KR101225695B1 - New high sensitive a-ketoximester photo compounds and photosensitive composition comprising the same - Google Patents
New high sensitive a-ketoximester photo compounds and photosensitive composition comprising the same Download PDFInfo
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- C07D209/80—[b, c]- or [b, d]-condensed
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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Abstract
Description
본 발명은 광개시제로 유용한 알파키토옥심에스테르 화합물 및 이를 이용한 광중합 개시제 조성물에 대한 것이다.
The present invention relates to an alpha chitooxime ester compound useful as a photoinitiator and a photopolymerization initiator composition using the same.
감광성 조성물은 에틸렌성 불포화결합을 가지는 중합성 화합물에 광중합 개시제를 첨가한 것이며, 이러한 감광성 조성물에 365nm, 405nm, 436nm의 혼합광을 조사함으로써 중합경화시킬 수 있기 때문에, 광경화성잉크, 감광성인쇄판, 각종포토레지스트 등으로 이용되고 있다. 단파장의 광원에 감도를 가지는 감광성 조성물은 미세한 인쇄가 가능하기 때문에, 특히 365nm의 광원에 뛰어난 감도를 가지는 광중합 개시제가 요구되고 있다. 이러한 고감도 광개시제로서옥심에스테르 화합물이 많이 사용되고 있으며, 그러한 특성은 여러 특허 문헌에 다양하게 기재되어 있고 또한 상용화된 몇 가지의 상품들이 있다. The photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized by irradiating mixed light of 365 nm, 405 nm, and 436 nm to the photosensitive composition. Thus, photocurable ink, photosensitive printing plate, various It is used as a photoresist or the like. Since the photosensitive composition which has a sensitivity to a short wavelength light source can be printed fine, the photoinitiator which has the outstanding sensitivity to the light source of 365 nm especially is calculated | required. As such a high sensitivity photoinitiator, many oxime ester compounds are used, and such characteristics are variously described in various patent documents and there are several commercially available products.
이러한 옥심에스테르 광개시제의 경우 주로 LCD분야의 포토레지스트에 현재 응용되고 있다. 이러한 기존 상품은 옥심에스테르 화합물과 알파키토옥심(a-ketoxime)에스테르 화합물로 나누어져 있으며, 알파키토옥심에스테르 광개시제의 경우 주로 레드, 그린, 블루와 같은 색을 가지는 포토레지스트에 이용되고 있다. Such oxime ester photoinitiators are mainly applied to photoresists in the LCD field. These conventional products are divided into oxime ester compounds and alpha-chitooxime ester compounds, and alpha-chitooxime ester photoinitiators are mainly used in photoresists having colors such as red, green, and blue.
옥심에스테르 화합물의 경우 UV를 받아 광분해가 일어날 경우 레지스트필름을 변색 시키는 반면 알파키토옥심에스테르 개시제의 경우 변색이 일어나지 않아 칼라레지스트에서의 색좌표 변화를 일으키지 않는다. 이러한 이유로 칼라포토레지스트에서 알파키토옥심에스테르 화합물을 주로 사용하고 있지만 현재의 상품화된 알파키토옥심에스테르 광중합개시제의 경우 그 감도가 높지 않아 높은 감도의 알파키토옥심에스테르 광중합 개시제가 요망되고 있다.
In the case of the oxime ester compound, the photoresist is discolored when UV is decomposed, whereas the alpha chito oxime ester initiator does not discolor and does not cause color coordinate change in the color resist. For this reason, the alpha chito oxime ester compound is mainly used in the color photoresist, but the current commercially available alpha chito oxime ester photopolymerization initiator has not been highly sensitive, and therefore, a high sensitivity alpha chito oxime ester photopolymerization initiator is desired.
본 발명은 UV 최대 흡광이 365nm 및 405nm에 가까운 고감도성이며 동시에 현상성, 밀착성, 내알칼리성이 우수한 알파키토옥심에스테르 화합물 및 이를 포함하는 광중합 개시제를 제공하는 것을 목적으로 한다.
An object of the present invention is to provide an alpha-chitooxime ester compound having a high UV absorbance close to 365 nm and 405 nm and having excellent developability, adhesion and alkali resistance, and a photopolymerization initiator comprising the same.
본 발명의 상기의 과제를 해결하기 위해 안출된 것으로서, 하기 화학식 1 및 화학식 2로 표현되는 알파케토옥심에스테르 화합물을 제공한다.
In order to solve the above problems of the present invention, there is provided an alpha keto oxime ester compound represented by the following formula (1) and (2).
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 화학식 1 및 2에서, In the above Formulas 1 and 2,
R은 1 내지 5개의 메틸기를 갖는 메틸벤젠기인 것으로, 다음 화학식 R과 같이 예시적으로 표현될 수 있다.R is a methylbenzene group having 1 to 5 methyl groups, and may be exemplarily represented by the following Chemical Formula R.
[화학식 R][Chemical formula R]
또한, 상기 화학식 1 및 2에서, R1은 탄소수 1 내지 10인 알킬기, 특히 메틸기, 벤조일기, 또는 탄소수 3 내지 6인 사이클로 알킬기이고, In addition, in Chemical Formulas 1 and 2, R 1 is an alkyl group having 1 to 10 carbon atoms, in particular a methyl group, benzoyl group, or a cycloalkyl group having 3 to 6 carbon atoms,
R2는 -CH3,-C2H5, -프로필, 또는 -벤조일이고, R 2 is —CH 3 , -C 2 H 5 , -propyl, or -benzoyl,
R3는 -H이거나, a가 메틸 또는 에틸기이고 b가 H 또는 메틸기이며 하기 화학식으로 표현되는 
X는, -O-, -S-, -Se-이다.X is -O-, -S-, -Se-.
또한, 본 발명은 상기 화학식 1의 화합물 및 화학식 2의 화합물에서 선택된 하나 이상의 화합물 및 용제 또는 알칼리 수용액에 가용인 고분자 화합물 및/또는 에틸렌성 불포화 결합을 갖는 광중합성 화합물을 포함하는 것을 특징으로 하는 감광성 수지 조성물을 제공한다. The present invention also provides a photosensitive compound comprising a photopolymerizable compound having a polymer compound and / or an ethylenically unsaturated bond soluble in at least one compound selected from the compound of Formula 1 and the compound of Formula 2 and a solvent or an aqueous alkali solution. It provides a resin composition.
여기에서 상기 조성물은 착색제 또는 안료를 더 포함할 수 있다.Here, the composition may further include a colorant or a pigment.
또한, 본 발명은 상기 감광성 수지 조성물로부터 형성된 칼럼 스페이서를 제공한다. The present invention also provides a column spacer formed from the photosensitive resin composition.
또한, 본 발명은 상기 감광성 수지 조성물로부터 형성된 블랙 매트릭스를 제공한다. The present invention also provides a black matrix formed from the photosensitive resin composition.
또한, 본 발명은 상기 감광성 수지 조성물로부터 형성된 컬러 필터 조성물을 제공한다. Moreover, this invention provides the color filter composition formed from the said photosensitive resin composition.
또한, 본 발명은 상기 감광성 수지 조성물로부터 형성된 유기 절연막을 갖는 기판을 제공한다. Moreover, this invention provides the board | substrate which has an organic insulating film formed from the said photosensitive resin composition.
또한, 본 발명은 상기 감광성 수지 조성물을 코팅하여 형성된 막을 갖는 기재를 제공한다. 여기에서 상기 막은 워드프로세서, 컴퓨터, 텔레비전 또는 플라즈마 디스플레이 패널, 액정표시장치에 사용되는 편광판의 표면, 선글라스 렌즈, 도수가 있는 안경렌즈, 카메라용 파인더 렌즈, 게기의 커버, 자동차의 유리, 전차의 유리, 광휘도 향상막, 또는 광도파로막으로 사용되는 것을 특징으로 하는 것이다.
The present invention also provides a substrate having a film formed by coating the photosensitive resin composition. Here, the film is a surface of a polarizing plate used in a word processor, a computer, a television or a plasma display panel, a liquid crystal display device, a sunglasses lens, a spectacle lens, a finder lens for a camera, a cover of a flag, a glass of an automobile, a glass of a tank , An optical brightness enhancing film or an optical waveguide film.
본 발명에 따르면 감광성 조성물의 용제로 유용한 PGMEA 등에 대한 용해성이 우수한 알파키토옥심에스테르 화합물을 제공할 수 있으며, 이로써 광가교 반응시에 사용되는 광개시제로서의 알파키토옥심에스테르 화합물의 양을 최소화할 수 있고, 이를 포함하는 감광성 조성을 박막 코팅한 후 용매를 휘발시켰을 때 바인더와 광개시제와의 상분리를 줄여 가교후의 박막 특성을 향상시킬 수 있다. 이로써 양질의 블랙 매트릭스, 컬러필터, 컬럼 스페이서, 절연막, 광가교성 피막 등을 제조할 수 있다.
According to the present invention, it is possible to provide an alpha chito oxime ester compound having excellent solubility in PGMEA, etc., which is useful as a solvent of the photosensitive composition, thereby minimizing the amount of the alpha chito oxime ester compound as a photoinitiator used in the photocrosslinking reaction, When the solvent is volatilized after the thin film coating of the photosensitive composition including the same, phase separation between the binder and the photoinitiator may be reduced to improve thin film properties after crosslinking. As a result, a good black matrix, color filter, column spacer, insulating film, photocrosslinkable film, and the like can be manufactured.
본원 발명은 용매에 대한 적절한 용해도와 우수한 광감도를 달성할 수 있는 하기 화학식 1 및 2로 표현되는 알파키토옥심에스테르 화합물을 제공한다. 하기 화학식 1 및 2에서 알파키토옥심에스테르 구조의 질소원자와 이중결합하는 탄소원자는 메틸벤젠기와 결합된 것을 특징으로 한다.
The present invention provides an alpha chito oxime ester compound represented by the following formulas (1) and (2) capable of achieving proper solubility in solvents and excellent photosensitivity. In the formulas (1) and (2), the carbon atom double-bonded with the nitrogen atom of the alpha-chitooxime ester structure is characterized in that it is bonded with a methylbenzene group.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 화학식 1 및 2에서, In the above Formulas 1 and 2,
R은 1 내지 5개의 메틸기를 갖는 메틸벤젠기인 것으로, 다음 화학식 R과 같이 예시적으로 표현될 수 있다.R is a methylbenzene group having 1 to 5 methyl groups, and may be exemplarily represented by the following Chemical Formula R.
[화학식 R][Chemical formula R]
R1은 탄소수 1 내지 10인 알킬기, 특히 메틸기, 벤조일기, 또는 탄소수 3 내지 6인 사이클로 알킬기이고, R 1 is an alkyl group having 1 to 10 carbon atoms, in particular a methyl group, benzoyl group, or a cycloalkyl group having 3 to 6 carbon atoms,
R2는 -CH3,-C2H5, -프로필, 또는 -벤조일이고, 특히 에틸기가 바람직하고,R 2 is —CH 3 , —C 2 H 5 , —propyl, or —benzoyl, especially an ethyl group is preferred,
R3는 -H이거나 a가 메틸 또는 에틸기이고 b가 H 또는 메틸기인 
또한, 상기 화학식 2에서 X는 -O-, -S-, 또는 -Se-이고 특히 -O-, -S-인 것이 바람직하다.
In addition, in Formula 2, X is -O-, -S-, or -Se-, and particularly preferably -O-, -S-.
상기 화학식 1 내지 2로 표현되는 화합물의 바람직한 구체예들은 다음의 화학식 3 내지 32로 표현되는 것들을 포함한다. 그러나, 본원 발명은 하기 예시에 의해 한정되지 않는다.
Preferred embodiments of the compound represented by Formula 1 to 2 include those represented by the following Formula 3 to 32. However, the present invention is not limited by the following examples.
[화학식 3](3)
[화학식 4][Formula 4]
[화학식 5][Chemical Formula 5]
[화학식 6] [Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Chemical Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[화학식 12][Chemical Formula 12]
[화학식 13][Chemical Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
[화학식 16][Chemical Formula 16]
[화학식 17][Chemical Formula 17]
[화학식 18][Chemical Formula 18]
[화학식 19][Formula 19]
[화학식 20][Chemical Formula 20]
[화학식 21][Chemical Formula 21]
[화학식 22][Formula 22]
[화학식 23]
(23)
[화학식 24]≪ EMI ID =
[화학식 25](25)
[화학식 26](26)
[화학식 27](27)
[화학식 28](28)
[화학식 29][Formula 29]
[화학식 30](30)
[화학식 31](31)
[화학식 32](32)
카바졸 구조를 포함하는 화학식 1의 알파키토옥심에스테르 화합물의 합성Synthesis of Alpha Chitooxime Ester Compounds of Formula 1 Containing Carbazole Structures
상기 화학식 1로 표현되는 화합물을 제조하는 방법은 예를 들면 하기의 반응식 1로 설명되는 합성과정에 의해 합성되어질 수 있다. 그러나 이에 한정되는 것은 아니다. The method for preparing the compound represented by Chemical Formula 1 may be synthesized by, for example, a synthesis process described by Scheme 1 below. However, the present invention is not limited thereto.
우선 카바졸 화합물과 카르본산 클로라이드와 나이트로 카르본산 클로라이드를 순차적으로 염화알루미늄 존재하에 반응시켜서 아실화합물을 얻는다. 이 아실화합물을 염기촉매하에서 이소아밀나이트리트와 반응시켜서 알파키토옥심화합물을 얻는다. 다음으로 알파키토옥심화합물과 카르본산클로라이드를 트리에틸아민 촉매하에서 반응시켜 상기 화학식 1로 표현되는 알파키토옥심에스테르 화합물을 얻는다.
First, the carbazole compound, carboxylic acid chloride, and nitro carboxylic acid chloride are sequentially reacted in the presence of aluminum chloride to obtain an acyl compound. The acyl compound is reacted with isoamyl nitrite under a base catalyst to obtain an alpha chitooxime compound. Next, the alpha chito oxime compound and the carboxylic acid chloride are reacted under a triethylamine catalyst to obtain an alpha chito oxime ester compound represented by Chemical Formula 1.
[반응식 1][Reaction Scheme 1]
디페닐Diphenyl 구조를 포함하는 화학식 2의 (2) < / RTI > 알파키토옥심에스테르Alpha chitooxime ester 화합물의 합성 Synthesis of compounds
상기 화학식 2로 표현되는 화합물을 제조하는 방법은 예를 들면 하기의 반응식 2로 설명되는 합성과정에 의해 합성되어질 수 있다. 그러나 이에 한정되는 것은 아니다. The method for preparing the compound represented by Chemical Formula 2 may be synthesized by, for example, a synthesis process described by Scheme 2 below. However, the present invention is not limited thereto.
우선 디페닐 화합물과 카르본산 클로라이드와 나이트로 카르본산 클로라이드를 순차적으로 염화알루미늄 존재하에 반응시켜서 아실화합물을 얻는다. 이 아실화합물을 염기촉매하에서 이소아밀나이트리트와 반응시켜서 알파키토옥심화합물을 얻는다. 다음으로 알파키토옥심화합물과 카르본산클로라이드를 트리에틸아민 촉매하에서 반응시켜 상기 화학식 2로 표현되는 알파키토옥심에스테르 화합물을 얻는다.
First, a diphenyl compound, carboxylic acid chloride, and nitro carboxylic acid chloride are sequentially reacted in the presence of aluminum chloride to obtain an acyl compound. The acyl compound is reacted with isoamyl nitrite under a base catalyst to obtain an alpha chitooxime compound. Next, the alpha chito oxime compound and the carboxylic acid chloride are reacted under a triethylamine catalyst to obtain an alpha chito oxime ester compound represented by Chemical Formula 2.
[반응식 2]Scheme 2
본 발명은 광개시제로서 상기 화학식 1 내지 2 중 어느 하나로 표현되는 알파키토옥심에스테르 화합물을 포함하는 감광성 수지 조성물을 제공한다.
The present invention provides a photosensitive resin composition comprising an alpha chito oxime ester compound represented by any one of Formulas 1 to 2 as a photoinitiator.
상기 감광성 수지 조성물은 광개시제로서 상기 화학식 1 내지 2 중 어느 하나로 표현되는 알파키토옥심에스테르 화합물을 하나 이상 포함할 수 있다. 또한, 상기 감광성 수지 조성물은 공지의 광개시제가 더 포함될 수 있다.
The photosensitive resin composition may include one or more alpha chito oxime ester compounds represented by any one of Formulas 1 to 2 as a photoinitiator. In addition, the photosensitive resin composition may further include a known photoinitiator.
본원 발명에 따른 알파키토옥심에스테르 화합물 1종 이상과 다른 공지의 광개시제를 혼합하여 사용하는 경우에는 본원 발명에 따른 알파키토옥심에스테르 화합물의 함량이 전체 광개시제 전체 중량 대비 50 중량% 이상 포함하는 것이 바람직하다. 즉, 전체 광개시제 전체 중량 대비 50중량%이 포함되도록 함으로써 본원 발명에 따른 알파키토옥심에스테르 화합물에 의한 광개시제의 감도의 유지 효과를 달성할 수 있다.
When one or more alpha chito oxime ester compounds according to the present invention are mixed with other known photoinitiators, the content of the alpha chito oxime ester compounds according to the present invention is preferably 50% by weight or more relative to the total weight of the total photoinitiator. . That is, by including 50% by weight relative to the total weight of the total photoinitiator it is possible to achieve the effect of maintaining the sensitivity of the photoinitiator by the alpha chito oxime ester compound according to the present invention.
여기에서 상기 공지의 광개시제의 일예로는, 아세토페논, 2,2-디에톡시아세토페논, p-디메틸아세토페논, p-디메틸아미노프로피오페논, 디클로로아세토페논, 트리클로로아세토페논, p-tert-부틸아세토페논 등의 아세토페논류나, 벤조페논, 2-클로로벤조페논, p,p'-비스디메틸아미노벤조페논 등의 벤조페논류나, 벤질, 벤조인, 벤조인메틸에테르, 벤조인이소프로필에테르, 벤조인이소부틸에테르 등의 벤조인에테르류나, 벤질디메틸케탈, 티오크산텐, 2-클로로티오크산텐, 2,4-디에틸티오크산텐, 2-메틸티오크산텐, 2-이소프로필티오크산텐 등의 설퍼화합물이나, 2-에틸안트라퀴논, 옥타메틸안트라퀴논, 1,2-벤즈안트라퀴논, 2,3-디페닐안트라퀴논 등의 안트라퀴논류나, 아조비스이소부티로니트릴, 벤조일퍼옥사이드, 쿠멘퍼옥사이드 등의 유기과산화물이나, 2-메르캅토벤조이미다졸, 2-메르캅토벤조옥사졸, 2-메르캅토벤조티아졸 등의 티올(thiol) 화합물이나, 2-(o-클로로페닐)-4,5-디(m-메톡시페닐)-이미다졸릴 이량체 등의 이미다졸릴 화합물이나, p-메톡시트리아진 등의 트리아진 화합물이나, 2,4,6-트리스(트리클로로메틸)-s-트리아진, 2-메틸-4,6-비스(트리클로로메틸)-s-트리아진, 2-[2-(5-메틸푸란-2-일)에테닐]-4,6-비스(트리클로로메틸)-s-트리아진, 2-[2-(푸란-2-일)에테닐]-4,6-비스(트리클로로메틸)-s-트리아진, 2-[2-(4-디에틸아미노-2-메틸페닐)에테닐]-4,6-비스(트리클로로메틸)-s-트라아진, 2-[2-(3,4-디메톡시페놀)에테닐]-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-메톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-에톡시스티릴)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-n-부톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진 등의 할로메틸기를 가지는 트리아진 화합물, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부탄-1온 등의 아미노케톤 화합물을 들 수 있다.
Examples of the known photoinitiator herein include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert- Acetophenones such as butyl acetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, Benzoin ethers such as benzoin isobutyl ether, benzyl dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethyl thioxanthene, 2-methylthioxanthene, and 2-isopropylthioke Sulfur compounds such as xanthene, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, azobisisobutyronitrile and benzoyl peroxide Organic peroxides such as cumene peroxide and 2-meth Thiol compounds, such as a lecaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl Imidazolyl compounds such as) -imidazolyl dimer, triazine compounds such as p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine To 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) Tenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenol) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Of halo-triazine compound having a methyl group, and 2-benzyl-1- (4-morpholinophenyl) - there may be mentioned amino ketone compounds, such as butane -1-one.
그리고, 본 발명의 감광성 수지 조성물은 증감제로서, 사이닌, 크산텐, 옥사진, 티아진, 디아릴메탄, 트리아릴메탄 및 피릴륨 등의 양이온 염료, 메로시아닌, 쿠마린, 인디고, 방향족 아민류, 프탈로시아닌, 아조, 퀴논 및 티오크산텐 감광 염료 등의 중성 염료, 및 벤조페논류, 아세토페논류, 벤조인류, 티오크산톤류, 안트라퀴논류, 이미다졸류, 비이미다졸류, 쿠마린류, 케토쿠마린류, 트리페닐피릴륨류, 트리아진류 및 벤조산 등의 화합물 등을 더 포함할 수 있다.
The photosensitive resin composition of the present invention may contain as sensitizers cationic dyes such as sinin, xanthene, oxazine, thiazine, diarylmethane, triarylmethane and pyrylium, merocyanine, coumarin, indigo, aromatic amines , A neutral dye such as phthalocyanine, azo, quinone and thioxanthine photosensitive dye and a neutral dye such as benzophenone, acetophenone, benzoin, thioxanthone, anthraquinone, imidazoles, Compounds such as ketocoumarins, triphenylphyryliums, triazines and benzoic acid, and the like.
본 발명의 감광성 수지 조성물에는 용제 또는 알칼리 수용액에 가용인 고분자 화합물 단독 또는 이들 고분자 화합물과 에틸렌성 불포화 결합을 갖는 광중합성 화합물의 혼합물을 포함할 수 있다. 여기서 용제 또는 알칼리 수용액에 가용인 고분자 화합물이나 에틸렌성 불포화 결합을 갖는 광중합성 화합물의 일예로는, 구체적으로는 아크릴산, 메타크릴산, 푸마르산, 말레산, 푸마르산 모노메틸, 푸마르산 모노에틸, 2-히드록시에틸아크릴레이트, 2-히드록시에틸메타크릴레이트, 에틸렌글리콜모노메틸에테르아크릴레이트, 에틸렌글리콜모노메틸에테르메타크릴레이트, 에틸렌글리콜모노에틸에테르아크릴레이트, 에틸렌글리콜모노에틸에테르메타크릴레이트, 글리세롤아크릴레이트, 글리세롤메타크릴레이트, 아크릴산아미드, 메타크릴산아미드, 아크릴로니트릴, 메타크릴로니트릴, 메틸아크릴레이트, 메틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 이소부틸아크릴레이트, 이소부틸메타크릴레이트, 2-에틸헥실아크릴레이트, 2-에틸헥실메타크릴레이트, 벤질아크릴레이트, 벤질메타크릴레이트, 에틸렌글리콜디아크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디아크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 부틸렌글리콜디메타크릴레이트, 프로필렌글리콜디아크릴레이트, 프로필렌글리콜디메타크릴레이트, 트리메틸롤프로판트리아크릴레이트, 트리메틸롤프로판트리메타크릴레이트, 테트라메틸롤프로판테트라아크릴레이트, 테트라메틸롤프로판테트라메타크릴레이트, 펜타에리스리톨트리아크릴레이트, 펜타에리스리톨트리메타크릴레이트, 펜타에리스리톨테트라아크릴레이트, 펜타에리스리톨테트라메타크릴레이트, 디펜타에리스리톨펜타아크릴레이트, 디펜타에리스리톨펜타메타크릴레이트, 디펜타에리스리톨헥사아크릴레이트, 디펜타에리스리톨헥사메타크릴레이트, 1,6-헥산디올디아크릴레이트, 1,6-헥산디올디메타크릴레이트, 카르도에폭시디아크릴레이트 등의 모노머, 올리고머류; 다가 알코올류와 1염기산 또는 다염기산을 축합하여 얻어지는 폴리에스테르 프리폴리머에 (메타)아크릴산을 반응하여 얻어지는 폴리에스테르(메타)아크릴레이트, 폴리올기와 2개의 이소시아네이트기를 가지는 화합물을 반응시킨 후, (메타)아크릴산을 반응하여 얻어지는 폴리우레탄(메타)아크릴레이트; 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 비스페놀 S형 에폭시 수지, 페놀 또는 크레졸 노볼락형 에폭시 수지, 레졸형 에폭시수지, 트리페놀메탄형 에폭시 수지, 폴리카르복시산 폴리글리시딜에스테르, 폴리올폴리글리시딜에스테르, 지방족 또는 지환식 에폭시 수지, 아민에폭시 수지, 디히드록시벤젠형 에폭시 수지 등의 에폭시 수지와 (메타)아크릴산을 반응하여 얻어지는 에폭시(메타)아크릴레이트 수지 등을 들 수 있다. 더욱이 상기 에폭시(메타)아크릴레이트 수지에 다염기산 무수물을 반응시킨 수지를 사용할 수 있다. 이들 광중합성 화합물은 카도계 수지일 수도 있다.
The photosensitive resin composition of the present invention may contain a polymeric compound solely soluble in a solvent or an aqueous alkali solution or a mixture of these polymeric compounds and a photopolymerizable compound having an ethylenic unsaturated bond. Examples of the polymer compound or the photopolymerizable compound having an ethylenically unsaturated bond soluble in a solvent or an aqueous alkali solution include acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, Hydroxyethyl methacrylate, ethyleneglycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate Acrylate, methacrylic acid amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, Acrylate, 2-ethylhexyl acrylate, 2- Hexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetra Ethylene glycol diacrylate, ethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Tetramethylol propane tetraacrylate, tetramethylol propane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol penta Acrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol dimethacrylate, cardo-epoxy acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate, Monomers such as diacrylate, oligomers; (Meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid, a polyester (meth) acrylate obtained by reacting a polyol group with a compound having two isocyanate groups, (Meth) acrylate obtained by reacting polyurethane (meth) acrylate; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, (Meth) acrylate resins obtained by reacting an epoxy resin such as a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, and a dihydroxybenzene type epoxy resin with (meth) acrylic acid. Further, a resin obtained by reacting the epoxy (meth) acrylate resin with a polybasic acid anhydride can be used. These photopolymerizable compounds may be cardade resins.
특히 용제 또는 알칼리 수용액에 가용성인 고분자는 투명성이 높은 고분자 중합체로, 현상액(용제 또는 알칼리 수용액)에 가용인 것이다. 이러한 고분자 중합체로는 열경화성 수지, 열가소성 수지, 감광성 수지 등을 들 수 있으며, 단독 또는 2종 이상의 혼합물로서 사용된다. 특히 내열성, 내용제성, 내약품성이 우수한 것이 바람직하다.
In particular, the polymer soluble in a solvent or an aqueous alkali solution is a highly transparent high polymer and soluble in a developer (solvent or alkaline aqueous solution). Examples of such a polymer include a thermosetting resin, a thermoplastic resin, and a photosensitive resin. They are used alone or as a mixture of two or more. Particularly excellent in heat resistance, solvent resistance and chemical resistance.
에틸렌성 불포화 결합을 갖는 화합물로는 노광 감도 및 효과 후의 여러 내성의 면에서 다작용성 (메타)아크릴계 모노머를 사용하는 것이 유리할 수 있다.
As the compound having an ethylenically unsaturated bond, it may be advantageous to use a polyfunctional (meth) acrylic monomer in view of exposure sensitivity and various resistance after effects.
한편 감광성 수지 조성물은 일예로 컬러 필터나 블랙 매트릭스 형성용 레지스트로 적용하기 위해 안료 또는 착색제를 함유할 수 있다.
On the other hand, the photosensitive resin composition may contain a pigment or a coloring agent, for example, to apply to a color filter or a resist for forming a black matrix.
착색제로는 레드, 그린, 블루와 감색 혼합계의 시안, 마젠다, 옐로우, 블랙 안료를 들 수 있다. 안료로는 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, 및 티탄 블랙 등을 들 수 있다.
Examples of the colorant include cyan, magenta, yellow and black pigments of red, green, blue and a mixture of blue and green. As the pigment, CI Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 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 Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15: 1, 15: 4, 15: , CI Pigment Green 7, 36, CI Pigment Brown 23, 25, 26, CI Pigment Black 7, and titanium black.
본 발명에 따르면 이와 같은 감광성 수지 조성물로부터 칼럼 스페이서, 블랙 매트릭스, 컬러 필터, 유기절연막을 갖는 기판, 이를 코팅하여 형성된 막을 갖는 기재를 제공하며, 여기서의 막은 플라즈마 디스플레이 패널, 액정표시장치에 사용되는 편광판의 표면, 선글라스 렌즈, 도수가 있는 안경렌즈, 카메라용 파인더 렌즈, 계기의 커버, 자동차의 유리, 전차의 유리, 광휘도 향상막, 또는 광도파로막으로 사용되는 것일 수 있다.
According to the present invention, there is provided a substrate having a column spacer, a black matrix, a color filter, an organic insulating film, and a film formed from such a photosensitive resin composition by coating such a photosensitive resin composition. The film is used for a plasma display panel, A sunglass lens, a spectacle lens with a frequency, a finder lens for a camera, a cover for a meter, a glass for an automobile, a glass for a train, a brightness enhancement film, or an optical waveguide film.
이와 같은 감광성 조성물을 사용하여 패턴을 형성하는 방법으로는, 기판 또는 기판 상에 감광성 수지 조성물을 도포하고, 도포된 감광성 조성물층으로부터 용제 등 휘발 성분을 제거하고, 포토마스크를 통해 휘발 성분이 제거된 층을 노광한 후 현상하는 방법을 들 수 있다. 이에 본 발명에서는 이와 같은 경화 과정을 거쳐 얻어지는 경화막을 제공한다.
As a method for forming a pattern using such a photosensitive composition, a photosensitive resin composition is coated on a substrate or a substrate, volatile components such as a solvent are removed from the applied photosensitive composition layer, and a volatile component is removed through a photomask And exposing the layer to light and then developing the layer. Accordingly, the present invention provides a cured film obtained through such a curing process.
기판으로는 예를 들면 유리 기판, 실리콘 기판, 폴리카보네이트 기판, 폴리에스테르 기판, 방향족 폴리아미드 기판, 폴리아미드이미드 기판, 폴리이미드 기판, 알루미늄 기판, GaAs 기판 등의 표면이 평탄한 기판 등을 들 수 있다.
Examples of the substrate include a substrate having a flat surface such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate or a GaAs substrate .
기판 위에 감광성 수지 조성물을 도포하는 방법으로는 한정이 없으나, 일예로 스핀 코팅법, 캐스팅법, 롤 도포법, 슬릿 & 스핀 코팅법, 스핀리스 코터 등의 코터를 사용하여 도포하는 등의 공지된 도포 방법 등으로 기판 등 위에 도포할 수 있다.
There is no limitation on the method of applying the photosensitive resin composition on the substrate, but a known coating method such as spin coating, casting, roll coating, slit & spin coating and coating using a coater such as a spinless coater Method or the like.
이어서 용제 등의 휘발 성분을 가열에 의해 휘발시킬 수 있다. 이와 같이하여 기판 등의 위에 감광성 조성물의 고형분으로 이루어진 층이 형성된다. 그 다음 감광성 조성물의 고형분으로 이루어진 층을 노광하는데, 예를 들면 포토마스크를 통해 선택적으로 활성 에너지선을 조사할 수 있다. 노광 광원으로는 통상 저압 수은등, 중압 수은등, 고압 수은등, 초고압 수은등, 크세논 램프, 금속 할로겐 램프 등이 적당하다. 또한 레이저 광선 등도 노광용 활성 에너지선으로 사용할 수 있다. 그밖에 전자선, α선, β선, γ선, χ선, 중성자선 등도 사용 가능하다. 활성 에너지선은 포토마스크를 통해 조사되며, 여기서 포토마스크는 예를 들면 유리판 표면에 활성 에너지선을 차페하는 차광층이 설치된 것이다. 유리판 중의 차광층이 설치되지않은 부분은 활성 에너지선이 투과하는 투광부이며, 이 투광부의 패턴에 따른 패턴으로 감광성 조성물이 노광되어 활성 에너지선이 조사되지 않은 미조사 영역과 활성 에너지선이 조사된 조사 영역이 생긴다.
Subsequently, volatile components such as solvents can be volatilized by heating. Thus, a layer made of the solid content of the photosensitive composition is formed on a substrate or the like. Then, a layer of the solid content of the photosensitive composition is exposed, for example, the active energy ray can be selectively irradiated through a photomask. As the exposure light source, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp and the like are suitable. A laser beam or the like can also be used as an active energy ray for exposure. In addition, electron beams, α rays, β rays, γ rays, χ rays, neutron rays, and the like can also be used. The active energy ray is irradiated through the photomask, where the photomask is provided with a light shielding layer for shielding the active energy ray, for example, on the surface of the glass plate. The portion of the glass plate where the light-shielding layer is not provided is a light-transmitting portion through which the active energy ray passes. The photosensitive composition is exposed in a pattern according to the pattern of the light-transmitting portion, An irradiation area is generated.
이와 같이 노광을 행한 기판은 일예로 묽은 알칼리 수용액으로 현상한다. 현상하는 데는 예를 들면 노광 후의 감광성 조성물층을 묽은 알칼리 수용액과 접촉시킬 수 있고 구체적으로는 그 표면 상에 감광성 조성물층이 형성된 상태의 기판을 묽은 알칼리 수용액에 침지하거나 묽은 알칼리 수용액을 샤워 형태로 내뿜을 수 있다. 묽은 알칼리 수용액으로서는 예를 들면 탄산나트륨, 탄산칼륨, 수산화나트륨, 수산화칼륨, 테트라메틸암모늄하이드록사이드, 유기 아민 등의 알칼리성 화합물의 수용액 등을 들 수 있다. 현상에 의해서 감광성 조성물층 중의 활성 에너지선이조사되지 않은 미조사 영역은 제거된다. 한편 활성 에너지선 조사 영역은 그대로 남아 패턴을 구성한다.
The substrate thus exposed is developed with a dilute alkali aqueous solution, for example. For example, the photosensitive composition layer after exposure can be contacted with a dilute alkali aqueous solution. Specifically, the substrate in a state in which a photosensitive composition layer is formed on the surface thereof is immersed in a diluted alkali aqueous solution, or a dilute alkali aqueous solution is sprayed in a shower form . Examples of the dilute alkali aqueous solution include aqueous solutions of alkaline compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and organic amines. The unirradiated area | region to which the active energy ray was not irradiated in the photosensitive composition layer is removed by image development. On the other hand, the active energy irradiation area remains as a pattern.
이와 같이 현상을 행한 기판은 통상적으로 수세하여 건조시킴으로써 목적하는 패턴을 얻을 수 있다.
The substrate which has been developed in this manner can be washed with water and dried, thereby obtaining a desired pattern.
실시예Example
이하 본 발명을 실시예를 통하여 보다 상세하게 설명한다. 그러나 이들 실시예는 본 발명을 예시적으로 설명하기 위한 것으로서 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only and the scope of the present invention is not limited by these examples.
[실시예 1]
[Example 1]
1 단계 : 2-(o-tolyl)acetyl chloride의 합성Step 1: Synthesis of 2- (o-tolyl) acetyl chloride
질소분위기 하에서 2-(o-tolyl)acetic acid (100g)과 티오닐클로라이드 (237g)을 넣고 온도를 서서히 올려 95℃에서 4시간 동안 환류시켰다. 4시간 후 동일 온도에서 증류장치를 설치하여 상압에서 티오닐클로라이드를 증류하였다. 반응기의 온도를 상온으로 냉각 후 진공 증류 장치를 이용하여 잔여의 티오닐클로라이드를 제거하였다. 잔류의 점성 액체를 석유에테르에 침전, 여과하여 노란색의 결정을 얻었다. 노란색 결정은 112g으로 수율은 71%이었다.2- (o-tolyl) acetic acid under nitrogen atmosphere (100 g) and thionyl chloride (237 g) were added thereto, and the temperature was gradually raised to reflux at 95 ° C. for 4 hours. After 4 hours, the distillation apparatus was installed at the same temperature to distill the thionyl chloride at atmospheric pressure. After the reactor was cooled to room temperature, residual thionyl chloride was removed using a vacuum distillation apparatus. The remaining viscous liquid was precipitated in petroleum ether and filtered to give yellow crystals. The yellow crystals were 112 g with a yield of 71%.
GC Purity : 99%GC Purity: 99%
GC MASS : m/z = 168.03
GC MASS: m / z = 168.03
2 단계: 1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)-2- (o-tolyl) ethanone의 합성Step 2: Synthesis of 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (o-tolyl) ethanone
질소 분위기하에서 N-에틸카바졸 20.0g과 건조된 CH2Cl2 120ml을 가하여 녹였다. 반응물을 0℃로 냉각한 후 AlCl3 14.07g을 천천히 투입하였다. 여기에 o-toluyl chloride 16.31g 을 내부온도 5℃ 이하에서 천천히 적가하였다. 반응 온도를 상온으로 하여 5시간 정도 교반 후 내부 온도를 0℃ 이하로 내리고 AlCl3 14.07g을 천천히 투입하였다. 이 반응물에 2-(o-tolyl)acetyl chloride 17.79g 을 내부온도 5℃ 이하에서 천천히 적가하였다. 반응 온도를 상온으로 하여 8시간 정도 교반 후 내부 온도를 0℃ 이하로 내리고, 얼음물 300ml에 반응기의 용액을 천천히 가하고 1시간 교반 후 층분리 하고 다시 1% NaOH 200ml로 중화, 세척한 후 유기층을 MgSO4로 건조시킨 후 회전증발기로 용매를 제거하여 에틸아세테이트와 메틸렌클로라이드로 재결정 하여 수율 77%의 흰색 고체 35g을 얻었다. 20.0 g of N-ethylcarbazole and 120 ml of dried CH 2 Cl 2 were added and dissolved in a nitrogen atmosphere. After cooling the reaction to 0 ℃ AlCl 3 14.07 g was slowly added. 16.31 g of o-toluyl chloride was slowly added dropwise at an internal temperature of 5 ° C. or lower. After stirring the reaction temperature at room temperature for about 5 hours, the internal temperature was lowered to 0 ° C. or lower, and AlCl 3 14.07 g was slowly added. 17.79 g of 2- (o-tolyl) acetyl chloride was slowly added dropwise to the reaction at an internal temperature of 5 ° C or lower. After stirring the reaction temperature at room temperature for about 8 hours, the internal temperature was lowered to 0 ° C. or lower, the solution of the reactor was slowly added to 300 ml of ice water, stirred for 1 hour, the layers were separated, neutralized and washed with 200 ml of 1% NaOH, and the organic layer was MgSO. After drying to 4 , the solvent was removed using a rotary evaporator, and recrystallized with ethyl acetate and methylene chloride to obtain 35 g of a white solid having a yield of 77%.
1H-NMR(d,ppm) CDCl3 : 1.37(t,3H), 2.34(s,3H), 2.48(s,3H), 4.14(s,2H), 4.51(q,2H), 7.14~7.16(m,2H), 7.34~7.36(m,2H), 7.40(m,2H), 7.52~7.66(m,4H), 7.83(d,1H), 7.98(d,1H), 8.65(s,1H), 8.74(s1H)
1 H-NMR (d, ppm) CDCl 3 : 1.37 (t, 3H), 2.34 (s, 3H), 2.48 (s, 3H), 4.14 (s, 2H), 4.51 (q, 2H), 7.14 ~ 7.16 (m, 2H), 7.34 ~ 7.36 (m, 2H), 7.40 (m, 2H), 7.52 ~ 7.66 (m, 4H), 7.83 (d, 1H), 7.98 (d, 1H), 8.65 (s, 1H ), 8.74 (s1H)
3단계: (E)-1-(9-Step 3: (E) -1- (9- ethylethyl -6-(2--6- (2- methylbenzoylmethylbenzoyl )-9H-) -9H- carbazolcarbazol -3--3- ylyl )-2-()-2-( hydroxyhydroxy imino)-2-(o-tolyl)ethanone의 합성 Synthesis of imino) -2- (o-tolyl) ethanone
반응기에 180mL의 디메틸포름아마이드을 넣고 상기 2 단계에서 수득한 화합물 30g을 첨가하여 녹였다. 반응물의 온도를 15℃에서 소듐메톡사이드 1.82g을 천천히 첨가하였다. 이 반응물에 이소펜틸니트리트 8.13g을 내부온도 15℃로 유지하면서 천천히 적가하였다. 그 후 25℃까지 승온한 후 8시간 교반하였다. 이 반응물에 용매 에틸아세테이트 200mL와 증류수 200mL를 첨가하여 수세하였다. 2회 추가 수세하여 디메틸포름아마이드를 제거한 후 포화 탄산칼슘으로 중화 세척한 후 유기층을 MgSO4로 건조시킨 후 감압 증류하여 액상의 화합물을 얻었다. 이 액상의 화합물에 메탄올과 메틸렌클로라이드 가하여 재결정하였다. 옅은 노란색의 결정 20g을 얻었으며, 수율은 63%였다.180 mL of dimethylformamide was added to the reactor, and 30 g of the compound obtained in step 2 was added to dissolve it. The temperature of the reaction was slowly added 1.82 g of sodium methoxide at 15 ° C. To the reaction was slowly added dropwise 8.13 g of isopentyl nitrite while maintaining the internal temperature at 15 ° C. Then, it heated up to 25 degreeC and stirred for 8 hours. 200 mL of solvent ethyl acetate and 200 mL of distilled water were added to the reaction product, and the resultant was washed with water. After further washing with water twice to remove dimethylformamide, and neutralized and washed with saturated calcium carbonate, the organic layer was dried over MgSO 4 and distilled under reduced pressure to obtain a liquid compound. Methanol and methylene chloride were added to this liquid compound to recrystallize. 20 g of pale yellow crystals were obtained, yield 63%.
1H-NMR(d,ppm) DMSOd6 : 1.29(t,3H), 2.44(s,6H), 4.53(q,2H), 7.14~7.16(m,2H), 7.34~7.36(m,2H), 7.40(m,2H), 7.52~7.66(m,4H), 7.83(d,1H), 7.98(d,1H), 8.60(s,1H), 8.74(s1H), 12.5(s, 1H, -OH)
1 H-NMR (d, ppm) DMSOd 6 : 1.29 (t, 3H), 2.44 (s, 6H), 4.53 (q, 2H), 7.14 ~ 7.16 (m, 2H), 7.34 ~ 7.36 (m, 2H) , 7.40 (m, 2H), 7.52 ~ 7.66 (m, 4H), 7.83 (d, 1H), 7.98 (d, 1H), 8.60 (s, 1H), 8.74 (s1H), 12.5 (s, 1H,- OH)
4 단계: (E)-2-(acetoxyimino)-1-(9-ethyl-6-(2-methylbenzoyl)-9H- carbazol -3-yl)-2-(o-tolyl)ethanoneStep 4: (E) -2- (acetoxyimino) -1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (o-tolyl) ethanone
질소분위기 하에서 내부온도를 0℃ 이하로 내리고, 상기 3 단계에서 수득한 화합물 20g, 메틸렌클로라이드 120mL와 트리에틸렌아민 4.40g을 첨가하고 아세틸 클로라이드 3.42g을 메틸렌클로라이드 10mL에 용해한 용액을 천천히 가하였다. 내부온도를 10℃로 올린 다음, 3시간 동안 교반하였다. 반응용액에 물을 여러 번 첨가하여 유기층을 씻어주고, 감압 증류하여 얻어진 고체 화합물을 에틸아세테이트와 메틸렌클로라이드을 가하여 재결정하였다. 여과하여 엷은 노란색 고체를 수율 78%, 17g을 얻었다. 상기 옅은 노란색 결정은 목적물인 화합물(화학식 3)임이 확인되었다. 분석결과를 이하에 정리하였다.Under a nitrogen atmosphere, the internal temperature was lowered to 0 ° C., 20 g of the compound obtained in step 3, 120 mL of methylene chloride and 4.40 g of triethyleneamine were added, and a solution of 3.42 g of acetyl chloride in 10 mL of methylene chloride was slowly added. The internal temperature was raised to 10 DEG C, and the mixture was stirred for 3 hours. Water was added to the reaction solution several times to wash the organic layer, and the solid compound obtained by distillation under reduced pressure was recrystallized by adding ethyl acetate and methylene chloride. Filtration gave a pale yellow solid, yield 78%, 17g. It was confirmed that the pale yellow crystals were the target compound (Formula 3). The results of the analysis are summarized below.
<분석결과><Analysis Result>
(1) 융점 : 172.8℃(1) Melting Point: 172.8 ℃
(2)1H-NMR(d,ppm) CDCl3 : 1.29(t,3H), 2.28(s,3H), 2.48(s,6H), 4.53(q,2H), 7.14~7.16(m,2H), 7.34~7.36(m,2H), 7.40(m,2H), 7.52~7.66(m,4H), 7.83(d,1H), 7.98(d,1H), 8.65(s,1H), 8.74(s1H)(2) 1 H-NMR (d, ppm) CDCl 3 : 1.29 (t, 3H), 2.28 (s, 3H), 2.48 (s, 6H), 4.53 (q, 2H), 7.14 ~ 7.16 (m, 2H ), 7.34-7.36 (m, 2H), 7.40 (m, 2H), 7.52-7.62 (m, 4H), 7.83 (d, 1H), 7.98 (d, 1H), 8.65 (s, 1H), 8.74 ( s1H)
(3) UV스펙트럼 측정 (메틸렌클로라이드)(3) UV spectrum measurement (methylene chloride)
λmax:242, 332
λmax: 242, 332
[실시예 2][Example 2]
1 단계: 2-(o-Step 1: 2- (o- tolyltolyl )) acetylacetyl chloridechloride 의 합성Synthesis of
실시예 1의 1 단계와 동일한 방법으로 2-(o-tolyl)acetyl chloride을 합성하였다.
2- (o-tolyl) acetyl chloride was synthesized in the same manner as in step 1 of Example 1.
2 단계: 1-(9-Step 2: 1- (9- ethylethyl -6-(-6- ( thiophenethiophene -2--2- carbonylcarbonyl )-9H-) -9H- carbazolcarbazol -3--3- ylyl )- 2- (o-)-2- (o- tolyltolyl ) ) ethanoneethanone 의 합성Synthesis of
질소 분위기하에서 N-에틸카바졸 30.0g과 건조된 CH2Cl2 180ml을 가하여 녹였다. 반응물을 0℃로 냉각한 후 AlCl3 21.1g을 천천히 투입하였다. 여기에 2-thyonyl chloride 23.19g 을 내부온도 5℃ 이하에서 천천히 적가하였다. 반응 온도를 상온으로 하여 5시간 정도 교반 후 내부 온도를 0℃ 이하로 내리고 AlCl3 21.1g을 천천히 투입하였다. 이 반응물에 2-(o-tolyl)acetyl chloride 26.68g 을 내부온도 5℃ 이하에서 천천히 적가하였다. 반응 온도를 상온으로 하여 8시간 정도 교반 후 내부 온도를 0℃ 이하로 내리고, 얼음물 500ml에 반응기의 용액을 천천히 가하고 1시간 교반 후 층분리 하고 다시 1% NaOH 500ml로 중화, 세척한 후 유기층을 MgSO4로 건조시킨 후 회전증발기로 용매를 제거하여 메탄올과 메틸렌클로라이드로 재결정하여 수율 76%의 옅은 노란색 고체 51g을 얻었다. 30.0 g of N-ethylcarbazole and 180 ml of dried CH 2 Cl 2 were added and dissolved in a nitrogen atmosphere. After cooling the reaction to 0 ℃ AlCl 3 21.1 g was slowly added. 23.19 g of 2-thyonyl chloride was slowly added dropwise at 5 ° C. or lower. After stirring the reaction temperature at room temperature for about 5 hours, the internal temperature was lowered to 0 ° C. or lower, and AlCl 3 21.1 g was slowly added. 26.68 g of 2- (o-tolyl) acetyl chloride was slowly added dropwise to the reaction at an internal temperature of 5 ° C or lower. After stirring the reaction temperature at room temperature for about 8 hours, the internal temperature was lowered to 0 ° C. or lower, the solution of the reactor was slowly added to 500 ml of ice water, stirred for 1 hour, the layers were separated, neutralized and washed with 500 ml of 1% NaOH, and the organic layer was MgSO. After drying to 4 , the solvent was removed using a rotary evaporator and recrystallized with methanol and methylene chloride to give 51 g of a pale yellow solid having a yield of 76%.
1H-NMR(d,ppm) CDCl3 : 1.28(t,3H), 2.32(s,3H), 4.16(s,2H), 4.53(q,2H), 7.14(m,1H), 7.27(t,1H), 7.34(d,1H), 7.42(m,2H), 7.61~7.66(m,2H), 7.92(d,1H), 7.98(d,1H), 8.13(d,1H), 8.64(s,1H), 8.84(s,1H)
1 H-NMR (d, ppm) CDCl 3 : 1.28 (t, 3H), 2.32 (s, 3H), 4.16 (s, 2H), 4.53 (q, 2H), 7.14 (m, 1H), 7.27 (t , 1H), 7.34 (d, 1H), 7.42 (m, 2H), 7.61 ~ 7.66 (m, 2H), 7.92 (d, 1H), 7.98 (d, 1H), 8.13 (d, 1H), 8.64 ( s, 1H), 8.84 (s, 1H)
3 단계: (E)-1-(9-Step 3: (E) -1- (9- ethylethyl -6-(-6- ( thiophenethiophene -2--2- carbonylcarbonyl )-9H-) -9H- carbazolcarbazol -3- -3- ylyl )-2- ()-2- ( hydroxyiminohydroxyimino )-2-(o-tolyl)ethanone의 합성Synthesis of) -2- (o-tolyl) ethanone
반응기에 180mL의 디메틸포름아마이드을 넣고 상기 2 단계에서 수득한 화합물 40g을 첨가하여 녹였다. 반응물의 온도를 15℃에서 소듐메톡사이드 2.46g을 천천히 첨가하였다. 이 반응물에 이소펜틸니트리트 11.03g을 내부 온도 15℃로 유지하면서 천천히 적가하였다. 적가 후 25℃까지 승온 한 후 8시간 교반하였다. 이 반응물에 용매 에틸아세테이트 200mL와 증류수 200mL를 첨가하여 수세하였다. 2회 추가 수세하여 디메틸포름아마이드를 제거한 후 포화 탄산칼슘으로 중화 세척한 후 유기층을 MgSO4로 건조시킨 후 감압 증류하여 액상의 화합물을 얻었다. 이 액상의 화합물에 에탄올과 메틸렌클로라이드 가하여 재결정하였다. 노란색의 결정 35g을 얻었으며, 수율은 82%였다.180 mL of dimethylformamide was added to the reactor, and 40 g of the compound obtained in step 2 was added and dissolved. The temperature of the reaction was slowly added 2.46 g of sodium methoxide at 15 ° C. 11.03 g of isopentylnitrite was slowly added dropwise to the reaction while maintaining the internal temperature at 15 ° C. After dropping, the mixture was heated up to 25 ° C and stirred for 8 hours. 200 mL of solvent ethyl acetate and 200 mL of distilled water were added to the reaction product, and the resultant was washed with water. After further washing with water twice to remove dimethylformamide, and neutralized and washed with saturated calcium carbonate, the organic layer was dried over MgSO 4 and distilled under reduced pressure to obtain a liquid compound. Ethanol and methylene chloride were added to this liquid compound to effect recrystallization. 35g of yellow crystals were obtained, and the yield was 82%.
1H-NMR(d,ppm) DMSOd6 : 1.30(t,3H), 2.46(s,3H), 4.53(q,2H), 7.23~7.27(m,4H), 7.56(d,1H), 7.73(m,2H), 7.92(d,1H), 7.98(d,1H), 8.06(d,1H), 8.14(d,1H), 8.62(s,1H), 8.85(s,1H), 12.1(s, 1H, -OH)
1 H-NMR (d, ppm) DMSOd 6 : 1.30 (t, 3H), 2.46 (s, 3H), 4.53 (q, 2H), 7.23 ~ 7.27 (m, 4H), 7.56 (d, 1H), 7.73 (m, 2H), 7.92 (d, 1H), 7.98 (d, 1H), 8.06 (d, 1H), 8.14 (d, 1H), 8.62 (s, 1H), 8.85 (s, 1H), 12.1 ( s, 1H, -OH)
4 단계: (E)-2-(Step 4: (E) -2- ( acetoxyiminoacetoxyimino )-1-(9-) -1- (9- ethylethyl -6-(-6- ( thiophenethiophene -2 --2 - carbonylcarbonyl )- 9H-)-9H- carbazolcarbazol -3--3- ylyl )-2-(o-) -2- (o- tolyltolyl )) ethanoneethanone
질소분위기 하에서 내부온도를 0℃ 이하로 내리고, 상기 3 단계에서 수득한 화합물 30g, 메틸렌 클로라이드 180mL와 트리 에틸렌 아민 6.70g을 첨가하고 아세틸 클로라이드 5.20g을 메틸렌 클로라이드 10mL에 용해한 용액을 천천히 가하였다.내부 온도를 10℃로 올린 다음, 4시간 동안 교반하였다. 반응용액에 물을 여러 번 첨가하여 유기층을 씻어주고, 감압 증류하여 얻어진 고체 화합물을 에틸아세테이트와 메탄올을 가하여 재결정하였다. 여과하여 엷은 노란색 고체를 수율 80%, 26g을 얻었다. 상기 옅은 노란색 결정은 목적한 화학식 9의 화합물임을 확인하였으며, 분석결과는 하기와 같다.Under nitrogen atmosphere, the internal temperature was lowered to 0 ° C. or lower, and 30 g of the compound obtained in step 3, 180 mL of methylene chloride and 6.70 g of triethylene amine were added, and a solution of 5.20 g of acetyl chloride dissolved in 10 mL of methylene chloride was slowly added. The temperature was raised to 10 ° C. and then stirred for 4 hours. Water was added to the reaction solution several times to wash the organic layer, and the solid compound obtained by distillation under reduced pressure was recrystallized by adding ethyl acetate and methanol. Filtration gave a pale yellow solid, yield 80%, and 26 g. The pale yellow crystals were identified to be the compound of formula 9, and the analysis results are as follows.
<분석결과><Analysis Result>
(1) 융점 : 176.4℃(1) Melting Point: 176.4 ℃
(2)1H-NMR(d,ppm) CDCl3 : 1.29(t,3H),2.27(s,3H),2.48(s,3H),4.53(q,2H), 7.23~7.28(m,4H),7.56(d,1H),7.72(m,2H),7.92(d,1H),8.01(d,1H),8.10(m,2H),8.60(s,1H),8.85(s,1H)(2) 1 H-NMR (d, ppm) CDCl 3 : 1.29 (t, 3H), 2.27 (s, 3H), 2.48 (s, 3H), 4.53 (q, 2H), 7.23 ~ 7.28 (m, 4H ), 7.56 (d, 1H), 7.72 (m, 2H), 7.92 (d, 1H), 8.01 (d, 1H), 8.10 (m, 2H), 8.60 (s, 1H), 8.85 (s, 1H)
(3) UV스펙트럼 측정 (메틸렌클로라이드)(3) UV spectrum measurement (methylene chloride)
λmax:278, 334
λmax: 278, 334
[실시예 3][Example 3]
1 단계: 2-(o-Step 1: 2- (o- tolyltolyl )) acetylacetyl chloridechloride 의 합성Synthesis of
실시예 1의 1 단계와 동일한 방법으로 2-(o-tolyl)acetyl chloride을 합성하였다. 2- (o-tolyl) acetyl chloride was synthesized in the same manner as in step 1 of Example 1.
2 단계: 1-(4-(Step 2: 1- (4- ( phenylthio메틸THIO )) phenylphenyl )-2-o-) -2-o- tolylethanonetolylethanone 의 합성Synthesis of
질소 분위기하에서 바이페닐설파이드 90.0g과 건조된 CH2Cl2 540ml을 가하여 녹였다. 반응물을 0℃로 냉각한 후 AlCl3 66.34g을 천천히 투입하였다. 여기에 2-(o-tolyl)acetyl chloride 83.9g 을 내부온도 5℃이하에서 천천히 적가하였다. 반응 온도를 상온으로 하여 5시간 정도 교반 후 내부 온도를 0℃ 이하로 내리고, 얼음물 700ml에 반응기의 용액을 천천히 가하고 1시간 교반 후 층분리 하고 다시 1% NaOH 700ml로 중화, 세척한 후 유기층을 MgSO4로 건조시킨 후 회전증발기로 용매를 제거하여 에틸아세테이트로 재결정하여 수율 91%의 흰색 고체 140g을 얻었다. 90.0 g of biphenylsulfide and dried CH 2 Cl 2 under nitrogen atmosphere 540 ml was added to dissolve. After cooling the reaction to 0 ℃ AlCl 3 66.34 g was slowly added. 83.9g of 2- (o-tolyl) acetyl chloride was slowly added dropwise at 5 ℃ or lower. After stirring the reaction temperature at room temperature for about 5 hours, the internal temperature was lowered to 0 ° C. or lower, the solution of the reactor was slowly added to 700 ml of ice water, stirred for 1 hour, the layers were separated, neutralized and washed with 700 ml of 1% NaOH, and the organic layer was MgSO. After drying to 4 , the solvent was removed using a rotary evaporator and recrystallized with ethyl acetate to obtain 140 g of a white solid having a yield of 91%.
1H-NMR(d,ppm) CDCl3 : 2.23(s,3H), 4.22(s,2H), 7.08~7.21(m,7H), 7.39~7.40(m,2H), 7.49~7.51(m,2H), 7.87(d,2H)
1 H-NMR (d, ppm) CDCl 3 : 2.23 (s, 3H), 4.22 (s, 2H), 7.08 ~ 7.21 (m, 7H), 7.39 ~ 7.40 (m, 2H), 7.49 ~ 7.51 (m, 2H), 7.87 (d, 2H)
3 단계: (E)-2-(Step 3: (E) -2- ( hydroxyiminohydroxyimino )-1-(4-() -1- (4- ( phenylthio메틸THIO )) phenylphenyl )-2-o-) -2-o- tolylethanonetolylethanone 의 합성Synthesis of
반응기에 540mL의 디메틸포름아마이드을 넣고 상기 2 단계에서 수득한 화합물 90g을 첨가하여 녹였다. 반응물의 온도를 15℃에서 소듐메톡사이드 7.63g을 천천히 첨가하였다. 이 반응물에 이소펜틸니트리트 36.42g을 내부온도 15℃로 유지하면서 천천히 적가하였다. 적가 후 25℃까지 승온 한 후 8시간 교반하였다. 이 반응물에 용매 에틸아세테이트 700mL와 증류수 700mL를 첨가하여 수세하였다. 2회 추가 수세하여 디메틸포름아마이드를 제거한 후 포화 탄산칼슘으로 중화 세척한 후 유기층을 MgSO4로 건조시킨 후 감압 증류하여 액상의 화합물을 얻었다. 이 액상의 화합물에 헥산과 메틸렌클로라이드 가하여 재결정하였다. 옅은 노란색의 결정 70g을 얻었으며, 수율은 71%였다.540 mL of dimethylformamide was added to the reactor, and 90 g of the compound obtained in step 2 was added to dissolve it. 7.63 g of sodium methoxide was slowly added at 15 ° C. 36.42 g of isopentyl nitrile was slowly added dropwise to the reaction while maintaining the internal temperature at 15 占 폚. After dropping, the mixture was heated up to 25 ° C and stirred for 8 hours. 700 mL of solvent ethyl acetate and 700 mL of distilled water were added to the reaction product, and the resultant was washed with water. After further washing with water twice to remove dimethylformamide, and neutralized and washed with saturated calcium carbonate, the organic layer was dried over MgSO 4 and distilled under reduced pressure to obtain a liquid compound. Hexane and methylene chloride were added to this liquid compound to recrystallize. 70 g of pale yellow crystals were obtained, with a yield of 71%.
1H-NMR(d,ppm) CDCl3 : 2.25(s,3H), 2.53(s,1H,-OH), 7.19~7.32(m,6H), 7.38~7.42(m,3H), 7.51~7.53(m,2H), 7.95(d,2H)
1 H-NMR (d, ppm) CDCl 3 : 2.25 (s, 3H), 2.53 (s, 1H, -OH), 7.19 ~ 7.32 (m, 6H), 7.38 ~ 7.42 (m, 3H), 7.51 ~ 7.53 (m, 2H), 7.95 (d, 2H)
4 단계: (E)-2-(Step 4: (E) -2- ( acetoxyiminoacetoxyimino )-1-(4-() -1- (4- ( phenylthio메틸THIO )) phenylphenyl )-2-o- ) -2-o- tolylethanonetolylethanone 의 합성Synthesis of
질소분위기 하에서 내부온도를 0℃ 이하로 내리고, 상기 3 단계에서 수득한 화합물 50g, 메틸렌클로라이드 300mL와 트리에틸렌아민 15.0g을 첨가하고 아세틸 클로라이드 11.6g을 메틸렌클로라이드 20mL에 용해한 용액을 천천히 가하였다. 내부 온도를 10℃로 올린 다음, 3시간 동안 교반하였다. 반응용액에 물을 여러 번 첨가하여 유기층을 씻어주고, 감압 증류하여 얻어진 고체 화합물을 석유에테르와 메틸렌클로라이드을 가하여 재결정하였다. 여과하여 엷은 노란색 고체를 수율 89%, 50g을 얻었다. 상기 옅은 노란색 결정은 목적물인 화학식 15의 화합물임을 확인하였으며, 분석결과는 하기와 같다.Under a nitrogen atmosphere, the internal temperature was lowered to 0 ° C. or less, 50 g of the compound obtained in step 3, 300 mL of methylene chloride and 15.0 g of triethyleneamine were added, and a solution of 11.6 g of acetyl chloride dissolved in 20 mL of methylene chloride was slowly added. The internal temperature was raised to 10 ° C. and then stirred for 3 hours. Water was added to the reaction solution several times to wash the organic layer, and the solid compound obtained by distillation under reduced pressure was recrystallized by adding petroleum ether and methylene chloride. Filtration gave a pale yellow solid, yield 89%, and 50 g. The pale yellow crystals were identified to be the compound of formula 15 as a target, and the analysis results are as follows.
<분석결과><Analysis Result>
(1) 융점 : 95.1℃(1) Melting Point: 95.1 ℃
(2)1H-NMR(d,ppm) CDCl3 : 2.09(s,3H), 2.26(s,3H), 7.17~7.27(m,5H), 7.32(t,1H), 7.42(t,3H), 7.53~7.55(m,2H), 8.07(d,2H)(2) 1 H-NMR (d, ppm) CDCl 3 : 2.09 (s, 3H), 2.26 (s, 3H), 7.17 ~ 7.27 (m, 5H), 7.32 (t, 1H), 7.42 (t, 3H ), 7.53-7.55 (m, 2H), 8.07 (d, 2H)
(3) UV스펙트럼 측정 (메틸렌클로라이드)(3) UV spectrum measurement (methylene chloride)
λmax:248, 334
λmax: 248, 334
[실시예 4]Example 4
1 단계: 2-(o-Step 1: 2- (o- tolyltolyl )) acetylacetyl chloridechloride 의 합성Synthesis of
실시예 1의 1 단계와 동일한 방법으로 2-(o-tolyl)acetyl chloride을 합성하였다.
2- (o-tolyl) acetyl chloride was synthesized in the same manner as in step 1 of Example 1.
2 단계: 1-(4-((4-(2-Step 2: 1- (4-((4- (2- methylbenzoylmethylbenzoyl )) phenylphenyl )) thiothio )) phenylphenyl )-2-(o-) -2- (o- tolyltolyl ) ) ethanoneethanone 의 합성Synthesis of
질소 분위기하에서 바이페닐설파이드 50.0g과 건조된 CH2Cl2 300ml을 가하여 녹였다. 반응물을 0℃로 냉각한 후 AlCl3 36.87g을 천천히 투입하였다. 여기에 o-toluyl chloride 42.74g 을 메틸렌클로라이드 80mL에 희석하여 천천히 적가하였다. 반응 온도를 상온으로 하여 8시간 교반 후 내부 온도를 0℃ 이하로 내리고 AlCl3 36.87g을 천천히 투입하였다. 이 반응물에 2-(o-tolyl)acetyl chloride 46.62g 을 메틸렌클로라이드 80mL에 희석하여 내부온도 5℃이하에서 천천히 적가하였다. 반응 온도를 상온으로 하여 5시간 정도 교반 후 내부 온도를 0℃ 이하로 내리고, 얼음물 500ml에 반응기의 용액을 천천히 가하고 1시간 교반 후 층분리 하고 다시 1% NaOH 500ml로 중화, 세척한 후 유기층을 MgSO4로 건조시킨 후 회전증발기로 용매를 제거하여 메탄올로 재결정하여 수율 64%의 흰색 고체 75g을 얻었다. 50.0 g of biphenylsulfide and dried CH 2 Cl 2 under nitrogen atmosphere 300 ml was added to dissolve it. After cooling the reaction to 0 ℃ AlCl 3 36.87 g was slowly added. 42.74 g of o-toluyl chloride was diluted in 80 mL of methylene chloride and slowly added dropwise thereto. After stirring the reaction temperature at room temperature for 8 hours, the internal temperature was lowered to 0 ° C. or lower, and the AlCl 3 36.87 g was slowly added. 46.62 g of 2- (o-tolyl) acetyl chloride was diluted in 80 mL of methylene chloride and slowly added dropwise thereto at an internal temperature of 5 ° C or lower. After stirring for 5 hours at room temperature, the internal temperature was lowered to 0 ° C. or lower, the solution of the reactor was slowly added to 500 ml of ice water, stirred for 1 hour, the layers were separated, neutralized and washed with 500 ml of 1% NaOH, and then the organic layer was MgSO. After drying to 4 , the solvent was removed using a rotary evaporator and recrystallized with methanol to obtain 75 g of a white solid having a yield of 64%.
1H-NMR(d,ppm) CDCl3 : 2.34(s,3H), 2.48(s,3H), 4.14(s,2H), 7.15(m,2H), 7.34~7.40(m,4H), 7.51~7.58(m,7H), 7.66(d,1H), 7.74(d,2H)
1 H-NMR (d, ppm) CDCl 3 : 2.34 (s, 3H), 2.48 (s, 3H), 4.14 (s, 2H), 7.15 (m, 2H), 7.34 ~ 7.40 (m, 4H), 7.51 ~ 7.58 (m, 7H), 7.66 (d, 1H), 7.74 (d, 2H)
3 단계: 1-(4-((4-(2-Step 3: 1- (4-((4- (2- methylbenzoylmethylbenzoyl )) phenylphenyl )) thiothio )) phenylphenyl )-2-(o-) -2- (o- tolyltolyl )) ethaneethane -1,2--1,2- dionedione 의 합성Synthesis of
반응기에 300mL의 디메틸포름아마이드을 넣고 상기 2 단계에서 얻은 화합물 50g을 첨가하여 녹였다. 반응물의 온도를 15℃에서 소듐메톡사이드 3.09g을 천천히 첨가하였다. 이 반응물에 이소펜틸니트리트 13.82g을 내부 온도 15℃로 유지하면서 천천히 적가하였다. 적가 후 25℃까지 승온한 후 8시간 교반한다. 이 반응물에 용매 에틸아세테이트 400mL와 증류수 400mL를 첨가하여 수세하였다. 2회 추가 수세하여 디메틸포름아마이드를 제거한 후 포화 탄산칼슘으로 중화 세척한 후 유기층을 MgSO4로 건조시킨 후 감압 증류하여 액상의 화합물을 얻었다. 이 액상의 화합물에 헥산과 메탄올 가하여 재결정하였다. 옅은 노란색의 결정 35g을 얻었으며, 수율은 66%였다.300 mL of dimethylformamide was added to the reactor, and 50 g of the compound obtained in step 2 was added to dissolve it. 3.09 g of sodium methoxide was slowly added at 15 ° C. 13.82 g of isopentyl nitrile was slowly added dropwise to the reaction while maintaining the internal temperature at 15 ° C. After dropping, the mixture was heated up to 25 ° C and stirred for 8 hours. 400 mL of solvent ethyl acetate and 400 mL of distilled water were added to the reaction product, and the resultant was washed with water. After further washing with water twice to remove dimethylformamide, and neutralized and washed with saturated calcium carbonate, the organic layer was dried over MgSO 4 and distilled under reduced pressure to obtain a liquid compound. Hexane and methanol were added to this liquid compound to recrystallize. 35 g of pale yellow crystals were obtained, yielding 66%.
1H-NMR(d,ppm) CDCl3 : 2.48(s,6H), 2.00(s,1H,-OH), 7.16~7.36(m,5H), 7.51~7.69(m,10H) 1 H-NMR (d, ppm) CDCl 3 : 2.48 (s, 6H), 2.00 (s, 1H, -OH), 7.16 to 7.36 (m, 5H), 7.51 to 7.69 (m, 10H)
4 단계: (Z)-2-(Step 4: (Z) -2- ( acetoxyiminoacetoxyimino )-1-(4-((4-(2-) -1- (4-((4- (2- methylbenzoylmethylbenzoyl )) phenylphenyl ) ) thiothio )) phenylphenyl )-2-(o-tolyl)ethanone의 합성Synthesis of) -2- (o-tolyl) ethanone
질소분위기 하에서 내부온도를 0℃ 이하로 내리고, 상기 3 단계에서 얻은 화합물 30g, 메틸렌 클로라이드 180mL와 트리 에틸렌 아민 6.72g을 첨가하고 아세틸 클로라이드 5.21g을 메틸렌 클로라이드 10mL에 용해한 용액을 천천히 가하였다. 내부온도를 10℃로 올린 다음, 3시간 동안 교반하였다. 반응용액에 물을 여러 번 첨가하여 유기층을 씻어주고, 감압 증류하여 얻어진 고체 화합물을 노르말헥산과 메틸렌 클로라이드을 가하여 재결정하였다. 여과하여 엷은 노란색 고체를 수율 79%, 26g을 얻었다. 상기 옅은 노란색 결정은 목적한 화합물인 화학식 21로 표현되는 화합물임을 확인하였으며, 이의 분석결과는 하기와 같다.Under a nitrogen atmosphere, the internal temperature was lowered to 0 ° C., 30 g of the compound obtained in step 3, 180 mL of methylene chloride and 6.72 g of triethyleneamine were added, and a solution of 5.21 g of acetyl chloride in 10 mL of methylene chloride was slowly added. The internal temperature was raised to 10 DEG C, and the mixture was stirred for 3 hours. Water was added to the reaction solution several times to wash the organic layer, and the solid compound obtained by distillation under reduced pressure was recrystallized by adding normal hexane and methylene chloride. Filtration gave a pale yellow solid, yield 79%, 26 g. The pale yellow crystals were confirmed to be the compound represented by Formula 21, which is a target compound, and the analysis results thereof are as follows.
<분석결과><Analysis Result>
(1) 융점 : 126.1℃(1) Melting Point: 126.1 ℃
(2)1H-NMR(d,ppm) CDCl3 : 2.27(s,3H),2.45(s,6H),7.16~77.36(m,5H), 7.51~7.71(m,11H)(2) 1 H-NMR (d, ppm) CDCl 3 : 2.27 (s, 3H), 2.45 (s, 6H), 7.16 ~ 77.36 (m, 5H), 7.51 ~ 7.71 (m, 11H)
(3) UV스펙트럼 측정 (메틸렌클로라이드)(3) UV spectrum measurement (methylene chloride)
λmax:249, 336
λmax: 249, 336
상기 실시예 1 내지 실시예 4와 같은 방법으로 다음 표 1과 같이 본원 발명에 따른 알파키토옥심에스테르 화합물을 합성하였다.
In the same manner as in Example 1 to Example 4, an alpha chitooxime ester compound according to the present invention was synthesized as shown in Table 1 below.
No.Example
No.
-S-
[실시예 11][Example 11]
투명 레지스트 조성물의 제조Preparation of Transparent Resist Composition
아크릴계 바인더수지 30g, 광중합 단량체(디펜타에리스리톨핵사아크릴레이트, Nihon Kayaku Kogyou사제, KAYARAD DPHA)30g, 상기 실시예 1에서 얻은 화합물 1.0g 및 PGMEA 200g, 계면활성제 (3M사제, FC-430) 500ppm을 포함하는 투명 감광성 레지스트 조성물을 제조하였다.
30 g of an acrylic binder resin, 30 g of a photopolymerizable monomer (Dipentaerythritol nucleated acrylate, manufactured by Nihon Kayaku Kogyou, KAYARAD DPHA), 1.0 g of the compound obtained in Example 1, 200 g of PGMEA, and 500 ppm of a surfactant (manufactured by 3M, FC-430) were prepared. A transparent photosensitive resist composition was prepared.
[실시예 12][Example 12]
블랙 레지스트 조성물의 제조Preparation of Black Resist Composition
카본블랙 30g, 티탄블랙 20g, 폴리에스테르바인더수지, 광중합 단량체(디펜타에리스리톨핵사아크릴레이트, Nihon Kayaku Kogyou사제, KAYARAD DPHA)10g, 상기 실시예 1에서 얻은 화합물 2.5g 및 PGMEA 300g, 계면활성제 (3M사제, FC-430) 500ppm을 포함하는 블랙 감광성 레지스트 조성물을 제조하였다.
Carbon Black 30g, Titanium Black 20g, Polyester Binder Resin, Photopolymerization Monomer (Dipentaerythritol Nucleoacrylate, 10g from Nihon Kayaku Kogyou, KAYARAD DPHA), 2.5g Compound P obtained in Example 1 and 300g PGMEA, Surfactant (3M Corporation, FC-430) to prepare a black photosensitive resist composition comprising 500ppm.
[실시예 13][Example 13]
레드 레지스트 조성물의 제조Preparation of Red Resist Composition
아크릴계공중합체 10g에 대해 광중합 단량체(디펜타에리스리톨핵사아크릴레이트, Nihon Kayaku Kogyou사제, KAYARAD DPHA)10g, 실시예 1에서 얻은 화합물 1.5g, 피그먼트레드 Red 177: Ciba社 CROMOPHTALRED A2B 10g 및 프로필렌글리콜모노에틸에테르 200g을 넣고 계면활성제 (DisperBYK-111) 500ppm을 포함하는 블랙 감광성 레지스트 조성물을 제조하였다.
10 g of photopolymerization monomer (Dipentaerythritol nucleated acrylate, manufactured by Nihon Kayaku Kogyou, KAYARAD DPHA), 10 g of the compound obtained in Example 1, Pigment Red Red 177: Ciba CROMOPHTALRED A2B 10 g and propylene glycol mono to 10 g of acrylic copolymer 200 g of ethyl ether was added thereto to prepare a black photosensitive resist composition including 500 ppm of a surfactant (DisperBYK-111).
[실시예 14]Example 14
투명 레지스트 조성물의 제조Preparation of Transparent Resist Composition
실시예 1에서 얻은 화합물 대신 실시예 2에서 얻은 화합물 1.0g을 첨가하는 것을 제외하고는 실시예 11과 동일한 조건으로 투명 감광성 레지스트 조성물을 제조하였다.
A transparent photosensitive resist composition was prepared under the same conditions as in Example 11 except that 1.0 g of the compound obtained in Example 2 was added instead of the compound obtained in Example 1.
[실시예 15]Example 15
블랙 레지스트 조성물의 제조Preparation of Black Resist Composition
실시예 1에서 얻은 화합물 대신 실시예 2에서 얻은 화합물 2.5g을 첨가하는 것을 제외하고는 실시예 12와 동일한 조건으로 블랙 감광성 레지스트 조성물을 제조하였다.
A black photosensitive resist composition was prepared under the same conditions as in Example 12, except that 2.5 g of the compound obtained in Example 2 was added instead of the compound obtained in Example 1.
[실시예 16][Example 16]
레드 레지스트 조성물의 제조Preparation of Red Resist Composition
실시예 1에서 얻은 화합물 대신 실시예 2에서 얻은 화합물 1.5g을 첨가하는 것을 제외하고는 실시예 13과 동일한 조건으로 블랙 감광성 레지스트 조성물을 제조하였다.
A black photosensitive resist composition was prepared under the same conditions as in Example 13 except that 1.5 g of the compound obtained in Example 2 was added instead of the compound obtained in Example 1.
[실시예 17]Example 17
투명 레지스트 조성물의 제조Preparation of Transparent Resist Composition
실시예 1에서 얻은 화합물 대신 실시예 3에서 얻은 화합물 1.0g을 첨가하는 것을 제외하고는 실시예 11과 동일한 조건으로 투명 감광성 레지스트 조성물을 제조하였다.
A transparent photosensitive resist composition was prepared under the same conditions as in Example 11 except that 1.0 g of the compound obtained in Example 3 was added instead of the compound obtained in Example 1.
[실시예 18][Example 18]
블랙 레지스트 조성물의 제조Preparation of Black Resist Composition
실시예 1에서 얻은 화합물 대신 실시예 3에서 얻은 화합물 2.5g을 첨가하는 것을 제외하고는 실시예 12와 동일한 조건으로 블랙 감광성 레지스트 조성물을 제조하였다.
A black photosensitive resist composition was prepared under the same conditions as in Example 12, except that 2.5 g of the compound obtained in Example 3 was added instead of the compound obtained in Example 1.
[실시예 19][Example 19]
레드 레지스트 조성물의 제조Preparation of Red Resist Composition
실시예 1에서 얻은 화합물 대신 실시예 3에서 얻은 화합물 1.5g을 첨가하는 것을 제외하고는 실시예 13과 동일한 조건으로 블랙 감광성 레지스트 조성물을 제조하였다.
A black photosensitive resist composition was prepared under the same conditions as in Example 13 except that 1.5 g of the compound obtained in Example 3 was added instead of the compound obtained in Example 1.
[실시예 20][Example 20]
투명 레지스트 조성물의 제조Preparation of Transparent Resist Composition
실시예 1에서 얻은 화합물 대신 실시예 4에서 얻은 화합물 1.0g을 첨가하는 것을 제외하고는 실시예 11과 동일한 조건으로 투명 감광성 레지스트 조성물을 제조하였다.
A transparent photosensitive resist composition was prepared under the same conditions as in Example 11 except that 1.0 g of the compound obtained in Example 4 was added instead of the compound obtained in Example 1.
[실시예 21]Example 21
블랙 레지스트 조성물의 제조Preparation of Black Resist Composition
실시예 1에서 얻은 화합물 대신 실시예 4에서 얻은 화합물 2.5g을 첨가하는 것을 제외하고는 실시예 12와 동일한 조건으로 블랙 감광성 레지스트 조성물을 제조하였다.
A black photosensitive resist composition was prepared under the same conditions as in Example 12 except that 2.5 g of the compound obtained in Example 4 was added instead of the compound obtained in Example 1.
[실시예 22][Example 22]
레드 레지스트 조성물의 제조Preparation of Red Resist Composition
실시예 1에서 얻은 화합물 대신 실시예 4에서 얻은 화합물 1.5g을 첨가하는 것을 제외하고는 실시예 13과 동일한 조건으로 블랙 감광성 레지스트 조성물을 제조하였다.
A black photosensitive resist composition was prepared under the same conditions as in Example 13 except that 1.5 g of the compound obtained in Example 4 was added instead of the compound obtained in Example 1.
비교예Comparative example
본 발명에 따른 알파키토옥심에스테르 화합물과의 특성 비교를 위해 하기 화학식 33 및 34로 표현되는 비교화합물들을 사용하여 감성 레지스트 조성물들을 제조하고 이를 상기 실시예들과 비교 평가하였다.
In order to compare the properties with the alpha chito oxime ester compound according to the present invention, the sensitive resist compositions were prepared using comparative compounds represented by the following Chemical Formulas 33 and 34, and compared with the above examples.
[화학식 33] (33)
[화학식 34] [Formula 34]
[비교예 1]Comparative Example 1
투명 레지스트 조성물의 제조Preparation of Transparent Resist Composition
아크릴계 바인더수지 30g, 광중합 단량체(디펜타에리스리톨핵사아크릴레이트, Nihon Kayaku Kogyou사제, KAYARAD DPHA)30g, 상기 화학식 33으로 표현되는 화합물 1.0g 및 PGMEA 200g, 계면활성제 (3M사제, FC-430) 500ppm을 포함하는 투명 감광성 레지스트 조성물을 제조하였다.
30 g of an acrylic binder resin, 30 g of a photopolymerization monomer (Dipentaerythritol nucleated acrylate, manufactured by Nihon Kayaku Kogyou, KAYARAD DPHA), 1.0 g of compound represented by the above formula (33), and 200 g of PGMEA, surfactant (manufactured by 3M, FC-430) 500 ppm A transparent photosensitive resist composition was prepared.
[비교예 2]Comparative Example 2
블랙 레지스트 조성물의 제조Preparation of Black Resist Composition
카본블랙 30g, 티탄블랙 20g, 폴리에스테르바인더수지, 광중합 단량체(디펜타에리스리톨핵사아크릴레이트, Nihon Kayaku Kogyou사제, KAYARAD DPHA)10g, 상기 화학식 33으로 표현되는 화합물 2.5g 및 PGMEA 300g, 계면활성제 (3M사제, FC-430) 500ppm을 포함하는 블랙 감광성 레지스트 조성물을 제조하였다.
Carbon Black 30g, Titanium Black 20g, Polyester Binder Resin, Photopolymerization Monomer (Dipentaerythritol Nucleoacrylate, manufactured by Nihon Kayaku Kogyou, KAYARAD DPHA) 10g, 2.5g Compound represented by Chemical Formula 33 and PGMEA 300g, Surfactant (3M Corporation, FC-430) to prepare a black photosensitive resist composition comprising 500ppm.
[비교예 3][Comparative Example 3]
레드 레지스트 조성물의 제조Preparation of Red Resist Composition
아크릴계공중합체 10g에 대해 광중합 단량체(디펜타에리스리톨핵사아크릴레이트, Nihon Kayaku Kogyou사제, KAYARAD DPHA)10g, 상기 화학식 33으로 표현되는 화합물 1.5g, 피그먼트레드 Red 177: Ciba社 CROMOPHTALRED A2B 10g 및 프로필렌글리콜모노에틸에테르 200g을 넣고 계면활성제 (DisperBYK-111) 500ppm을 포함하는 블랙 감광성 레지스트 조성물을 제조하였다.
10 g of photopolymerizable monomers (Dipentaerythritol nucleated acrylate, manufactured by Nihon Kayaku Kogyou, KAYARAD DPHA) with respect to 10 g of acrylic copolymer, 1.5 g of the compound represented by the above Chemical Formula 33, Pigment Red Red 177: Ciba CROMOPHTALRED A2B 10 g and propylene glycol 200 g of monoethyl ether was added thereto to prepare a black photosensitive resist composition including 500 ppm of a surfactant (DisperBYK-111).
[비교예 4][Comparative Example 4]
투명 레지스트 조성물의 제조Preparation of Transparent Resist Composition
화학식 33으로 표현되는 화합물 대신 화학식 34로 표현되는 화합물 1.0g을 첨가하는 것을 제외하고는 비교예 1과 동일한 조건으로 투명 감광성 레지스트 조성물을 제조하였다.
A transparent photosensitive resist composition was prepared under the same conditions as in Comparative Example 1 except that 1.0 g of the compound represented by Chemical Formula 34 was added instead of the compound represented by Chemical Formula 33.
[비교예 5][Comparative Example 5]
블랙 레지스트 조성물의 제조Preparation of Black Resist Composition
화학식 33으로 표현되는 화합물 대신 화학식 34로 표현되는 화합물 2.5g을 첨가하는 것을 제외하고는 비교예 2와 동일한 조건으로 블랙 감광성 레지스트 조성물을 제조하였다.
A black photosensitive resist composition was prepared under the same conditions as in Comparative Example 2, except that 2.5 g of the compound represented by Chemical Formula 34 was added instead of the compound represented by Chemical Formula 33.
[비교예 6][Comparative Example 6]
레드 레지스트 조성물의 제조Preparation of Red Resist Composition
화학식 33으로 표현되는 화합물 대신 화학식 34로 표현되는 화합물 1.5g을 첨가하는 것을 제외하고는 비교예 3과 동일한 조건으로 블랙 감광성 레지스트 조성물을 제조하였다.
A black photosensitive resist composition was prepared under the same conditions as in Comparative Example 3 except that 1.5 g of the compound represented by Chemical Formula 34 was added instead of the compound represented by Chemical Formula 33.
물성 평가Property evaluation
상기 실시예 11 내지 22 및 비교예 1 내지 6에서 얻은 감광성 조성물의 평가는 아래와 같이 행하였다. Evaluation of the photosensitive composition obtained in Examples 11-22 and Comparative Examples 1-6 was performed as follows.
상기 감광성 조성물을 스핀코터에 800~900rpm으로 15초 동안 도포한 후 핫플레이트에서 90에서 100초동안 건조하였다. 소정의 마스크를 이용해, 광원으로서 초고압수은램프를 이용해서 노광한 후 0.04% 수산화칼륨용액에 25에서 60초간 스핀 현상한 후 수세하였다. 수세 건조 후, 230에서 40분간 베이크해서 패턴을 얻었다. 얻어진 패턴에 대해서 이하의 평가를 진행하였다. 각 감광성 조성물로 이용한 광중합 개시제와 각종 평가 결과를 표 1에 나타내었다.
The photosensitive composition was applied to the spin coater at 800 to 900 rpm for 15 seconds and then dried in a hot plate for 90 to 100 seconds. After exposure using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, the resultant was spin-developed in 0.04% potassium hydroxide solution for 25 to 60 seconds and washed with water. After washing with water, baking was carried out at 230 for 40 minutes to obtain a pattern. The following evaluation was performed about the obtained pattern. Table 1 shows the photopolymerization initiators used in each photosensitive composition and various evaluation results.
(1) 밀착성 (1) adhesion
JIS D 0202의 시험방법에 따라, 노광현상 후 200에서 30분간 가열한 도막에 격자모양으로 크로서컷을 넣고, 이어서 셀로판테이크에 의해 필링테스트를 행하고, 격자모양의 박리 상태를 관찰하여 평가하였다. 전혀 박리가가 없을 경우 ○, 박리가 인정된 것을 ×로 하였다.
In accordance with the test method of JIS D 0202, a croissant was cut into a lattice shape in a coating film heated for 200 to 30 minutes after exposure development, and then peeling test was performed by cellophane take, and the peeling state of lattice shape was observed and evaluated. When there was no peeling at all, the thing which (circle) and peeling were recognized was made into x.
(2) 내알칼리성(2) alkali resistance
현상 후 230네거 30분간 베이크한 후 도막을 5% NaOH에 24사간, 4% KOH 50에서 10분간, 1% NaOH 80에서 5분간 담근 후 상태를 관찰 하였다. 외관변화도 없고 박리도 없는 경우 ○, 레지스트 들뜸이 보여진 것을 △, 레지스트의 박리가 보여진 것을 ×로 하였다.
After the development, the oven was baked for 30 minutes at 230 neger, and then the film was immersed in 5% NaOH for 24 minutes, 4 minutes in K% 50 for 10 minutes, and 1% in NaOH 80 for 5 minutes. The case where there was no appearance change and no peeling was observed, the case where the resist peeling was observed and the case where peeling of the resist was observed was evaluated as " C ".
(3) 감도 평가(3) sensitivity evaluation
상기 조성된 각각의 감광성 수지 조성물을 스핀코터로 유리기판(삼성코닝사제, Eagle2000)에 도포하고, 핫플레이트로 90도, 1분간 건조했다. 건조 후 촉침식 막두께 측정기 (KLA-Tencor사제, a-step 500)으로 측정하여 얻어진 블랙레지스트 및 투명 네가티브 레지스트의 막두께는 각각 1미크론 및 5미크론이었다. 다음에 이 샘플을 마스크를 통하여 고압수은등으로 노광했다. 이후 농도 0.04% 수산화칼륨 수용액으로 스프레이 현상하여 레지스트 패턴을 얻었다. 40미크론의 마스크 패턴과 같은 치수를 형성할 수 있는 적정 노광량(mJ/sqcm)을 표시하였다. 즉, 노광량이 적은 레지스트는 적은 광에너지로도 화상 형성이 가능하기 때문에 고감도인 것을 나타낸다.
Each of the thus-formed photosensitive resin compositions was applied to a glass substrate (Eagle 2000, manufactured by Samsung Corning Incorporated) with a spin coater and dried at 90 degrees for 1 minute with a hot plate. After drying, the film thicknesses of the black resist and the transparent negative resist obtained by measuring with a tactile film thickness gauge (a-step 500 manufactured by KLA-Tencor) were 1 micron and 5 microns, respectively. This sample was then exposed to a high pressure mercury lamp through a mask. Thereafter, the resultant was spray-developed with 0.04% aqueous potassium hydroxide solution to obtain a resist pattern. (MJ / sqcm) capable of forming the same dimensions as the mask pattern of 40 microns. That is, the resist with a small exposure amount shows high sensitivity since image formation is possible even with a small amount of light energy.
(4) 백화 현상(4) whitening phenomenon
합성된 광개시제를 포함하여 조성된 각각의 감광성 수지 조성물을 스핀코터로 유기기판에 도포하였다. 이때 광개시제의 용해도에 따라 회전 도포시 결정이 생성되어 도포면이 매우 불량한 경우를 X로, 필름 생성 이후 건조 중 결정이 생성되어 표면이 뿌옇게 흐려지는 경우를 △로 나타내며, 레지스트 조성물에 잘 용해된 상태로 필름 형성시 결정이 생성되지 않고 표면이 깨끗한 경우를 ○로 나타내었다.
Each photosensitive resin composition including the synthesized photoinitiator was applied to the organic substrate with a spin coater. In this case, X is a case in which crystals are formed during rotational coating according to the solubility of the photoinitiator and the coating surface is very poor, and X is a case in which crystals are formed during drying after film formation, and the surface becomes cloudy. The case where no crystal is formed at the time of formation and the surface is clean is shown by (circle).
이와 같은 평가 결과를 다음 표 2 에 나타내었다.
Such evaluation results are shown in Table 2 below.
(mJ)Sensitivity
(mJ)
(백화현상)Thin film characteristics
(Whitening phenomenon)
상기에서 살펴본 바와 같이 본 발명에 따른 알파키토옥심에스테르 화합물 및 이를 포함한 감광성 조성물의 경우 밀착성 및 내알칼리성이 우수하며 박막의 백화현상도 없음을 알 수 있다. 또한, 본 발명에 따른 알파키토옥심에스테르 화합물은 감도가 우수한 것을 확인할 수 있었다.
As described above, in the case of the alpha chitooxime ester compound and the photosensitive composition including the same according to the present invention, it can be seen that the adhesion and alkali resistance are excellent and there is no whitening of the thin film. In addition, it was confirmed that the alpha chito oxime ester compound according to the present invention has excellent sensitivity.
(5) 변색성(5) discoloration property
알파키토옥심에스테르 광중합개시제의 변색 여부를 확인하기 위하여 Lambda Vision사의 현미 분광기(model:TFCAM700)를 사용하여 레드에 해당하는 조성물을 노광 전 후에 대하여 색좌표를 측정하였다. 그 결과를 아래 표 3에 나타내었다.
In order to confirm the discoloration of the alpha chito oxime ester photoinitiator, color coordinates were measured before and after exposing the composition corresponding to red using a Lambda Vision microscopic spectrometer (model: TFCAM700). The results are shown in Table 3 below.
상기 표 3에서 확인한 바와 같이 본 발명에 따른 알파키토옥심에스테르 화합물을 포함하는 감광성 조성물의 경우 노광 전 및 노광 후의 색좌표를 비교했을 때 그 차이가 거의 없었다. 따라서 본 발명에 따른 감광성 조성물의 경우 변색이 쉽게 일어나지 않음을 확인할 수 있었다. As confirmed in Table 3, in the photosensitive composition including the alpha-chitooxime ester compound according to the present invention, there was almost no difference in color coordinates before and after exposure. Therefore, in the case of the photosensitive composition according to the present invention it was confirmed that discoloration does not occur easily.
Claims (10)
[화학식 1]
여기에서, R은 1 내지 5개의 메틸기를 갖는 메틸벤젠기이며,
R1은 탄소수 1 내지 10인 알킬기 또는 페닐기이고,
R2는 -CH3,-C2H5, 또는 -프로필이고,
R3는 -H,
Alpha keto oxime ester compound represented by the following general formula (1):
[Formula 1]
Here, R is a methylbenzene group having 1 to 5 methyl groups,
R 1 is an alkyl group or phenyl group having 1 to 10 carbon atoms,
R 2 is —CH 3 , —C 2 H 5 , or —propyl,
R 3 is -H,
At least one compound selected from compounds of formula 1 according to claim 1; And acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumaric acid, monoethyl fumaric acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether Methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile, methyl acrylate , Methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, Ethylene Glycol Diacrylate, Ethylene Glycol Dimethacrylate, Die Ethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, Propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacryl Latex, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6- Di oldi acrylate, 1,6-hexanediol dimethacrylate, di-Cardo epoxy monomers or oligomers of acrylates; (Meth) acrylic acid is reacted with a polyester (meth) acrylate obtained by reacting (meth) acrylic acid to a polyester prepolymer obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid, and a compound having a polyol group and two isocyanate groups. Polyurethane (meth) acrylate obtained by reaction; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycol At least one compound selected from the group consisting of cylyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, dihydroxybenzene type epoxy resins, and epoxy (meth) acrylate resins obtained by reacting (meth) acrylic acid; The photosensitive resin composition.
상기 조성물은 착색제 또는 안료를 더 포함하는 것인 감광성 수지 조성물.
The method of claim 2,
Wherein the composition further comprises a colorant or a pigment.
A column spacer formed from the photosensitive resin composition according to claim 2.
A black matrix formed from the photosensitive resin composition according to claim 2.
The color filter composition formed from the photosensitive resin composition of Claim 2.
A substrate having an organic insulating film formed from the photosensitive resin composition according to claim 2.
A substrate having a film formed by coating the photosensitive resin composition according to claim 2.
상기 막은 워드프로세서, 컴퓨터, 텔레비전 또는 플라즈마 디스플레이 패널, 액정표시장치에 사용되는 편광판의 표면, 선글라스 렌즈, 도수가 있는 안경렌즈, 카메라용 파인더 렌즈, 게기의 커버, 자동차의 유리, 전차의 유리, 광휘도 향상막, 또는 광도파로막으로 사용되는 것을 특징으로 하는 기재. 9. The method of claim 8,
The film is a surface of a polarizing plate used in a word processor, a computer, a television or a plasma display panel, a liquid crystal display device, a sunglasses lens, a spectacle lens, a finder lens for a camera, a cover of a flag, a glass of a vehicle, a glass of a tank, a brightness The base material used as a figure improvement film | membrane or an optical waveguide film | membrane.
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| KR1020120006575A KR101225695B1 (en) | 2012-01-20 | 2012-01-20 | New high sensitive a-ketoximester photo compounds and photosensitive composition comprising the same |
| JP2012074092A JP5514854B2 (en) | 2012-01-20 | 2012-03-28 | Novel high sensitivity alpha ketoxime ester photoinitiator and photopolymerizable composition containing this compound |
| JP2014064963A JP5868449B2 (en) | 2012-01-20 | 2014-03-27 | Novel high-sensitivity alpha ketoxime ester photoinitiator and photopolymerization composition containing the same |
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| CN104276995A (en) * | 2013-07-01 | 2015-01-14 | 塔科马科技有限公司 | High-photosensibility oxime ester photopolymerization initiator and photopolymerization composition containing same |
| KR101491975B1 (en) | 2014-03-14 | 2015-02-11 | (주)휴넷플러스 | Positive Type Chemically-amplified Photosensitive Resin Composition, Method for Producing a Cured Film Using The Same and Electronic Device Comprising The Cured Film |
| WO2015036910A1 (en) | 2013-09-10 | 2015-03-19 | Basf Se | Oxime ester photoinitiators |
| WO2017155176A1 (en) * | 2016-03-08 | 2017-09-14 | 삼성에스디아이 주식회사 | Photosensitive resin composition, and black column spacer and color filter using same |
| WO2020152120A1 (en) | 2019-01-23 | 2020-07-30 | Basf Se | Oxime ester photoinitiators having a special aroyl chromophore |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015036910A1 (en) | 2013-09-10 | 2015-03-19 | Basf Se | Oxime ester photoinitiators |
| KR101491975B1 (en) | 2014-03-14 | 2015-02-11 | (주)휴넷플러스 | Positive Type Chemically-amplified Photosensitive Resin Composition, Method for Producing a Cured Film Using The Same and Electronic Device Comprising The Cured Film |
| WO2017155176A1 (en) * | 2016-03-08 | 2017-09-14 | 삼성에스디아이 주식회사 | Photosensitive resin composition, and black column spacer and color filter using same |
| WO2020152120A1 (en) | 2019-01-23 | 2020-07-30 | Basf Se | Oxime ester photoinitiators having a special aroyl chromophore |
| WO2021175855A1 (en) | 2020-03-04 | 2021-09-10 | Basf Se | Oxime ester photoinitiators |
Also Published As
| Publication number | Publication date |
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| JP2013147483A (en) | 2013-08-01 |
| JP5514854B2 (en) | 2014-06-04 |
| JP5868449B2 (en) | 2016-02-24 |
| JP2014159433A (en) | 2014-09-04 |
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