

MS(m/e):613
MS ( m / e ): 613

(실시예 7) 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-아세틸 옥심)(14)의 제조(Example 7) 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, tetra 2,2`- Preparation of kiss ( O- acetyloxime) (14)

Figure 112015034569412-pat00023
Figure 112015034569412-pat00023

반응 1. 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(13)의 합성Reaction 1. 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, 2,2`- tetrakis ( Oxime) (13) Synthesis of

실시예 1의 반응 3 조건으로 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(7)으로부터 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(13) (58.3 %)을 얻었다. Example 1 reaction conditions 3 the 1,1`- of (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (oxime ) (1,1`- (9,9-diethyl -9 H from 7)-2,7-diyl) bis-1, 2-propanedione--1,1`, tetra 2,2`- The kiss (oxime) 13 (58.3%) was obtained.

1H-NMR(δ ppm; DMSO-d 6 ) : 0.98(6H, t), 1.88-1.92 (10H, m), 8.01-8.10 (4H, m), 8.15-8.19 (2H, m), 11.04(2H, s), 11.08 (2H, s) 1 H-NMR (? Ppm; DMSO- d 6 ): 0.98 (6H, t), 1.88-1.92 (10H, m), 8.01-8.10 (4H, m), 8.15-8.19 2H, s), 11.08 (2H, s)

MS(m/e):422
MS ( m / e ): 422

반응 2. 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-아세틸 옥심) (14)의 합성2. reaction 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, 2,2`- tetrakis ( O- acetyloxime) (14) Synthesis of

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(13)과 염화아세틸을 반응하여1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-아세틸 옥심) (14) (65.2 %)을 얻었다.Example 1 Reaction of the 4 conditions 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--1,1` 2,2 `1,1`- by reacting a tetrakis (oxime) (13) and acetyl chloride (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-1, 2-propanedione- 1,1`, 2,2'-tetrakis ( O- acetyloxime) (14) (65.2%).

1H-NMR(δ ppm; CDCl3) : 0.96(6H, t), 1.88-1.91 (10H, m), 2.08 (12H, s), 8.0-8.10 (4H, m), 8.18-8.21 (2H, m) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.88-1.91 (10H, m), 2.08 (12H, s), 8.0-8.10 (4H, m), 8.18-8.21 (2H, m)

MS(m/e):591
MS ( m / e ): 591

(실시예 8) 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-벤조일 옥심)(15)의 제조(Example 8) 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, tetra 2,2`- Preparation of kiss ( O- benzoyloxime) (15)

Figure 112015034569412-pat00024
Figure 112015034569412-pat00024

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(13)과 염화벤조일을 반응하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-벤조일 옥심) (15) (56.3 %)을 얻었다.Example 1 Reaction of the 4 conditions 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--1,1` 2,2 `1,1`- by reacting a tetrakis (oxime) (13) and benzoyl chloride (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-1, 2-propanedione- 1,1`, 2,2'-tetrakis ( O- benzoyloxime) (15) (56.3%).

1H-NMR(δ ppm; CDCl3) : 0.96(6H, t), 1.89-1.92 (10H, m), 7.62-7.68 (8H, m), 7.75-7.80 (4H, m), 8.01-8.16 (12H, m), 8.19-8.22 (2H, m) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.89-1.92 (10H, m), 7.62-7.68 (8H, m), 7.75-7.80 (4H, m), 8.01-8.16 ( 12H, m), 8.19-8.22 (2H, m)

MS(m/e):839
MS ( m / e ): 839

(실시예 9) 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-시클로헥산카보닐 옥심)(16)의 제조(Example 9) 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, tetra 2,2`- Preparation of kiss ( O -cyclohexanecarbonyloxime) (16)

Figure 112015034569412-pat00025
Figure 112015034569412-pat00025

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(13)과 염화시클로헥산카보닐을 반응하여 1,1`-(9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-시클로헥산카보닐 옥심) (16) (55.9 %)을 얻었다.Example 1 Reaction of the 4 conditions 1,1`- (9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--1,1` 2,2 '- tetrakis (oxime) (13) and the chloride-cyclohexane 1,1`- by reacting a carbonyl (9,9-diethyl -9 H-fluorene-2,7-diyl) bis-1,2- Propanedione-1,1`, 2,2'-tetrakis ( O -cyclohexanecarbonyloxime) (16) (55.9%).

1H-NMR(δ ppm; CDCl3) : 0.98(6H, t), 1.2 (12H, s) 1.38-1.55 (20H, m), 1.60-1.63 (10H, m), 1.88-2.30 (12H, m), 8.02-8.08 (4H, m), 8.18 (2H, s) 1 H-NMR (δ ppm; CDCl 3): 0.98 (6H, t), 1.2 (12H, s) 1.38-1.55 (20H, m), 1.60-1.63 (10H, m), 1.88-2.30 (12H, m ), 8.02-8.08 (4 H, m), 8.18 (2 H, s)

MS(m/e):863
MS ( m / e ): 863

(실시예 10) 1-(9,9-디에틸-7-(1-(아세틸옥시이미노)프로필)-9H-플루오렌-2일)-1-헵탄온-O-아세틸 옥심 (20)의 제조(Example 10) 1- (9,9-diethyl-7- (1- (acetyl oksiyi mino) propyl) -9 H - fluorene -2-yl) -1-heptanone - O - acetyl-oxime-20 Manufacturing

Figure 112015034569412-pat00026
Figure 112015034569412-pat00026

반응 1. 1-(9,9-디에틸-9H-플루오렌-2-일)-1-프로판온(17)의 합성Synthesis of a - (fluoren-2-yl 9,9-diethyl -9 H) -1- propanone 17 1 1 reaction

9,9-디에틸-9H-플루오렌(2) 100.5 g (0.45 mol)을 디클로로메탄 1 L에 용해시키고 반응물을 -5 ℃로 냉각한 후, 염화알루미늄 72.3 g (0.54 mol)을 천천히 가해준 다음 반응물의 온도가 승온되지 않도록 주의 하면서 디클로로메탄 50 ml에 희석시킨 염화프로피오닐 50.1 g (0.54 mol)을 2시간에 걸쳐서 천천히 가해주고 -5 ℃에서 1시간 동안 반응물을 교반하였다. 그런 다음 반응물을 얼음물 1 L에 천천히 붓고 30분 동안 교반하여 유기층을 분리한 후, 증류수 500 ml로 씻어주고 회수한 유기층을 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토 그래피(전개용매 ; 에틸아세테이트 : n-헥산 = 1 : 4)로 정제하여 연한 노란색의 고체 1-(9,9-디에틸-9H-플루오렌-2-일)-1-프로판온(17) 75.8 g (60.6 %)을 얻었다. 9,9-diethyl -9 H - fluorene (2) After dissolving 100.5 g (0.45 mol) in 1 L of dichloromethane, the reaction was cooled to -5 캜, and then 72.3 g (0.54 mol) of aluminum chloride was slowly added. While taking care not to raise the temperature of the reaction, 50 ml of dichloromethane 50.1 g (0.54 mol) of diluted propionyl chloride was slowly added over 2 hours and the reaction was stirred at -5 ° C for 1 hour. Then, the reaction mixture was poured slowly into 1 L of ice water and stirred for 30 minutes. The organic layer was separated, washed with 500 ml of distilled water, and the recovered organic layer was distilled under reduced pressure. The product was purified by silica gel column chromatography (eluent: ethyl acetate: n- hexane = 1: 4) -9 H to give solid 1- (9,9-diethyl of a pale yellow-fluorene-2-yl) -1-propanone to obtain the (17) 75.8 g (60.6% ).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.20 (3H, t), 1.93 (4H, q), 2.54 (2H, q), 7.25-7.35(2H, m), 7.52-7.54 (1H, m), 7.84-7.92 (2H, m), 8.03-8.15 (2H, m) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.20 (3H, t), 1.93 (4H, q), 2.54 (2H, q), 7.25-7.35 (2H, m), 7.52 -7.54 (1H, m), 7.84-7.92 (2H, m), 8.03-8.15 (2H, m)

MS(m/e):278
MS ( m / e ): 278

반응 2. 1-(9,9-디에틸-7-프로피오닐-9H-플루오렌-2-일)-1-헵탄온(18)의 합성Synthesis of a - (fluoren-2-yl 9,9-diethyl-7-propionyl -9 H) -1- heptanone 18. 2. Reaction 1

1-(9,9-디에틸-9H-플루오렌-2-일)-1-프로판온(17) 10.0 g (0.036 mol)을 디클로로메탄 100 mL에 용해시키고 반응물을 -5 ℃로 냉각한 후, 염화알루미늄 5.76 g (0.043 mol)을 천천히 가해준 다음 반응물의 온도가 승온되지 않도록 주의 하면서 디클로로메탄 10 ml에 희석시킨 헵타노일클로라이드 6.39 g (0.043 mol)을 천천히 가해주고 -5 ℃에서 1시간 동안 반응물을 교반하였다. 그런 다음 반응물을 얼음물 100 mL에 천천히 붓고 30분 동안 교반하여 유기층을 분리한 후, 증류수 50 ml로 씻어주고 회수한 유기층을 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토 그래피(전개용매 ; 에틸아세테이트 : n-헥산 = 1 : 4)로 정제하여 1-(9,9-디에틸-7-프로피오닐-9H-플루오렌-2-일)-1-헵탄온(18) 7.83 g (55.7 %)을 얻었다. 1- (9,9-diethyl -9 H - fluoren-2-yl) -1-propanone (17) 10.0 g (0.036 mol ) which was dissolved in 100 mL of dichloromethane The reaction was cooled to -5 ℃ Then, 5.76 g (0.043 mol) of aluminum chloride was added slowly, and then 6.39 g (0.043 mol) of heptanoyl chloride diluted in 10 ml of dichloromethane was slowly added thereto while being careful not to raise the temperature of the reaction, Lt; / RTI > Then, the reaction mixture was slowly poured into 100 mL of ice water and stirred for 30 minutes to separate the organic layer. The organic layer was washed with 50 mL of distilled water and the recovered organic layer was distilled under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate: n- hexane = 1: 4) to give 1- (9,9-diethyl-7-propionyl -9 H - fluoren-2-yl) -1-heptanone to obtain a (18) 7.83 g (55.7% ) .

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.28-1.35 (6H, m), 1.46-1.48 (2H, m), 1.92 (4H, q), 2.60 (2H, q), 2.96 (2H, t), 7.89-7.92 (2H, m), 8.03-8.13 (4H, m) 1 H-NMR (? Ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.28-1.35 (6H, m), 1.46-1.48 , 1.92 (4H, q), 2.60 (2H, q), 2.96 (2H, t), 7.89-7.92 (2H, m), 8.03-8.13

MS(m/e):390
MS ( m / e ): 390

반응 3. 1-(9,9-디에틸-7-(1-(히드록시이미노)프로필)-9H-플루오렌-2-일)-1-헵탄온 옥심(19)의 합성Synthesis of a - (fluoren-2-yl 9,9-diethyl-7- (1- (hydroxyimino) propyl) -9 H) -1- heptanone oxime (19) 3. reaction 1

실시예 1의 반응 3 조건으로 1-(9,9-디에틸-7-프로피오닐-9H-플루오렌-2-일)-1-헵탄온(18)으로부터 1-(9,9-디에틸-7-(1-(히드록시이미노)프로필)-9H-플루오렌-2-일)-1-헵탄온 옥심(19) (65.3 %)을 얻었다. The reaction conditions of Example 1 to 3 1- (9,9-diethyl-7-propionyl -9 H - fluoren-2-yl) 1- (9,9-1-heptanone from 18 D ethyl-7- (1- (hydroxyimino) propyl) -9 H - fluoren-2-yl) -1-heptane to give the oxime 19 (65.3%).

1H-NMR(δ ppm; DMSO-d 6 ) : 0.91 (3H, t), 0.96 (6H, t), 1.09 (3H, t), 1.29-1.33 (6H, m), 1.48-1.50 (2H, m), 1.92 (4H, q), 2.72-2.76 (4H, m), 8.02-8.08 (4H, m), 8.18 (2H, s), 11.01 (1H, s), 11.09 (1H, s) 1 H-NMR (δ ppm; DMSO- d 6): 0.91 (3H, t), 0.96 (6H, t), 1.09 (3H, t), 1.29-1.33 (6H, m), 1.48-1.50 (2H, m), 1.92 (4H, q), 2.72-2.76 (4H, m), 8.02-8.08 (4H, m), 8.18 (2H, s), 11.01

MS(m/e):420
MS ( m / e ): 420

반응 4. 1-(9,9-디에틸-7-(1-(아세틸옥시이미노)프로필)-9H-플루오렌-2일)-1-헵탄온-O-아세틸 옥심 (20)의 합성Synthesis of acetyl-oxime (20) - 4. The reaction of 1- (9,9-diethyl-7- (1- (acetyl oksiyi mino) propyl) -9 H-fluorene -2-yl) -1-heptanone-O

실시예 1의 반응 4 조건으로 1-(9,9-디에틸-7-(1-(히드록시이미노)프로필)-9H-플루오렌-2-일)-1-헵탄온 옥심(19)과 염화아세틸을 반응하여 1-(9,9-디에틸-7-(1-(아세틸옥시이미노)프로필)-9H-플루오렌-2일)-1-헵탄온-O-아세틸 옥심(20) (71.3 %)을 얻었다.4 with reaction conditions of Example 1 1- (9,9-diethyl-7- (1- (hydroxyimino) propyl) -9 H - fluoren-2-yl) -1-heptanone-oxime 19 and in response to the acetyl chloride 1- (9,9-diethyl-7- (1- (acetyl oksiyi mino) propyl) -9 H - fluorene -2-yl) -1-heptanone - O - acetyl oxime (20 ) (71.3%).

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.29-1.33 (6H, m), 1.51 (2H, m), 1.92 (4H, q), 2.20 (4H, s), 2.72-2.76 (4H, m), 8.02-8.08 (4H, m), 8.18 (2H, s) 1 H-NMR (? Ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.29-1.33 (4H, s), 2.72-2.76 (4H, m), 8.02-8.08 (4H, m), 8.18 (2H, s)

MS(m/e):504
MS ( m / e ): 504

(실시예 11) 1-(9,9-디에틸-7-(1-(벤조일옥시이미노)프로필)-9H-플루오렌-2일)-1-헵탄온-O-벤조일 옥심 (21)의 제조(Example 11) 1- (9,9-diethyl-7- (1- (benzoyl oksiyi mino) propyl) -9 H - fluorene -2-yl) -1-heptanone - O - benzoyl oxime 21 Manufacturing

Figure 112015034569412-pat00027
Figure 112015034569412-pat00027

실시예 1의 반응 4 조건으로 1-(9,9-디에틸-7-(1-(히드록시이미노)프로필)-9H-플루오렌-2-일)-1-헵탄온 옥심(19)과 염화벤조일을 반응하여 1-(9,9-디에틸-7-(1-(벤조일옥시이미노)프로필)-9H-플루오렌-2일)-1-헵탄온-O-벤조일 옥심 (21) (60.3 %)을 얻었다.4 with reaction conditions of Example 1 1- (9,9-diethyl-7- (1- (hydroxyimino) propyl) -9 H - fluoren-2-yl) -1-heptanone-oxime 19 and 1 by reacting a benzoyl chloride (9,9-diethyl-7- (1- (benzoyl oksiyi mino) propyl) -9 H - fluorene -2-yl) -1-heptanone - O - benzoyl oxime (21 ) (60.3%).

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.29-1.33 (6H, m), 1.51 (2H, m), 1.92 (4H, q), 2.72-2.76 (4H, m), 7.60-7.65 (4H, m), 7.76-7.79 (2H, m), 8.02-8.08 (4H, m), 8.18-8.22 (6H, m) 1 H-NMR (? Ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.29-1.33 (4H, m), 7.60-7.65 (4H, m), 7.76-7.79 (2H, m), 8.02-8.08 (4H, m), 8.18-8.22

MS(m/e):628
MS ( m / e ): 628

(실시예 12) 1-(9,9-디에틸-7-(1-(시클로헥산카보닐옥시이미노)프로필)-9H-플루오렌-2일)-1-헵탄온-O-시클로헥산카보닐 옥심 (22)의 제조(Example 12) 1- (9,9-diethyl-7- (1- (cyclohexane carbonyl oksiyi mino) propyl) -9 H - fluorene -2-yl) -1-heptanone - O - cyclohexane Preparation of Carbonyloxime (22)

Figure 112015034569412-pat00028
Figure 112015034569412-pat00028

실시예 1의 반응 4 조건으로 1-(9,9-디에틸-7-(1-(히드록시이미노)프로필)-9H-플루오렌-2-일)-1-헵탄온 옥심(19)과 염화벤조일을 반응하여 1-(9,9-디에틸-7-(1-(벤조일옥시이미노)프로필)-9H-플루오렌-2일)-1-헵탄온-O-벤조일 옥심 (21) (60.3 %)을 얻었다.4 with reaction conditions of Example 1 1- (9,9-diethyl-7- (1- (hydroxyimino) propyl) -9 H - fluoren-2-yl) -1-heptanone-oxime 19 and 1 by reacting a benzoyl chloride (9,9-diethyl-7- (1- (benzoyl oksiyi mino) propyl) -9 H - fluorene -2-yl) -1-heptanone - O - benzoyl oxime (21 ) (60.3%).

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.29-1.33 (6H, m), 1.51 (2H, m), 1.92 (4H, q), 2.72-2.76 (4H, m), 7.60-7.65 (4H, m), 7.76-7.79 (2H, m), 8.02-8.08 (4H, m), 8.18-8.22 (6H, m) 1 H-NMR (? Ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.29-1.33 (4H, m), 7.60-7.65 (4H, m), 7.76-7.79 (2H, m), 8.02-8.08 (4H, m), 8.18-8.22

MS(m/e):628
MS ( m / e ): 628

(실시예 12) 1-(9,9-디에틸-7-(1-(시클로헥산카보닐옥시이미노)프로필)-9H-플루오렌-2일)-1-헵탄온-O-시클로헥산카보닐 옥심 (22)의 제조(Example 12) 1- (9,9-diethyl-7- (1- (cyclohexane carbonyl oksiyi mino) propyl) -9 H - fluorene -2-yl) -1-heptanone - O - cyclohexane Preparation of Carbonyloxime (22)

Figure 112015034569412-pat00029
Figure 112015034569412-pat00029

실시예 1의 반응 4 조건으로 1-(9,9-디에틸-7-(1-(히드록시이미노)프로필)-9H-플루오렌-2-일)-1-헵탄온 옥심(19)과 염화시클로헥산카보닐을 반응하여 1-(9,9-디에틸-7-(1-(시클로헥산카보닐옥시이미노)프로필)-9H-플루오렌-2일)-1-헵탄온-O-시클로헥산카보닐 옥심 (22) (58.1 %)을 얻었다.4 with reaction conditions of Example 1 1- (9,9-diethyl-7- (1- (hydroxyimino) propyl) -9 H - fluoren-2-yl) -1-heptanone-oxime 19 and cyclohexane carbonyl chloride to react the carbonyl of 1- (9,9-diethyl-7- (1- (cyclohexane carbonyl oksiyi mino) propyl) -9 H-fluorene -2-yl) -1-heptanone - O -cyclohexanecarbonyloxime (22) (58.1%).

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.12-1.14 (6H, m), 1.29-1.33 (6H, m), 1.38-1.50 (6H, m), 1.52-1.54 (2H, m), 1.59-1.62 (5H, m), 1.76-1.79 (4H, m), 1.92-2.23 (5H, m), 2.72-2.76 (4H, m) 8.02-8.08 (4H, m), 8.18-8.22 (2H, m) 1 H-NMR (δ ppm; CDCl 3): 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.12-1.14 (6H, m), 1.29-1.33 (6H, m) , 1.38-1.50 (6H, m), 1.52-1.54 (2H, m), 1.59-1.62 (5H, m), 1.76-1.79 (4H, m), 1.92-2.23 (5H, m), 2.72-2.76 4H, m) 8.02-8.08 (4H, m), 8.18-8.22 (2H, m)

MS(m/e):641
MS ( m / e ): 641

(실시예 13) 1-(9,9-디에틸-7-(2-(아세틸옥시이미노)프로피오닐)-9H-플루오렌-2일)-1,2-헵탄디온-2-O-아세틸 옥심(24)의 제조(Example 13) 1- (9,9-diethyl-7- (2- (acetylamino oksiyi Mino) propionyl) -9 H - fluorene -2-yl) -1, 2-heptanedione -2- O - Preparation of acetyl oxime (24)

Figure 112015034569412-pat00030
Figure 112015034569412-pat00030

반응 1. 1-(9,9-디에틸-7-(2-(히드록시이미노)프로피오닐)-9H-플루오렌-2-일)-1,2-헵탄디온-2-옥심(23)의 합성1. reaction of 1- (9,9-diethyl-7- (2- (hydroxyimino) propionyl) -9 H - fluoren-2-yl) -1,2-heptane-dione-2-oxime (23 ) Synthesis of

실시예 2의 반응 2 조건으로 1-(9,9-디에틸-7-프로피오닐-9H-플루오렌-2-일)-1-헵탄온(18)으로부터 1-(9,9-디에틸-7-(2-(히드록시이미노)프로피오닐)-9H-플루오렌-2-일)-1,2-헵탄디온-2-옥심(23) (48.0 %)을 얻었다. A second reaction conditions of Example 2 1- (9,9-diethyl-7-propionyl -9 H - fluoren-2-yl) 1- (9,9-1-heptanone from 18 D ethyl 7- (2- (hydroxyimino) propionyl) -9 H - fluoren-2-yl) -1,2-heptane-dione-2-oxime to give the 23 (48.0%).

1H-NMR(δ ppm; DMSO-d 6 ) : 0.91 (3H, t), 0.96 (6H, t), 1.29-1.33 (6H, m), 1.45-1.50 (2H, m), 1.88-1.92 (7H, m) 7.90-7.93 (2H, m), 8.02-8.08 (4H, m), 11.09 (1H, s), 11.11 (1H, s) 1 H-NMR (δ ppm; DMSO- d 6): 0.91 (3H, t), 0.96 (6H, t), 1.29-1.33 (6H, m), 1.45-1.50 (2H, m), 1.88-1.92 ( (2H, m), 8.02-8.08 (4H, m), 11.09 (1H, s), 11.11

MS(m/e) : 449
MS ( m / e ): 449

반응 2. 1-(9,9-디에틸-7-(2-(아세틸옥시이미노)프로피오닐)-9H-플루오렌-2일)-1,2-헵탄디온-2-O-아세틸 옥심(24)의 합성2. reaction of 1- (9,9-diethyl-7- (2- (acetylamino oksiyi Mino) propionyl) -9 H - fluorene -2-yl) -1, 2-heptanedione -2- O - acetyl oxime (24) Synthesis of

실시예 1의 반응 4 조건으로 1-(9,9-디에틸-7-(2-(히드록시이미노)프로피오닐)-9H-플루오렌-2-일)-1,2-헵탄디온-2-옥심(23)과 염화아세틸을 반응하여 1-(9,9-디에틸-7-(2-(아세틸옥시이미노)프로피오닐)-9H-플루오렌-2일)-1,2-헵탄디온-2-O-아세틸 옥심(24) (65.1 %)을 얻었다.Example 1 reaction conditions with 4 l of (9,9-diethyl-7- (2- (hydroxyimino) propionyl) -9 H-fluoren-2-yl) -1,2-heptane dione - 2-oxime (23) with acetyl chloride and the reaction with 1- (9,9-diethyl-7- (2- (acetylamino oksiyi Mino) propionyl) -9 H - fluorene -2-yl) 1,2 -Heptanedione-2- O -acetyloxime (24) (65.1%).

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.96 (6H, t), 1.29-1.33 (6H, m), 1.45-1.50 (2H, m), 1.88-1.92 (7H, m), 2.09 (6H, s), 7.90-7.93 (2H, m), 8.02-8.10 (4H, m) 1 H-NMR (? Ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.29-1.33 (6H, m), 1.45-1.50 (2H, m), 1.88-1.92 m), 2.09 (6H, s), 7.90-7.93 (2H, m), 8.02-8.10 (4H, m)

MS(m/e):532
MS ( m / e ): 532

(실시예 14) 1-(9,9-디에틸-7-(2-(벤조일옥시이미노)프로피오닐)-9H-플루오렌-2일)-1,2-헵탄디온-2-O-벤조일 옥심(25)의 제조(Example 14) 1- (9,9-diethyl-7- (2- (benzoyl oksiyi Mino) propionyl) -9 H - fluorene -2-yl) -1, 2-heptanedione -2- O - Preparation of benzoyloxime (25)

Figure 112015034569412-pat00031
Figure 112015034569412-pat00031

실시예 1의 반응 4 조건으로 1-(9,9-디에틸-7-(2-(히드록시이미노)프로피오닐)-9H-플루오렌-2-일)-1,2-헵탄디온-2-옥심(23)을 염화벤조일을 반응하여 1-(9,9-디에틸-7-(2-(벤조일옥시이미노)프로피오닐)-9H-플루오렌-2일)-1,2-헵탄디온-2-O-벤조일 옥심(25) (55.3 %)을 얻었다.Example 1 reaction conditions with 4 l of (9,9-diethyl-7- (2- (hydroxyimino) propionyl) -9 H-fluoren-2-yl) -1,2-heptane dione - 2-oxime (23) 1-benzoyl chloride by reacting (9,9-diethyl-7- (2- (benzoyl oksiyi Mino) propionyl) -9 H - fluorene -2-yl) -1, 2 Heptanedione-2- O -benzoyloxime (25) (55.3%).

1H-NMR(δ ppm; CDCl3) : 0.90 (3H, t), 0.97 (6H, t), 1.29-1.35 (6H, m), 1.47-1.50 (2H, m), 1.88-1.93 (7H, m), 7.63-7.67 (4H, m), 7.75-7.78 (2H, m), 7.93-8.03 (4H, m), 8.10-8.15 (6H, m) 1 H-NMR (? Ppm; CDCl 3 ): 0.90 (3H, t), 0.97 (6H, t), 1.29-1.35 (6H, m), 1.47-1.50 (2H, m), 1.88-1.93 m), 7.63-7.67 (4H, m), 7.75-7.78 (2H, m), 7.93-8.03 (4H, m), 8.10-8.15

MS(m/e):657
MS ( m / e ): 657

(실시예 15) 1-(9,9-디에틸-7-(2-(시클로헥산카보닐옥시이미노)프로피오닐)-9H-플루오렌-2일)-1,2-헵탄디온-2-O-시클로헥산카보닐 옥심(26)의 제조(Example 15) 1- (9,9-diethyl-7- (2 (cyclohexane carbonyl oksiyi Mino) propionyl) -9 H - fluorene -2-yl) -1, 2-heptanedione -2 Preparation of O -cyclohexanecarbonyl oxime (26)

Figure 112015034569412-pat00032
Figure 112015034569412-pat00032

실시예 1의 반응 4의 조건으로 1-(9,9-디에틸-7-(2-(히드록시이미노)프로피오닐)-9H-플루오렌-2-일)-1,2-헵탄디온-2-옥심(23)과 염화시클로헥산카보닐을 반응하여 1-(9,9-디에틸-7-(2-(시클로헥산카보닐옥시이미노)프로피오닐)-9H-플루오렌-2일)-1,2-헵탄디온-2-O-시클로헥산카보닐 옥심(26) (55.0 %)을 얻었다.Carried out under the conditions of reaction 4 of Example 1, 1- (9,9-diethyl-7- (2- (hydroxyimino) propionyl) -9 H - fluoren-2-yl) -1,2-heptanedione 2-oxime (23) and cyclohexane carbonyl chloride to react the carbonyl of 1- (9,9-diethyl-7- (2 (cyclohexane carbonyl oksiyi Mino) propionyl) -9 H - fluorene -2 Yl) -1,2-heptanedione-2- O -cyclohexanecarbonyloxime (26) (55.0%).

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.96 (6H, t), 1.12-1.14 (6H, m), 1.29-1.33 (6H, m), 1.52-1.54 (2H, m), 1.59-1.62 (5H, m), 1.69-1.81 (10H, m), 1.92-2.23 (8H, m), 7.91-7.93 (2H, m), 8.02-8.10 (4H, m) 1 H-NMR (δ ppm; CDCl 3): 0.91 (3H, t), 0.96 (6H, t), 1.12-1.14 (6H, m), 1.29-1.33 (6H, m), 1.52-1.54 (2H, m), 7.91-7.93 (2H, m), 8.02-8.10 (4H, m), 1.59-1.62 (5H, m), 1.69-1.81

MS(m/e):669
MS ( m / e ): 669

(실시예 16) 1-(7-(1,2-(비스아세틸옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(O-아세틸 옥심) (28)의 제조(Example 16) 1- (7- (1,2 (bis-acetyl oksiyi Mino) propionyl) 9,9-diethyl -9 H - fluorene -2-yl) -1, 2-heptanedione -1 , Preparation of 2-bis ( O- acetyloxime) (28)

Figure 112015034569412-pat00033
Figure 112015034569412-pat00033

반응 1. 1-(7-(1,2-(비스아세틸옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(옥심)(27)의 합성1. reaction of 1- (7- (1,2 (bis-acetyl oksiyi Mino) propionyl) 9,9-diethyl -9 H - fluorene -2-yl) -1, 2-heptane-1,2-dione - Synthesis of bis (oxime) (27)

실시예 1의 반응 3 조건으로 1-(9,9-디에틸-7-(2-(히드록시이미노)프로피오닐)-9H-플루오렌-2-일)-1,2-헵탄디온-2-옥심(23)으로부터 1-(7-(1,2-(비스아세틸옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(옥심)(27) (51.2 %)을 얻었다. Example 1 The reaction conditions in 3 l of (9,9-diethyl-7- (2- (hydroxyimino) propionyl) -9 H-fluoren-2-yl) -1,2-heptane dione - 2-oxime from 1-23 ((bis-acetyl oksiyi 7- (1,2-diamino) propionyl) 9,9-diethyl -9 H - fluorene -2-yl) -1, 2-heptanedione -1,2-bis (oxime) (27) (51.2%).

1H-NMR(δ ppm; DMSO-d 6 ) : 0.91 (3H, t), 0.98 (6H, t), 1.29-1.35 (6H, m), 1.49-1.51 (2H, m), 1.89-1.92 (7H, m), 8.01-8.10 (4H, m), 8.19 (2H, s), 11.01(1H, s), 11.03(1H,s), 11.06(1H,s), 11.08 (1H, s) 1 H-NMR (δ ppm; DMSO- d 6): 0.91 (3H, t), 0.98 (6H, t), 1.29-1.35 (6H, m), 1.49-1.51 (2H, m), 1.89-1.92 ( (1H, s), 11.08 (1H, s), 11.08 (1H, s)

MS(m/e):479
MS ( m / e ): 479

반응 2. 1-(7-(1,2-(비스아세틸옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(O-아세틸 옥심)(28)의합성2. reaction of 1- (7- (1,2 (bis-acetyl oksiyi Mino) propionyl) 9,9-diethyl -9 H - fluorene -2-yl) -1, 2-heptane-1,2-dione - Synthesis of bis ( O- acetyloxime) (28)

실시예 1의 반응 4 조건으로 1-(7-(1,2-(비스아세틸옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(옥심)(27)과 염화아세틸을 반응하여 1-(7-(1,2-(비스아세틸옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(O-아세틸 옥심)(28) (66.3 %)을 얻었다.Carried out in reaction conditions of Example 1 4 1- (7- (1,2 (bis-acetyl oksiyi Mino) propionyl) 9,9-diethyl -9 H - fluorene -2-yl) -1, 2-heptane dione-1, 2-bis (oxime) (27) and acetyl chloride by the reaction of 1- (7- (1,2 (bis-acetyl oksiyi a mino) propionyl) 9,9-diethyl -9 H - FLOUR 2-heptanedione-1,2-bis ( O- acetyloxime) (28) (66.3%).

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.98 (6H, t), 1.29-1.35 (6H, m), 1.49-1.51 (2H, m), 1.89-1.92 (7H, m), 2.10 (12H, s), 8.01-8.10 (4H, m), 8.19 (2H, s) 1 H-NMR (? Ppm; CDCl 3 ): 0.91 (3H, t), 0.98 (6H, t), 1.29-1.35 (6H, m), 1.49-1.51 (2H, m), 1.89-1.92 m), 2.10 (12H, s), 8.01-8.10 (4H, m), 8.19 (2H, s)

MS(m/e):647
MS ( m / e ): 647

(실시예 17) 1-(7-(1,2-(비스벤조일옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(O-벤조일 옥심) (29)의 제조(Example 17) 1- (7- (1,2 (bis-benzoyl oksiyi Mino) propionyl) 9,9-diethyl -9 H - fluorene -2-yl) -1, 2-heptanedione -1 , 2-bis ( O- benzoyloxime) (29)

Figure 112015034569412-pat00034
Figure 112015034569412-pat00034

실시예 1의 반응 4 조건으로 1-(7-(1,2-(비스아세틸옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(옥심)(27)과 염화벤조일을 반응하여 1-(7-(1,2-(비스벤조일옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(O-벤조일 옥심)(29) (52.1 %)을 얻었다.Carried out in reaction conditions of Example 1 4 1- (7- (1,2 (bis-acetyl oksiyi Mino) propionyl) 9,9-diethyl -9 H - fluorene -2-yl) -1, 2-heptane dione-1, 2-bis (oxime) (27) and benzoyl chloride by reaction of 1- (7- (1,2 (bis-benzoyl oksiyi a mino) propionyl) 9,9-diethyl -9 H - FLOUR 2-heptanedione-1,2-bis ( O- benzoyloxime) (29) (52.1%).

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.97 (6H, t), 1.29-1.35 (6H, m), 1.49-1.51 (2H, m), 1.89-1.92 (7H, m), 7.63-7.66 (8H, m), 7.78-7.80 (4H, m), 8.01-8.10 (4H, m), 8.14-8.20 (10H, m) 1 H-NMR (? Ppm; CDCl 3 ): 0.91 (3H, t), 0.97 (6H, t), 1.29-1.35 (6H, m), 1.49-1.51 (2H, m), 1.89-1.92 m), 7.63-7.66 (8H, m), 7.78-7.80 (4H, m), 8.01-8.10 (4H, m), 8.14-8.20

MS(m/e):895
MS ( m / e ): 895

(실시예 18) 1-(7-(1,2-(비스시클로헥산카보닐옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(O-시클로헥산카보닐 옥심)(30)의 제조(Example 18) 1- (7- (1,2 (bis-cyclohexane-carbonyl oksiyi Mino) propionyl) 9,9-diethyl -9 H - fluorene -2-yl) -1, 2-heptane Preparation of dione-1,2-bis ( O -cyclohexanecarbonyloxime) (30)

Figure 112015034569412-pat00035
Figure 112015034569412-pat00035

실시예 1의 반응 4 조건으로 1-(7-(1,2-(비스아세틸옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(옥심)(27)과 염화시클로헥산카보닐을 반응하여 1-(7-(1,2-(비스시클로헥산카보닐옥시이미노)프로피오닐)-9,9-디에틸-9H-플루오렌-2일)-1,2-헵탄디온-1,2-비스(O-시클로헥산카보닐 옥심)(30) (50.3 %)을 얻었다.Carried out in reaction conditions of Example 1 4 1- (7- (1,2 (bis-acetyl oksiyi Mino) propionyl) 9,9-diethyl -9 H - fluorene -2-yl) -1, 2-heptane Dione-1,2-bis (oxime) (27) with cyclohexanecarbonyl chloride to give 1- (7- (1,2- (biscyclohexanecarbonyloxyimino) propionyl) -9,9-di ethyl -9 H - fluorene -2-yl) -1, 2-heptane-dione-1,2-bis (O- cyclohexane carbonyl-oxime) (30) (to give an 50.3%).

1H-NMR(δ ppm; CDCl3) : 0.91 (3H, t), 0.96 (6H, t), 1.12-1.14 (12H, m), 1.29-1.33 (6H, m), 1.52-1.54 (2H, m), 1.59-1.62 (10H, m), 1.69-1.81 (20H, m), 1.92-2.23 (9H, m), 7.91-7.93 (2H, m), 8.02-8.10 (4H, m) 1 H-NMR (δ ppm; CDCl 3): 0.91 (3H, t), 0.96 (6H, t), 1.12-1.14 (12H, m), 1.29-1.33 (6H, m), 1.52-1.54 (2H, m), 1.59-1.62 (10H, m), 1.69-1.81 (20H, m), 1.92-2.23 (9H, m), 7.91-7.93

MS(m/e):919
MS ( m / e ): 919

(실시예 19) 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-아세틸 옥심)(35)의 제조(Example 19) 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-acetyl oxime ) ≪ / RTI > (35)

Figure 112015034569412-pat00036
Figure 112015034569412-pat00036

반응 1. 9,9-디에틸-4-니트로-9H-플루오렌(32)합성 Reaction 1. 9,9-Diethyl-4-nitro -9 H - fluoren-32 Synthetic

실시예 1의 반응 1 조건으로 4-니트로플루오렌(31)과 브로모에탄을 반응하여 9,9-디에틸-4-니트로-9H-플루오렌(32) (88.2 %)을 얻었다.Example 1 the reaction conditions of the 1 4-nitro-fluoren-9,9-diethyl by reacting (31) with dibromoethane-nitro -9 H - fluorene (32) was obtained (88.2%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 2.0 (4H, q), 7.26-7.30 (2H, m), 7.54-7.55 (2H, m), 7.84-7.93 (3H, m) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 2.0 (4H, q), 7.26-7.30 (2H, m), 7.54-7.55 (2H, m), 7.84-7.93 (3H, m)

MS(m/e): 267
MS ( m / e ): 267

반응 2. 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온(33)의 합성 Synthesis of ethanone 33-1,1`- reaction 2. (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis

실시예 1의 반응 2 조건으로 9,9-디에틸-4-니트로-9H-플루오렌(2)과 염화아세틸을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온(33) (59.2 %)을 얻었다. Example 1 2 Reaction conditions in 9,9-diethyl-4-nitro -9 H of-fluorene (2) and acetyl 1,1`- (9,9-diethyl-4-nitro-reacted chloride - 9 H -fluorene-2,7-diyl) bis-ethanone (33) (59.2%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.90 (4H, q), 2.55 (6H, s), 7.94-7.95 (2H, m), 8.15 (1H, s), 8.54 (1H, s), 8.91 (1H, s) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.90 (4H, q), 2.55 (6H, s), 7.94-7.95 (2H, m), 8.15 (1H, s), 8.54 (1 H, s), 8.91 (1 H, s)

MS(m/e):351
MS ( m / e ): 351

반응 3. 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(34)의 합성3. reaction 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (oxime) (34) synthesis

실시예 1의 반응 3 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온(33)으로부터 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(34) (61.3 %)을 얻었다. Example 1 reaction conditions 3 the 1,1`- of (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-1,1`- from ethanone 33 (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- give the bis (oxime) 34 (61.3%).

1H-NMR(δ ppm; DMSO-d 6 ) : 0.96 (6H, t), 1.89 (6H, s), 1.92 (4H, q), 8.02-8.08 (2H, m), 8.19 (1H, s), 8.58 (1H, s), 8.91 (1H, s), 11.01 (1H, s), 11.03 (2H, s) 1 H-NMR (δ ppm; DMSO- d 6): 0.96 (6H, t), 1.89 (6H, s), 1.92 (4H, q), 8.02-8.08 (2H, m), 8.19 (1H, s) , 8.58 (1H, s), 8.91 (1H, s), 11.01 (1H, s), 11.03

MS(m/e):381
MS ( m / e ): 381

반응 4. 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-아세틸 옥심)(35)의 합성4. reaction 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-acetyl oxime) ( 35)

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(34)과 염화아세틸을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-아세틸 옥심)(35) (70.7 %)을 얻었다.Example 4 1,1`- the reaction conditions of the 1 (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (oxime 34) and in response to the acetyl chloride 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis ( O -acetyloxime) (35) (70.7%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.89 (6H, s), 1.92 (4H, q), 2.08 (6H, s), 8.02-8.08 (2H, m), 8.19 (1H, s), 8.58 (1H, s), 8.91 (1H, s) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.89 (6H, s), 1.92 (4H, q), 2.08 (6H, s), 8.02-8.08 (2H, m), 8.19 (1H, s), 8.58 (1H, s), 8.91 (1H, s)

MS(m/e):465
MS ( m / e ): 465

(실시예 20) 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-벤조일 옥심)(36)의 제조(Example 20) 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-benzoyl oxime ) ≪ / RTI > (36)

Figure 112015034569412-pat00037
Figure 112015034569412-pat00037

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(34)과 염화벤조일을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-벤조일 옥심)(36) (63.2 %)을 얻었다.Example 4 1,1`- the reaction conditions of the 1 (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (oxime ) 34 and 1,1`- (9,9-diethyl-4-nitro -9 H by reaction with benzoyl chloride-2,7-diyl fluorenyl) bis-ethanone -1,1`- bis ( O -benzoyloxime) (36) (63.2%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.89 (6H, s), 1.92 (4H, q), 7.64-7.66 (4H, m), 7.78-7.80 (2H, m), 8.02-8.05 (2H, m), 8.14-8.19 (5H, s), 8.58 (1H, s), 8.91 (1H, s) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.89 (6H, s), 1.92 (4H, q), 7.64-7.66 (4H, m), 7.78-7.80 (2H, m) , 8.02-8.05 (2H, m), 8.14-8.19 (5H, s), 8.58 (1H, s), 8.91

MS(m/e):590
MS ( m / e ): 590

(실시예 21) 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-시클로헥산카보닐 옥심)(37)의 제조(Example 21) 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (O-cyclohexane Carbonyloxime) (37)

Figure 112015034569412-pat00038
Figure 112015034569412-pat00038

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(옥심)(34)과 염화시클로헥산카보닐을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-에탄온-1,1`-비스(O-시클로헥산카보닐 옥심)(37) (61.3 %)을 얻었다.Example 4 1,1`- the reaction conditions of the 1 (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1`- bis (oxime 34) and cyclohexane carbonyl chloride by reacting a carbonyl 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-ethanone -1,1 -Bis ( O -cyclohexanecarbonyloxime) (37) (61.3%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.1-1.2 (6H, m), 1.39-1.54 (5H, m), 1.60-1.62 (5H, m), 1.89-1.91 (7H, m), 2.25-2.27 (1H, m), 8.02-8.05 (2H, m), 8.19 (1H, s), 8.58 (1H, s), 8.91 (1H, s) 1 H-NMR (? Ppm; CDCl 3 ): 0.96 (6H, t), 1.1-1.2 (6H, m), 1.39-1.54 (5H, m), 1.60-1.62 (5H, m), 1.89-1.91 (2H, m), 8.19 (1H, s), 8.58 (1H, s), 8.91

MS(m/e):602
MS ( m / e ): 602

(실시예 22) 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-아세틸 옥심) (40)의 제조(Example 22) 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis ( O -acetyloxime) (40)

Figure 112015034569412-pat00039
Figure 112015034569412-pat00039

반응 1. 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1-프로판온(38)의 합성 Synthesis of - (9,9-diyl-2,7-diethyl-4-nitro -9 H) bis-1-propanone 38 1 reaction 1,1`-

실시예 1의 반응 2 조건으로 9,9-디에틸-4-니트로-9H-플루오렌(32) 과 염화프로피오닐을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1-프로판온(38) (57.2 %)을 얻었다. Example 2 The reaction conditions of the first 9,9-diethyl-4-nitro -9 H - by reaction of fluorene (32) and propionyl chloride 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1-propanone to give the 38 (57.2%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.18 (6H, t), 1.91 (4H, q), 2.54 (4H, q), 7.92 (1H, d), 8.01 (1H, d), 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s) 1 H-NMR (? Ppm; CDCl 3 ): 0.96 (6H, t), 1.18 (6H, t), 1.91 (4H, q), 2.54 , 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s)

MS(m/e):379
MS ( m / e ): 379

반응 2. 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(39)의 합성2. reaction 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (oxime) (39) Synthesis of

실시예 2의 반응 2 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1-프로판온(38)으로부터 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(39) (48.1 %)을 얻었다. Example 2 The reaction 2 in terms of 1,1`- - from (9,9-diethyl-4-nitro -9 H-2,7-diyl) bis-1-propanone (38) 1,1 '- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-1, 2-propanedione--2,2`- bis (oxime) 39 (48.1% ).

1H-NMR(δ ppm; DMSO-d 6 ) : 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 7.92 (1H, d), 8.01 (1H, d), 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s), 10.95 (1H, s), 11.02 (1H, s) 1 H-NMR (? Ppm; DMSO- d 6 ): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 7.92 (1H, s), 8.57 (1H, s), 8.94

MS(m/e) : 437
MS ( m / e ): 437

반응 3. 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-아세틸 옥심)(40)의 합성3. reaction 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (O - Acetyl oxime) (40) Synthesis of

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(39)과 염화아세틸을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-아세틸 옥심)(40) (67.1 %)을 얻었다.Example 1 reaction conditions with 4 1,1`- of (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--2,2` - bis (oxime) (39) by reacting with acetyl chloride 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-1,2-propane Dione-2,2'-bis ( O -acetyloxime) (40) (67.1%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 2.08 (6H, s), 7.92 (1H, d), 8.01 (1H, d), 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s) 1 H-NMR (? Ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 2.08 , 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s)

MS(m/e):522
MS ( m / e ): 522

(실시예 23) 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-벤조일 옥심)(41)의 제조(Example 23) 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis ( O -benzoyloxime) (41)

Figure 112015034569412-pat00040
Figure 112015034569412-pat00040

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(39)과 염화벤조일을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-벤조일 옥심)(41) (61.2 %)을 얻었다.Example 1 reaction conditions with 4 1,1`- of (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--2,2` - bis (oxime) (39) and by reaction of benzoyl chloride 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-1,2-propane Dione-2,2'-bis ( O -benzoyloxime) (41) (61.2%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 7.63-7.65 (4H, m), 7.78-7.80 (2H, m), 7.93-8.03 (2H, m), 8.03-8.14 (5H, m), 8.49 (1H, m), 8.84 (1H, s) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 7.63-7.65 (4H, m), 7.78-7.80 (2H, m) , 7.93-8.03 (2H, m), 8.03-8.14 (5H, m), 8.49 (1H, m), 8.84

MS(m/e):646
MS ( m / e ): 646

(실시예 24) 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-시클로헥산카보닐 옥심)(42)의 제조(Example 24) 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis ( O -cyclohexanecarbonyl oxime) (42)

Figure 112015034569412-pat00041
Figure 112015034569412-pat00041

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(39)과 염화시클로헥산카보닐을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-시클로헥산카보닐 옥심)(42) (56.2 %)을 얻었다.Example 1 reaction conditions with 4 1,1`- of (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--2,2` - bis (oxime) (39) and chlorinated cyclo hexane by reacting carbonyl 1,1`- (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-1, 2-propanedione-2,2'-bis ( O -cyclohexanecarbonyloxime) (42) (56.2%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.11-1.13 (6H, m), 1.39-1.54 (10H, m), 1.59-1.61 (5H, m), 1.88 (6H, s), 1.91 (4H, q), 2.27 (1H, m), 7.93-8.03 (2H, m), 8.14 (1H, m), 8.49 (1H, m), 8.84 (1H, s) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.11-1.13 (6H, m), 1.39-1.54 (10H, m), 1.59-1.61 (5H, m), 1.88 (6H, m), 8.49 (1H, m), 8.84 (1H, s), 1.91 (4H, q), 2.27 (1H, m), 7.93-8.03

MS(m/e):658
MS ( m / e ): 658

(실시예 25) 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-아세틸 옥심)(44)의 제조(Example 25) 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, 2, Preparation of 2'-tetrakis ( O- acetyloxime) (44)

Figure 112015034569412-pat00042
Figure 112015034569412-pat00042

반응 1. 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(43)의 합성Reaction 1. 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, 2,2` - Synthesis of tetrakis (oxime) (43)

실시예 1의 반응 3 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(39)으로부터 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(43) (61.3 %)을 얻었다. Example 1 reaction conditions 3 the 1,1`- of (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--2,2` - bis (oxime) 1,1`- from 39 (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-1, 2-propanedione--1,1 (2,2'-tetrakis (oxime) (43) (61.3%).

1H-NMR(δ ppm; DMSO-d 6 ) : 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 8.01-8.08 (2H, m), 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s), 10.98(1H, s), 11.03 (1H, s), 11.05n (1H, s), 11.08 (1H, s) 1 H-NMR (δ ppm; DMSO- d 6): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 8.01-8.08 (2H, m), 8.18 (1H, s) , 8.57 (IH, s), 8.94 (IH, s), 10.98 (IH, s), 11.03

MS(m/e):381
MS ( m / e ): 381

반응 2. 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-아세틸 옥심)(44)의 합성2. reaction 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, 2,2` - Synthesis of tetrakis ( O- acetyloxime) (44)

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(43)과 염화아세틸을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-아세틸 옥심)(44) (66.2 %)을 얻었다.Example 4 1,1`- the reaction conditions of the 1 (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-1, 2-propanedione--1,1` , 2,2`- tetrakis (oxime) (43) and in response to the acetyl chloride 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis -1,2-propanedione-1,1`, 2,2'-tetrakis ( O- acetyloxime) (44) (66.2%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 2.08 (12H, s), 8.01-8.08 (2H, m), 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 2.08 (12H, s), 8.01-8.08 (2H, m), 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s)

MS(m/e):636
MS ( m / e ): 636

(실시예 26) 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-벤조일 옥심) (45)의 제조(Example 26) 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, 2, Preparation of 2'-tetrakis ( O- benzoyloxime) (45)

Figure 112015034569412-pat00043
Figure 112015034569412-pat00043

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(43)과 염화벤조일을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-벤조일 옥심) (45) (56.1 %)을 얻었다.Example 4 1,1`- the reaction conditions of the 1 (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-1, 2-propanedione--1,1` , 2,2`- tetrakis (oxime) 43 and 1,1`- by reacting a benzoyl chloride (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis -1,2-propanedione-1,1`, 2,2'-tetrakis ( O- benzoyloxime) (45) (56.1%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 7.63-7.65 (8H, m), 7.77-7.79 (4H, m), 8.01-8.08 (2H, m), 8.14-8.19 (9H, m), 8.57 (1H, s), 8.94 (1H, s) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 7.63-7.65 (8H, m), 7.77-7.79 (4H, m) , 8.01-8.08 (2H, m), 8.14-8.19 (9H, m), 8.57 (1H, s), 8.94

MS(m/e):884
MS ( m / e ): 884

(실시예 27) 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-시클로헥산카보닐 옥심)(46)의 제조(Example 27) 1,1`- (9,9-diethyl-4-nitro -9 H --2,7-diyl) bis-1, 2-propanedione--1,1`, 2, Preparation of 2'-tetrakis ( O -cyclohexanecarbonyloxime) (46)

Figure 112015034569412-pat00044
Figure 112015034569412-pat00044

실시예 1의 반응 4 조건으로 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(옥심)(43)과 염화시클로헥산카보닐을 반응하여 1,1`-(9,9-디에틸-4-니트로-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-1,1`,2,2`-테트라키스(O-시클로헥산카보닐 옥심)(46) (55.1 %)을 얻었다.Example 4 1,1`- the reaction conditions of the 1 (9,9-diethyl-4-nitro -9 H-fluorene-2,7-diyl) bis-1, 2-propanedione--1,1` , 2,2`- tetrakis (oxime) in response to 43 and cyclohexane carbonyl chloride 1,1`- (9,9-diethyl-4-nitro -9 H --2,7- 1,2-propanedione-1,1`, 2,2'-tetrakis ( O -cyclohexanecarbonyloxime) (46) (55.1%).

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.12-1.14 (12H, m), 1.59-1.62 (10H, m), 1.69-1.81 (20H, m), 1.87-1.89 (6H, s), 1.90-1.92 (4H, q), 2.25-2.28 (2H, m), 8.01-8.08 (2H, m), 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s) 1 H-NMR (? Ppm; CDCl 3 ): 0.96 (6H, t), 1.12-1.14 (12H, m), 1.59-1.62 (10H, m), 1.69-1.81 (20H, m), 1.87-1.89 (2H, m), 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s), 1.90-1.92 (4H, q), 2.25-2.28 s)

MS(m/e):908
MS ( m / e ): 908

(실시예 28) 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-아세틸 옥심)(52)의 제조(Example 28) 1,1`- (4-cyano-9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione-bis -2,2`- ( O -acetyloxime) (52)

Figure 112015034569412-pat00045
Figure 112015034569412-pat00045

반응 1. 4-브로모-9,9-디에틸-9H-플루오렌(48)의 합성Reaction 1. 4-bromo-9,9-diethyl -9 H - Synthesis of fluoren-48

실시예 1의 반응 1 조건으로 4-브로모플루오렌(47)과 브로모에탄을 반응하여 4-브로모-9,9-디에틸-9H-플루오렌(48) (78.2 %)을 얻었다.Example 1 the reaction conditions of the 1 4-Bromo-fluorene (47) and the blower in response to the burnt Moe 4-bromo-9,9-diethyl -9 H - to give a fluorene fluorene (48) (78.2%) .

1H-NMR(δ ppm; CDCl3) : 0.96 (6H, t), 1.92 (4H, q), 7.17-7.28 (2H, m), 7.54-7.55 (2H, m), 7.84-7.93 (3H, m) 1 H-NMR (δ ppm; CDCl 3): 0.96 (6H, t), 1.92 (4H, q), 7.17-7.28 (2H, m), 7.54-7.55 (2H, m), 7.84-7.93 (3H, m)

MS(m/e):301
MS ( m / e ): 301

반응 2. 4-시아노-9,9-디에틸-9H-플루오렌(49)의 합성Reaction 2. 4-cyano-9,9-diethyl -9 H - Synthesis of fluoren-49

4-브로모-9,9-디에틸-9H-플루오렌(48) 30.1 g (0.10 mol)을 N-메틸-2-피롤리디논(NMP) 200 mL에 용해시키고 시안화구리 13.43 g (0.15 mol)을 가해준 다음 반응용액을 서서히 승온하여 3 시간 동안 환류 반응하였다. 반응물에 증류수와 초산 에틸을 가해주고 30분 정도 교반 후, 유기 층을 분리하고, 분리한 유기층을 포화 염화암모늄 수용액과 증류수로 3회의 순서로 씻어준 다음 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류한 후 실리카겔 칼럼 그로마토그래피(전개용매 ; 디클로로메탄 : n-헥산 = 1 : 4)로 정제하여 4-시아노-9,9-디에틸-9H-플루오렌(49) 12.66 g (51.6%)을 얻었다.4-bromo-9,9-diethyl -9 H - fluorene (48) 30.1 g (0.10 mol ) of N - methyl-2-pyrrolidinone (NMP) 200 mL dissolved copper cyanide 13.43 g (0.15 to mol), and then the reaction solution was slowly heated to reflux reaction for 3 hours. Distilled water and ethyl acetate were added to the reaction mixture. After stirring for about 30 minutes, the organic layer was separated, and the separated organic layer was washed with saturated aqueous ammonium chloride solution and distilled water three times in succession. The recovered organic layer was dried over anhydrous magnesium sulfate, after the pressure of distillation thereof was subjected to silica gel column chromatographic purification (developing solvent; dichloromethane: n-hexane = 1: 4) to give 4-cyano-9,9-diethyl -9 H in-fluorene (49) 12.66 g (51.6%).

1H-NMR(δ ppm; CDCl3) : 0.95 (6H, t), 1.91 (4H, q), 7.17-7.28 (2H, m), 7.64-7.69 (2H, m), 7.84-7.93 (3H, m) 1 H-NMR (δ ppm; CDCl 3): 0.95 (6H, t), 1.91 (4H, q), 7.17-7.28 (2H, m), 7.64-7.69 (2H, m), 7.84-7.93 (3H, m)

MS(m/e):247
MS ( m / e ): 247

반응 3. 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1-프로판온(50)의 합성Synthesis of (-2,7-diyl 4-cyano-9,9-diethyl -9 H) bis-1-propanone (50) 3. reaction 1,1`-

실시예 1의 반응 2 조건으로 4-시아노-9,9-디에틸-9H-플루오렌(49)과 염화프로피오닐을 반응하여 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1-프로판온(50) (51.2 %)을 얻었다. Carried out in two reaction conditions of Example 1, 4-cyano-9,9-diethyl -9 H - fluoren-49 and reacted with propionyl chloride 1,1`- (4-cyano-9,9- diethyl -9 H --2,7-diyl) bis-1-propanone to give the 50 (51.2%).

1H-NMR(δ ppm; CDCl3) : 0.94 (6H, t), 1.19 (6H, t), 1.91 (4H, q), 2.52 (4H, q), 7.92 (1H, d), 8.01 (1H, d), 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s) 1 H-NMR (? Ppm; CDCl 3 ): 0.94 (6H, t), 1.19 (6H, t), 1.91 (4H, q), 2.52 , 8.18 (1H, s), 8.57 (1H, s), 8.94 (1H, s)

MS(m/e):359
MS ( m / e ): 359

반응 4. 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(51)의 합성4. reaction 1,1`- (4-cyano-9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (oxime ) (51) Synthesis of

실시예 2의 반응 2 조건으로 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1-프로판온(50)으로부터 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(51) (46.3 %)을 얻었다. Example 2 The reaction 2 in terms of 1,1`- - from (4-cyano-9,9-diethyl -9 H-2,7-diyl) bis-1-propanone 50 1, 1`- (4-cyano-9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (oxime) (51) ( 46.3%).

1H-NMR(δ ppm; DMSO-d 6 ) : 0.95 (6H, t), 1.89 (6H, s), 1.91 (4H, q), 7.93 (1H, d), 8.00 (1H, d), 8.17 (1H, s), 8.55 (1H, s), 8.92 (1H, s), 10.96 (1H, s), 11.00 (1H, s) 1 H-NMR (δ ppm; DMSO- d 6): 0.95 (6H, t), 1.89 (6H, s), 1.91 (4H, q), 7.93 (1H, d), 8.00 (1H, d), 8.17 (IH, s), 8.55 (IH, s), 8.92

MS(m/e) : 417
MS ( m / e ): 417

반응 5. 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-아세틸 옥심)(52)의 합성5. reaction 1,1`- (4-cyano-9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propanedione--2,2`- bis (O -Acetyloxime) (52) Synthesis of

실시예 1의 반응 4 조건으로 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(옥심)(51)과 염화아세틸을 반응하여 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1,2-프로판디온-2,2`-비스(O-아세틸 옥심)(52) (60.1 %)을 얻었다.Carried out in reaction conditions of Example 1, 4 1,1`- (4-cyano-9,9-diethyl -9 H --2,7-diyl) bis-1, 2-propane-2,2-dione '- bis (oxime) by reacting 51 with acetyl chloride 1,1`- (4-cyano-9,9-diethyl -9 H-fluorene-2,7-diyl) bis 1,2 -Propanedione-2,2'-bis ( O -acetyloxime) (52) (60.1%).

1H-NMR(δ ppm; CDCl3) : 0.95 (6H, t), 1.88 (6H, s), 1.90 (4H, q), 2.08 (6H, s), 7.92 (1H, d), 8.02 (1H, d), 8.17 (1H, s), 8.55 (1H, s), 8.92 (1H, s) 1 H-NMR (? Ppm; CDCl 3 ): 0.95 (6H, t), 1.88 (6H, s), 1.90 (4H, q), 2.08 , 8.17 (1H, s), 8.55 (1H, s), 8.92 (1H, s)

MS(m/e):501
MS ( m / e ): 501

(실시예 29) 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-프로판온-1,1`-비스(O-아세틸 옥심)(54)의 제조(Example 29) 1,1`- (4-cyano-9,9-diethyl -9 H-fluorene-2,7-diyl) bis-propanone -1,1`- bis (O-acetyl Oxime) (54)

Figure 112015034569412-pat00046
Figure 112015034569412-pat00046

반응 1. 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-프로판온-1,1`-비스(옥심)(53)의 합성의 합성Reaction 1. 1,1`- (4-cyano-9,9-diethyl -9 H-fluorene-2,7-diyl) bis-propanone -1,1`- bis (oxime) (53) Synthesis of

실시예 1의 반응 3 조건으로 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-1-프로판온(50)으로부터 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-프로판온-1,1`-비스(옥심)(53) (62.3 %)을 얻었다. Example 3 by the reaction conditions of the first 1,1`- - from (4-cyano-9,9-diethyl -9 H-2,7-diyl) bis-1-propanone 50 1, 1`- (4-cyano-9,9-diethyl -9 H-fluorene-2,7-diyl) bis-propanone -1,1`- bis (oxime) 53 (62.3%) of .

1H-NMR(δ ppm; DMSO-d 6 ) : 0.96 (6H, t), 1.04 (6H, t), 1.92 (4H, q), 2.75 (4H, q), 8.02-8.08 (2H, m), 8.19 (1H, s), 8.58 (1H, s), 8.91 (1H, s), 11.01 (1H, s), 11.03 (2H, s) 1 H-NMR (δ ppm; DMSO- d 6): 0.96 (6H, t), 1.04 (6H, t), 1.92 (4H, q), 2.75 (4H, q), 8.02-8.08 (2H, m) , 8.19 (1H, s), 8.58 (1H, s), 8.91

MS(m/e):389
MS ( m / e ): 389

반응 2. 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-프로판온-1,1`-비스(O-아세틸 옥심)(54)의 합성2. reaction 1,1`- (4-cyano-9,9-diethyl -9 H-fluorene-2,7-diyl) bis-propanone -1,1`- bis (O-acetyl oxime) (54) Synthesis of

실시예 1의 반응 4 조건으로 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-프로판온-1,1`-비스(옥심)(53)과 염화아세틸을 반응하여 1,1`-(4-시아노-9,9-디에틸-9H-플루오렌-2,7-디일)비스-프로판온-1,1`-비스(O-아세틸 옥심)(54) (71.7 %)을 얻었다.Example 1 reaction conditions with 4 1,1`- of (4-cyano-9,9-diethyl -9 H-fluorene-2,7-diyl) bis-propanone -1,1`- bis ( 1,1`- by reaction of the oxime, 53) and acetyl chloride (4-cyano-9,9-diethyl -9 H-fluorene-2,7-diyl) bis-propanone -1,1` - bis ( O -acetyloxime) (54) (71.7%).

1H-NMR(δ ppm; CDCl3) : 0.95 (6H, t), 1.05 (6H, t), 1.89 (6H, s), 2.08 (6H, s), 2.73 (4H, q), 8.02-8.08 (2H, m), 8.19 (1H, s), 8.58 (1H, s), 8.91 (1H, s) 1 H-NMR (δ ppm; CDCl 3): 0.95 (6H, t), 1.05 (6H, t), 1.89 (6H, s), 2.08 (6H, s), 2.73 (4H, q), 8.02-8.08 (2H, m), 8.19 (1H, s), 8.58 (1H, s), 8.91

MS(m/e):473
MS ( m / e ): 473

(바인더 수지 제조)(Binder resin production)

a) 바인더 수지 1의 제조a) Preparation of binder resin 1

500 mL 중합용기에 프로필렌글리콜메틸에테르아세테이트 (Propylene Glycol Methyl Ether Acetate ; PGMEA) 200 mL과 AIBN(azobisisobutyronitrile) 1.5 g을 첨가한 후, 메타아크릴산, 글리시딜메타아크릴산, 메틸메타아크릴산 및 디시클로펜타닐아크릴산을 각각 20:20:40:20의 몰비로 아크릴 모노머의 고형분을 40 중량%로 첨가한 다음, 질소 분위기 하에서 70℃에서 5시간 동안 교반하며 중합시켜 아크릴 중합체인 바인더 수지 1을 제조하였다. 이와 같이 제조된 공중합체의 평균 분자량은 25,000, 분산도는 1.9로 확인되었다.
After adding 200 mL of propylene glycol methyl ether acetate (PGMEA) and 1.5 g of AIBN (azobisisobutyronitrile) to a 500 mL polymerization vessel, a solution of methacrylic acid, glycidyl methacrylic acid, methyl methacrylic acid, and dicyclopentanyl acrylic acid Was added in an amount of 40 wt% of the solid content of the acrylic monomer at a molar ratio of 20: 20: 40: 20, and then the mixture was stirred at 70 ° C for 5 hours under a nitrogen atmosphere to prepare an acrylic polymer binder resin 1. The copolymer thus prepared had an average molecular weight of 25,000 and a degree of dispersion of 1.9.

b) 바인더 수지 2의 제조b) Preparation of binder resin 2

500 mL 중합용기에 프로필렌글리콜메틸에테르아세테이트 200 mL과 AIBN 1.0 g을 첨가한 후, 메타아크릴산, 스틸렌, 메틸메타아크릴산 및 시클로헥실 메타아크릴산을 각각 40:20:20:20의 몰비로 아크릴 모노머의 고형분을 40 중량%로 첨가한 다음, 질소 분위기 하에서 70℃에서 5시간 동안 교반하며 중합시켜 공중합체를 합성하였다. 이 반응기에 N,N-디메틸아닐린 0.3 g과 전체 단량체의 고형분 100몰에 대하여 글리시딜메타아크릴산 20 몰비를 첨가한 후 100℃에서 10시간 동안 교반하여 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체인 바인더 수지 2를 제조하였다. 이와 같이 제조된 공중합체의 평균 분자량은 2O,O00, 분산도는 2.0로 확인되었다.
200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN were added to a 500 mL polymerization vessel, and then a solution of acrylic acid, styrene, methyl methacrylic acid, and cyclohexyl methacrylic acid in a molar ratio of 40:20:20:20, respectively, Was added in an amount of 40% by weight, and the mixture was polymerized under stirring in a nitrogen atmosphere at 70 캜 for 5 hours to synthesize a copolymer. To this reactor was added 0.3 g of N, N -dimethylaniline and 20 molar ratio of glycidyl methacrylic acid to 100 mol of the solid content of the whole monomers, followed by stirring at 100 DEG C for 10 hours to obtain an acrylic polymer binder having an acrylic unsaturated bond Resin 2 was prepared. The average molecular weight of the copolymer thus prepared was found to be 20, 00, and the degree of dispersion was 2.0.

c) 바인더 수지 3의 제조c) Preparation of binder resin 3

500 mL 중합용기에 프로필렌글리콜메틸에테르아세테이트 200 mL과 AIBN 1.0 g을 첨가한 후, 글리시딜메타아크릴산, 스틸렌, 메틸메타 아크릴산 및 시클로헥실메타아크릴산을 각각 40:20:20:20의 몰비로 아크릴 모노머의 고형분을 40 중량%로 첨가한 다음, 질소 분위기 하에서 70 ℃에서 5시간 동안 교반하며 중합시켜 공중합체를 합성하였다. 이 반응기에 N,N-디메틸아닐린 0.3 g과 전체 단량체의 고형분 100몰에 대하여 아크릴산 20 몰비를 첨가한 후 100 ℃에서 10시간 동안 교반하여 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체인 바인더 수지 3을 제조하였다. 이와 같이 제조된 공중합체의 평균 분자량은 18,000, 분산도는 1.8로 확인되었다.
200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN were added to a 500 mL polymerization vessel and glycidyl methacrylic acid, styrene, methyl methacrylic acid, and cyclohexyl methacrylic acid were added to the acrylic resin solution at a molar ratio of 40: 20: 20: The solid content of the monomer was added in an amount of 40% by weight, and the resulting mixture was polymerized under stirring in a nitrogen atmosphere at 70 캜 for 5 hours to synthesize a copolymer. To this reactor was added 0.3 g of N, N -dimethylaniline and 20 molar ratio of acrylic acid to 100 mol of the solid content of the entire monomer, and the mixture was stirred at 100 DEG C for 10 hours to prepare an acrylic polymer having acrylic unsaturated bonds in its side chain Respectively. The copolymer thus prepared had an average molecular weight of 18,000 and a dispersion degree of 1.8.

(실시예 30 내지 45) 포토레지스트 조성물의 제조(Examples 30 to 45) Preparation of photoresist composition

자외선 차단막과 교반기가 설치되어 있는 반응 혼합조에 하기 표 1에 기재된 성분과 함량에 따라 바인더 수지 1 내지 3; 광반응성 화합물; 본 발명에 따른 광중합 개시제; 및 첨가제로 FC-430(3M사의 레벨링제)을 순차적으로 첨가하고, 상온(23 ℃)에서 교반한 다음, 조성물이 총 100 중량%가 되도록 용매로 PGMEA(프로필렌 글리콜 모노메틸 에테르 아세테이트)를 가하여 포토레지스트 조성물을 제조하였다.
In a reaction mixture tank equipped with an ultraviolet shielding film and a stirrer, binder resins 1 to 3 were prepared according to the components and contents shown in Table 1 below. Photoreactive compounds; A photopolymerization initiator according to the present invention; And PGMEA (propylene glycol monomethyl ether acetate) was added as a solvent so that the total amount of the composition became 100% by weight. Then, the mixture was stirred at room temperature (23 ° C) A resist composition was prepared.

(실시예 46) Black Matrix 포토레지스트 조성물의 제조(Example 46) Preparation of Black Matrix photoresist composition

하기 표 1에 기재된 바와 같이, 자외선 차단막과 교반기가 설치되어 있는 반응 혼합조에 바인더 수지 1을 20 중량%, 디펜타에리스리톨헥사아크릴레이트 10 중량%, 실시예 2를 0.5 중량%, 고형분 25 중량%로 PGMEA에 분산된 카본블랙 50 중량% 및 FC-430(3M사의 레벨링제, 0.1중량%)을 순차적으로 첨가하고, 상온에서 교반한 다음, 조성물이 총 100 중량%가 되도록 용매로 PGMEA를 가하여 Black Matrix 포토레지스트 조성물을 제조하였다.As shown in Table 1, 20 wt% of binder resin 1, 10 wt% of dipentaerythritol hexaacrylate, 0.5 wt% of Example 2, and 25 wt% of solids were added to a reaction mixture tank equipped with an ultraviolet shielding film and a stirrer 50% by weight of carbon black dispersed in PGMEA and FC-430 (leveling agent of 3M, 0.1% by weight) were sequentially added and stirred at room temperature. PGMEA was then added to the mixture so that the total amount of the composition was 100% Thereby preparing a photoresist composition.

상기 방법으로 제조된 Black Matrix 포토레지스트 조성물에 대한 평가는 또한 유리 기판 위에서 실시하였으며, 이의 감도, 잔막율, 패턴 안정성, 내화학성 및 연성 등의 성능을 측정하여 그 평가 결과를 하기 표 2에 나타내었다.
Evaluation of the Black Matrix photoresist composition prepared by the above method was also performed on a glass substrate, and its performance such as sensitivity, residual film ratio, pattern stability, chemical resistance and ductility was measured and the evaluation results are shown in Table 2 below .

(실시예 47) Red 포토레지스트 조성물의 제조(Example 47) Preparation of Red photoresist composition

하기 표 1에 기재된 바와 같이, 상기 실시예 46에서 카본블랙 대신에 고형분 25 중량%의 Pigment Red 177(P.R. 177) 분산액을 50 중량%를 사용한 것을 제외하고는 동일한 방법으로 Red 포토레지스트 조성물을 제조하였다.
A red photoresist composition was prepared in the same manner as in Example 46 except that 50% by weight of Pigment Red 177 (PR 177) dispersion having a solid content of 25% by weight was used instead of carbon black .

Figure 112015034569412-pat00047
Figure 112015034569412-pat00047

[비교예 1] 포토레지스트 조성물의 제조[Comparative Example 1] Preparation of photoresist composition

광중합 개시제로 실시예 2 대신에 하기 화학식 B의 광중합 개시제를 사용한 것을 제외하고는 상기 실시예 31과 동일한 방법으로 포토레지스트 조성물을 제조하였다.A photoresist composition was prepared in the same manner as in Example 31 except that the photopolymerization initiator of the following formula (B) was used instead of the photopolymerization initiator.

[화학식 B][Chemical Formula B]

Figure 112015034569412-pat00048
Figure 112015034569412-pat00048

[비교예 2] 포토레지스트 조성물의 제조[Comparative Example 2] Preparation of photoresist composition

광중합 개시제로 실시예 2를 대신에 “3-(아세톡시이미노)-1-(6-니트로-9H-플루오렌-3-일)프로판-1-온"을 광중합 개시제로 사용한 것을 제외하고는 상기 실시예 31과 동일한 방법으로 포토레지스트 조성물을 제조하였다.
Instead of the second embodiment as a photopolymerization initiator-, except that "3- (acetoxy toksiyi mino) -1- (6-nitro -9 H-fluoren-3-yl) propan-1-one" a photopolymerization initiator A photoresist composition was prepared in the same manner as in Example 31.

<평가><Evaluation>

상기 방법으로 제조된 상기 실시예 30 내지 47 및 비교예 1, 2에 따른 포토레지스트 조성물에 대한 평가는 유리 기판 위에서 실시하였으며, 포토레지스트 조성물의 감도, 잔막율, 패턴 안정성, 내화학성 및 연성 등의 성능을 측정하여 그 평가 결과를 하기 표 2에 나타내었다.The evaluation of the photoresist compositions according to Examples 30 to 47 and Comparative Examples 1 and 2 prepared above was performed on a glass substrate and the sensitivity, residual film ratio, pattern stability, chemical resistance and ductility of the photoresist composition And the evaluation results are shown in Table 2 below.

1) 감도1) Sensitivity

유리 기판 위에 각각의 포토레지스트 조성물을 스핀 코팅하여 100 ℃에서 1분 동안 핫플레이트에서 건조한 후 스텝 마스크를 이용하여 노광한 후 0.04 % KOH 수용액에서 현상하였다. 스텝 마스크 패턴이 초기 두께 대비 80 % 두께를 유지하는 노광량을 감도로 평가하였다. Each of the photoresist compositions was spin-coated on a glass substrate, dried on a hot plate at 100 ° C for 1 minute, exposed using a step mask, and developed in a 0.04% KOH aqueous solution. The exposure amount at which the step mask pattern was maintained at 80% thickness with respect to the initial thickness was evaluated as sensitivity.

2) 잔막율2)

각각의 포토레지스트 조성물을 기판위에 스핀 코터를 이용하여 도포한 후, 100 ℃에서 1분간 프리베이크(prebake)하고, 365 nm에서 노광시킨 후, 230 ℃에서 20분 동안 포스트베이크(postbake)를 실시하여 레지스트 막의 포스트베이크 전 후의 두께 비율(%)을 측정하였다.Each of the photoresist compositions was applied on a substrate using a spin coater, prebaked at 100 DEG C for 1 minute, exposed at 365 nm, postbaked at 230 DEG C for 20 minutes (%) Of the resist film before and after post-baking was measured.

3) 패턴 안정성3) Pattern stability

각각의 포토레지스트 조성물을 이용하여 패턴을 형성한 실리콘 웨이퍼를 홀(Hole) 패턴의 수직방향에서부터 절단하고, 패턴의 단면 방향에서 전자현미경으로 관찰하였다. 패턴 사이드 벽(side wall)이 기판에 대하여 55도 이상의 각도로 세워져 있고, 막이 감소되지 않은 것을 '양호'로 하고, 막의 감소가 인정된 것을 '막감(膜減)'으로 판정하였다.The silicon wafer on which the pattern was formed using each photoresist composition was cut from the vertical direction of the hole pattern and observed with an electron microscope in the cross-sectional direction of the pattern. The side wall of the pattern was erected at an angle of 55 degrees or more with respect to the substrate, the film was not reduced and the film was judged to be 'good'.

4) 내화학성4) Chemical resistance

각각의 포토레지스트 조성물을 기판 위에 스핀 코터를 이용하여 도포한 후, 프리베이크(prebake) 및 포스트베이크(postbake) 등의 공정을 거쳐 형성된 레지스트 막을 스트리퍼(Stripper) 용액에 40 ℃에서 10분 동안 담근 후 레지스트 막의 투과율 및 두께의 변화가 있는지 살펴보았다. 투과율 및 두께의 변화가 2 % 이하인 경우 '양호'로 하고, 투과율 및 두께의 변화가 2% 이상이면 '불량'으로 판정하였다.Each of the photoresist compositions was coated on a substrate using a spin coater, and then the resist film formed by a process such as prebake and postbake was immersed in a stripper solution at 40 DEG C for 10 minutes It was examined whether there was a change in the transmittance and the thickness of the resist film. It was judged as 'good' when the transmittance and thickness were less than 2% and 'bad' when the transmittance and thickness were more than 2%.

5) 연성5) ductility

각각의 포토레지스트 조성물을 기판위에 스핀 코터를 도포한 후, 100 ℃에서 1분 동안 프리베이크(prebake)하고, 포토레지스트의 감도로 노광시킨 후, KOH 수용액으로 현상하여 20 um x 20 um의 패턴을 형성하였다. 형성된 패턴을 230 ℃에서 20분 동안 포스트베이크(postbake)를 실시하여 가교시키고, 이 패턴을 나노인덴터 (Nano indentor)를 이용하여 연성을 측정하였다. 나노인덴터의 측정은 5g.f 로딩으로 총 변이량이 500 nm 이상이면 '양호', 500 nm 이하이면 '불량'으로 판정하였다.Each of the photoresist compositions was coated with a spin coater on a substrate, prebaked at 100 ° C for 1 minute, exposed with a photoresist sensitivity, and developed with a KOH aqueous solution to form a pattern of 20 um x 20 um . The formed pattern was post-baked at 230 캜 for 20 minutes to crosslink, and the pattern was measured for ductility using a nanoindentor. The nanoindenter was evaluated as "good" when the total amount of shift was 500 nm or more, and "poor" when the total amount was 500 nm or less.

Figure 112015034569412-pat00049
Figure 112015034569412-pat00049

상기 표 2에 나타낸 바와 같이, 본 발명에 따른 플루오렌일 옥심 에스테르 화합물을 포토레지스트 조성물의 광중합 개시제로 사용할 경우, 소량을 사용하여도 비교예에 비해 감도가 월등히 우수하며, 잔막율, 패턴안정성, 내화학성 및 연성 등의 물성 또한 뛰어나 TFT-LCD 제조 공정 중의 노광 및 포스트베이크 공정 등에서 광중합 개시제로부터 발생하는 아웃개싱을 최소화할 수 있어 오염을 줄일 수 있고 이로 인해 발생할 수 있는 불량을 최소화할 수 있어 고품질의 박막을 제공할 수 있다.As shown in Table 2, when the fluorenyl oxime ester compound according to the present invention was used as a photopolymerization initiator in a photoresist composition, even when a small amount of fluorenyl oxime ester compound was used, the sensitivity was far superior to that of the comparative example, It is possible to minimize the outgassing caused by the photopolymerization initiator in the exposure and post-baking processes in the TFT-LCD manufacturing process, thereby reducing the contamination and minimizing the defects that may occur. Can be provided.

Claims (9)

삭제delete 하기 화학식 2 또는 화학식 3으로 표시되는 플루오렌일 옥심 에스테르 화합물:
[화학식 2]
Figure 112017092642353-pat00052

[화학식 3]
Figure 112017092642353-pat00053

[상기 화학식 2 및 화학식 3에서,
R1 내지 R4는 각각 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C1-C20)알콕시, (C6-C20)아릴(C1-C20)알킬, 히드록시(C1-C20)알킬, 히드록시(C1-C20)알콕시(C1-C20)알킬, (C3-C20)사이클로알킬 또는 (C3-C20)사이클로알킬(C1-C20)알킬이고;
A는 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, 니트로 또는 시아노이고;
n은 0 또는 1 이다.]A fluorenyl oxime ester compound represented by the following formula (2) or (3):
(2)
Figure 112017092642353-pat00052

(3)
Figure 112017092642353-pat00053

[In the formulas (2) and (3)
R 1 to R 4 are independently hydrogen, halogen, (C 1 -C 20) alkyl, respectively, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl (C 1 -C 20) alkyl, hydroxy (C 1 -C 20) alkyl, hydroxy (C 1 -C 20) alkoxy (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl or (C 3 -C 20) cycloalkyl (C 1 -C 20) alkyl;
A is hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, nitro or cyano;
n is 0 or 1.] 제 2항에 있어서,
하기 화합물로부터 선택되는 것을 특징으로 하는 플루오렌일 옥심 에스테르 화합물.
Figure 112017092642353-pat00054

Figure 112017092642353-pat00055

Figure 112017092642353-pat00056

Figure 112017092642353-pat00057

Figure 112017092642353-pat00058

Figure 112017092642353-pat00059

Figure 112017092642353-pat00060

Figure 112017092642353-pat00061

Figure 112017092642353-pat00062
Figure 112017092642353-pat00063
3. The method of claim 2,
A fluorenyl oxime ester compound characterized by being selected from the following compounds.
Figure 112017092642353-pat00054

Figure 112017092642353-pat00055

Figure 112017092642353-pat00056

Figure 112017092642353-pat00057

Figure 112017092642353-pat00058

Figure 112017092642353-pat00059

Figure 112017092642353-pat00060

Figure 112017092642353-pat00061

Figure 112017092642353-pat00062
Figure 112017092642353-pat00063
 제 2항 또는 제 3항의 플루오렌일 옥심 에스테르 화합물을 포함하는 광중합 개시제.A photopolymerization initiator comprising the fluorenyl oxime ester compound of claim 2 or 3. 제 2항 또는 제 3항의 플루오렌일 옥심 에스테르 화합물, 바인더 수지 및 광반응성 화합물을 포함하는 포토레지스트 조성물.A photoresist composition comprising the fluorenyl oxime ester compound of claim 2 or 3, a binder resin, and a photoreactive compound. 제5항에 있어서,
상기 플루오렌일 옥심 에스테르 화합물은 상기 포토레지스트 조성물 총 100 중량%에 대하여, 0.01 내지 15 중량%로 포함되는 것인 포토레지스트 조성물.6. The method of claim 5,
Wherein the fluorenyloxime ester compound is contained in an amount of 0.01 to 15% by weight based on 100% by weight of the total photoresist composition. 제 5항의 포토레지스트 조성물은 색재를 더 포함하는 착색 포토레지스트 조성물.The color photoresist composition of claim 5, further comprising a colorant. 제7항에 따른 착색 포토레지스트 조성물로 제조되는 것을 특징으로 하는 블랙 매트릭스.A black matrix produced from the colored photoresist composition according to claim 7. 제 7항에 따른 착색 포토레지스트 조성물로 제조되는 것을 특징으로 하는 컬러 필터.A color filter, characterized in that it is made of the colored photoresist composition according to claim 7.
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