KR20200136559A - Highly photosensitive oxime ester based photoinitiator and photosensitive compositions including the same - Google Patents

Highly photosensitive oxime ester based photoinitiator and photosensitive compositions including the same Download PDF

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KR20200136559A
KR20200136559A KR1020190062220A KR20190062220A KR20200136559A KR 20200136559 A KR20200136559 A KR 20200136559A KR 1020190062220 A KR1020190062220 A KR 1020190062220A KR 20190062220 A KR20190062220 A KR 20190062220A KR 20200136559 A KR20200136559 A KR 20200136559A
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oxime ester
ortho
formula
aryl
methyl
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KR1020190062220A
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Korean (ko)
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정인
이상은
이정원
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인오켐 주식회사
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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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Indole Compounds (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention relates to a highly soluble oxime ester benzo alpha-carbazole compound which shows high radical-generating efficiency even with a low exposure light dose to realize high sensitivity and causes no precipitation even when being added in an excessive amount to a solvent used for a photopolymerizable composition. Particularly, the compound is characterized in that a 2-halo ethylether group containing a monomer to trimer of ethyl ether is introduced to a nitrogen atom in a benzo alpha-carbazole ring substituted with a nitro group. In addition, since a phenyl substituted with a methyl group at the ortho-position, phenyl substituted with methyl groups at the ortho-, meta- and para-positions, phenyl substituted with Cl or F at the ortho-position, or an ether functional group having a methyl or ethyl group at the para-position is introduced to the oxime ester benzo alpha-carbazole compound, it shows high light absorption in a long-wavelength region to provide high sensitivity and excellent solubility in combination with improved pattern stability, chemical resistance and close contact properties. The present invention also relates to a photosensitive composition including an oxime ester-based photoinitiator prepared from the benzo alpha-carbazole ring, and useful for photocurable ink, a photosensitive printed board, various photoresists, a color filter photoresist for LCD, a photoresist for a resin black matrix or a transparent photosensitive material.

Description

고감도 옥심 에스테르계 광개시제 및 이를 포함하는 감광성 조성물 {Highly photosensitive oxime ester based photoinitiator and photosensitive compositions including the same}Highly photosensitive oxime ester based photoinitiator and photosensitive compositions including the same}

본 명세서에 개시된 기술은 장파장 영역의 빛의 흡수가 우수한 벤조알파카바졸 고리와 이웃하는 치환체를 갖는 페닐기 사이에 옥심 에스테르기를 도입한 광개시제 및 이를 포함하는 감광성 조성물에 관한 것으로서, 벤조알파카바졸 고리의 우수한 장파장 영역에서의 흡수와 이웃하는 페닐기들에 의한 전자 주개 효과로 고감도를 구현하면서 특히 벤조알파카바졸 고리 내 질소 원자에 1 단위체 내지 3 단위체 에틸에테르를 포함하는 2-할로 에틸에테르기를 도입함으로써 유기 용제에 대한 우수한 용해성을 갖는 옥심 에스테르계 광개시제 및 이를 포함하는 감광성 조성물에 관한 것이다.The technology disclosed in the present specification relates to a photoinitiator in which an oxime ester group is introduced between a benzoalphacarbazole ring having excellent light absorption in a long wavelength region and a phenyl group having a neighboring substituent, and a photosensitive composition comprising the same, wherein the benzoalphacarbazole ring is In particular, by introducing a 2-halo ethyl ether group containing 1 to 3 units ethyl ether to the nitrogen atom in the benzoalphacarbazole ring, while realizing high sensitivity through absorption in the excellent long wavelength range and electron donating effect by neighboring phenyl groups. It relates to an oxime ester photoinitiator having excellent solubility in a solvent and a photosensitive composition comprising the same.

광개시제는 빛을 흡수하여 분해됨으로써 화학적으로 활성을 지닌 원자 또는 분자를 생성하는 물질이며, 감광성 조성물 등에 널리 사용된다. 화학적 활성을 지닌 물질의 예로는 산이나 염기 그리고 라디칼 등이 있다. 특히, 라디칼이 생성되는 광개시제는 라디칼과 함께 중합 반응을 일으키는 아크릴기를 함께 사용하여 코팅된 막의 강도를 향상시키는 목적으로 사용될 수 있다. 이러한 용도의 감광성 조성물로는 잉크젯용 잉크 또는 자동차나 휴대폰 등의 투명하거나 착색된 보호막 그리고 빛에 의한 중합 반응에 따른 용해도가 감소되는 현상을 이용하는 광식각법용 감광성 수지 조성물에 광개시제가 응용될 수 있다. Photoinitiators are substances that absorb light and decompose to produce chemically active atoms or molecules, and are widely used in photosensitive compositions. Examples of chemically active substances include acids, bases and radicals. In particular, the photoinitiator from which radicals are generated may be used for the purpose of improving the strength of the coated film by using an acrylic group that causes a polymerization reaction with the radical. As a photosensitive composition for such a use, a photoinitiator may be applied to an inkjet ink, a transparent or colored protective film such as an automobile or mobile phone, and a photosensitive resin composition for photolithography using a phenomenon in which the solubility decreases due to polymerization reaction by light.

대표적인 예로는 액정표시소자의 컬러 필터 제조에 사용되는 광중합형 감광성 수지 조성물이나, 수지 블랙 매트릭스용 감광성 조성물 등이 있다. 감광성 조성물은 기판상에 도포되어 도막을 형성하고, 이 도막의 특정 부분에 포토마스크 등을 이용하여 광조사에 의한 노광을 실시한 후, 비노광부를 현상처리하여 제거함으로써 패턴을 형성하는데 사용될 수 있다. 이러한 감광성 조성물은 광을 조사하여 중합하고 경화시키는 것이 가능하므로 광경화성 잉크, 감광성 인쇄판, 각종 포토레지스트, LCD용 컬러 필터 포토레지스트, 수지 블랙 매트릭스용 포토레지스트 또는 투명 감광재 등에 널리 이용되고 있다.Representative examples include a photopolymerizable photosensitive resin composition used for manufacturing a color filter for a liquid crystal display device, a photosensitive composition for a resin black matrix, and the like. The photosensitive composition may be applied to a substrate to form a coating film, and exposed to light by light irradiation using a photomask or the like on a specific portion of the coating film, and then developed to remove the non-exposed portion, thereby forming a pattern. Since such a photosensitive composition can be polymerized and cured by irradiating light, it is widely used in photocurable inks, photosensitive printing plates, various photoresists, color filter photoresists for LCDs, photoresists for resin black matrices, or transparent photosensitive materials.

감광성 조성물은 통상적으로 고분자 수지 화합물과 에틸렌성 불포화 결합을 포함하는 중합성 화합물, 용매, 그리고 광개시제를 포함한다. 감광성 조성물은 LCD의 용도가 고급화, 다양화됨에 따라 종래의 노트북, 모바일 등의 용도 외에 TV, 모니터 등의 액정표시소자를 구성하는 용도로 제작되고 있으며, 생산성 및 내구성 향상을 위해 빛에 빠르게 반응하고, 기계적으로 우수한 물성에 대한 요구가 높아지고 있다.The photosensitive composition typically includes a polymeric resin compound and a polymerizable compound including an ethylenically unsaturated bond, a solvent, and a photoinitiator. Photosensitive compositions are being produced for constituting liquid crystal display devices such as TVs and monitors in addition to conventional notebooks and mobiles as the use of LCDs becomes more advanced and diversified, and responds quickly to light to improve productivity and durability. , The demand for mechanically excellent physical properties is increasing.

포토리소그래피(Photo-lithography) 법에 의해 패턴을 형성시키거나, 전면 노광을 통해 절연 보호막을 형성하는 경우에 있어 빛에 빠르게 반응하는 특성, 즉 광감도는 매우 중요한 역할을 하는 요인이 된다. 또한, 외부에서 가한 충격에 의해 액정표시소자가 파손되지 않고 원래의 성능을 발휘하게 하기 위해서 지지대 역할을 하는 컬럼 스페이서 또는 보호막의 역할을 하는 오버코트와 패시베이션 막은 기계적 물성이 우수해야 한다. 따라서, 광감도가 우수한 광중합 개시제를 사용하면 이러한 문제들을 해결할 수 있다.In the case of forming a pattern by a photolithography method or forming an insulating protective film through full exposure, a property that reacts quickly to light, that is, photosensitivity, becomes a very important factor. In addition, in order to exhibit the original performance without damaging the liquid crystal display by external impact, the column spacer serving as a support or the overcoat and passivation layer serving as a protective layer must have excellent mechanical properties. Therefore, these problems can be solved by using a photopolymerization initiator having excellent photosensitivity.

감광성 수지 조성물에 사용되는 광 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, 감광성수지 조성물 재료들과의 상용성 및 안정성이 우수한 장점을 갖고 있다. 그러나 초기에 개발된 옥심에스테르 유도체 화합물은 광중합 개시 효율이 낮으며, 특히 패턴 노광 공정 시 감도가 낮아 노광량을 늘려야 하고 이로 인해 생산량이 줄어드는 문제가 있다.General examples of photoinitiators used in the photosensitive resin composition are known as acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives and oxime ester derivatives, and the oxime ester derivatives are It absorbs ultraviolet rays, shows little color, has high radical generation efficiency, and has excellent compatibility and stability with photosensitive resin composition materials. However, the initially developed oxime ester derivative compound has a low photopolymerization initiation efficiency, and in particular, has a low sensitivity during the pattern exposure process, so that the exposure amount must be increased, thereby reducing the production amount.

최근에 대면적 고화질 디스플레이의 수요가 증가하면서 해상도를 높이기 위해 미세패턴특성이 요구됨에 따라 고감도 및 유기용제에 대한 용해성이 우수한 광개시제를 포함하는 감광성 조성물에 대한 요구가 증가하고 있다.In recent years, as the demand for large-area high-definition displays is increasing and fine pattern characteristics are required to increase resolution, there is an increasing demand for a photosensitive composition including a photoinitiator having high sensitivity and excellent solubility in organic solvents.

따라서 본 발명은 적은 노광량으로 라디칼 생성효율이 우수하여 고감도를 구현할 수 있고 광중합 조성물에 사용되는 용매에 대해 과량을 첨가해도 침전이 발생하지 않는 고용해성 광개시제 화합물 및 이를 포함하는 감광성 조성물을 제공하는 것이다. 또 한 노광 시 광 분해물에 의한 마스크 오염이 없는 동시에 밀착성과 패턴안정성이 우수한 고감도 및 고용해성 옥심 에스테르계 광개시제를 제공하는 것을 목적으로 한다. Accordingly, the present invention provides a highly soluble photoinitiator compound and a photosensitive composition comprising the same, which can realize high sensitivity due to excellent radical generation efficiency with a small exposure amount, and does not cause precipitation even when an excessive amount is added to the solvent used in the photopolymerization composition. Another object of the present invention is to provide a highly sensitive and high-solubility oxime ester-based photoinitiator with excellent adhesion and pattern stability at the same time that there is no mask contamination by photodecomposition products during exposure.

본 발명의 또 다른 목적은 이와 같은 옥심 에스테르계 광개시제를 포함하는 감광성 조성물로서, 광경화성 잉크, 감광성 인쇄판, 각종 포토레지스트, LCD용 컬러 필터 포토레지스트, 수지 블랙 매트릭스용 포토레지스트 또는 투명 감광재 등과 같은 감광성 수지 조성물을 제공하는 것이다.Another object of the present invention is a photosensitive composition containing such an oxime ester-based photoinitiator, such as photocurable ink, photosensitive printing plate, various photoresist, color filter photoresist for LCD, photoresist for resin black matrix, or transparent photosensitive material. It is to provide a photosensitive resin composition.

본 발명에 의하면, 하기 화학식 1로 표현되는 옥심 에스테르계 광개시제가 제공된다.According to the present invention, an oxime ester-based photoinitiator represented by the following formula (1) is provided.

[화학식 1] [Formula 1]

Figure pat00001
Figure pat00001

상기 화학식 1에서 X는 Cl 또는 Br이며, n은 1 단위체 내지 3 단위체 In Formula 1, X is Cl or Br, and n is 1 to 3 units

할로 에틸에테르이다. Ar1 또는 Ar2 는 C6-C30 아릴에테르, C6-C30 할로아릴, C6-C30 아릴, C7-C30 아르알킬, C5-C30 헤테로아릴이며 R1 는 C1-C3 알킬 또는 페닐기 등이 포함 될 수 있다.It is halo ethyl ether. Ar 1 or Ar 2 is C 6 -C 30 aryl ether, C 6 -C 30 haloaryl, C 6 -C 30 aryl, C 7 -C 30 aralkyl, C 5 -C 30 heteroaryl and R 1 is C 1 -C 3 alkyl or phenyl group, etc. may be included.

보다 바람직하게는 상기 화학식 1에서 X는 Cl이며 n은 1 단위체 내지 2 단위체 할로 에틸에테르기를 포함할 수 있고 Ar1 또는 Ar2 는 C6-C12 아릴에테르, C6-C12 할로아릴, C6-C12 아릴, C7-C15 아르알킬이다. R1 는 C1-C3 알킬 또는 페닐이며 보다 바람직하게는 메틸 및 페닐기 들이 포함 될 수 있다.More preferably, in Formula 1, X is Cl and n may include a 1 to 2 unit halo ethyl ether group, and Ar 1 or Ar 2 is C 6 -C 12 aryl ether, C 6 -C 12 haloaryl, C 6 -C 12 aryl, C 7 -C 15 aralkyl. R 1 is C 1 -C 3 alkyl or phenyl, more preferably methyl and phenyl groups may be included.

Ar1 또는 Ar2 는 오르소 또는 오르소와 메틸 및 파라 위치에 알킬기로 치환된 C6-C20 아릴이며 Ar1 또는 Ar2 는 C6-C20 아릴이나 오르소 또는 오르소와 메틸 및 파라 위치에 할로겐 및 에테르기로 치환된 C6-C20 아릴기 들이 포함될 수 있다.Ar 1 or Ar 2 is a C 6 -C 20 aryl substituted with an alkyl group at the position of ortho or ortho and methyl and para, and Ar 1 or Ar 2 is a C 6 -C 20 aryl or ortho or ortho and methyl and para. C 6 -C 20 aryl groups substituted with halogen and ether groups at the position may be included.

Ar1 또는 Ar2 는 오르소 위치에 메틸기로 치환된 페닐이나 오르소, 메타 및 파라 위치에 메틸기로 치환된 페닐기일 수 있고 Ar1 또는 Ar2 는 오르소 위치에 Cl 또는 F 기로 치환된 페닐이나 파라 위치에 메틸, 에틸, 프로필, 이소프로필, 부틸, 펜틸, 이소펜틸기를 갖는 에테르 작용기를 포함할 수 있다.Ar 1 or Ar 2 may be a phenyl group substituted with a methyl group at the ortho position or a phenyl group substituted with a methyl group at the ortho, meta and para positions, and Ar 1 or Ar 2 is a phenyl group substituted with a Cl or F group at the ortho position or It may include an ether functional group having a methyl, ethyl, propyl, isopropyl, butyl, pentyl, isopentyl group in the para position.

상기 화학식 1로 대표되는 옥심에스테르 벤조알파카바졸 유도체 화합물을 광중합용 개시제로 사용하며 에틸렌계 불포화 결합을 가지는 화합물을 포함하는 감광성 수지 조성물을 포함할 수 있다. 또 한 상기 화학식 1로 대표되는 옥심에스테르 벤조알파카바졸 유도체 광개시제, 에틸렌계 불포화 결합을 가지는 화합물 및 현상성 바인더수지를 포함하는 감광성 수지 조성물을 포함할 수 있다.The oxime ester benzoalphacarbazole derivative compound represented by Formula 1 is used as an initiator for photopolymerization, and a photosensitive resin composition comprising a compound having an ethylenically unsaturated bond may be included. In addition, it may include a photosensitive resin composition including an oxime ester benzoalphacarbazole derivative photoinitiator represented by Formula 1, a compound having an ethylenically unsaturated bond, and a developable binder resin.

본 발명에 따르면 적은 노광량으로 라디칼 생성효율이 우수한 고감도이며, 감광성 조성물의 용제로 유용한 프로필렌글리콜메틸에테르아세테이트(PGMEA) 등에 대한 용해성이 우수한 옥심 에스테르계 광개시제를 제공할 수 있다. 특히 고감도 특성은 광가교 반응 시 사용되는 광개시제의 양을 최소화하여 감광성 조성물의 가격 경쟁력 확보와 함께 성능 향상을 위한 조성물 비율을 최적화를 통해 품질 경쟁력을 확보할 수 있다. 또 한 본 발명은 니트로기를 포함하는 카바졸을 골격으로 하는 옥심 에스테르계 광개시제의 낮은 용해성을 개선함으로써 조성물 내 침전 발생을 방지할 수 있으며 고용해성으로 사용양에 대한 조절이 가능하여 감광제의 성능을 향상시킬 수 있다. According to the present invention, it is possible to provide an oxime ester-based photoinitiator excellent in solubility in propylene glycol methyl ether acetate (PGMEA), etc., which is excellent in radical generation efficiency with a small exposure amount, and is useful as a solvent for a photosensitive composition. Particularly, high sensitivity characteristics minimize the amount of photoinitiator used in the photo-crosslinking reaction, thereby securing price competitiveness of the photosensitive composition and optimizing the composition ratio for improving performance, thereby securing quality competitiveness. In addition, the present invention can prevent the occurrence of precipitation in the composition by improving the low solubility of the oxime ester-based photoinitiator having a carbazole-containing nitro group as a skeleton, and improve the performance of the photosensitizer by controlling the amount of use due to its solubility. I can make it.

상기 옥심 에스테르계 광개시제를 적용한 감광성 조성물은 광경화성 잉크, 감광성 인쇄판, 각종 포토레지스트, LCD용 컬러 필터 포토레지스트, 수지 블랙 매트릭스용 포토레지스트 또는 투명 감광재 등을 제조할 수 있다.The photosensitive composition to which the oxime ester-based photoinitiator is applied may prepare a photocurable ink, a photosensitive printing plate, various photoresists, a color filter photoresist for LCD, a photoresist for a resin black matrix, or a transparent photosensitive material.

본 발명에 의한 에틸렌계 불포화 결합을 가지는 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 폴리에틸렌글리콜모노(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 에틸렌 옥사이드기의 수가 2 내지 14인 폴리에틸렌글리콜디(메타)아크릴레이트, 프로필렌옥사이드기의 수가 2 내지 14인 프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타) 아크릴레이트, 비스페놀 A 디글리시딜에테르아크릴산 부가물,

Figure pat00002
-히드록시 에틸(메타)아크릴레이트의 프탈산디에스테르,
Figure pat00003
-히드록시에틸(메타) 아크릴레이트의 톨루엔디이소시아네이트 부가물, 트리메틸올프로판트리(메타) 아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트, 디펜타에리스리톨트리(메타)아크릴레이트와 같이 다가 알콜과 α,
Figure pat00004
-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.Compounds having an ethylenically unsaturated bond according to the present invention are specifically methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) ) Alkyl ester of (meth)acrylic acid such as acrylate, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate having 2 to 14 ethylene oxide groups, ethylene glycol di (meth)acrylate, ethylene Polyethylene glycol di(meth)acrylate with 2 to 14 oxide groups, propylene glycol di(meth)acrylate with 2 to 14 propylene oxide groups, trimethylolpropanedi(meth)acrylate, bisphenol A diglyci Dietheracrylic acid adduct,
Figure pat00002
-Phthalic acid diester of hydroxy ethyl (meth) acrylate,
Figure pat00003
-Toluene diisocyanate adduct of hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Polyhydric alcohols and α, such as acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tri(meth)acrylate,
Figure pat00004
-A compound obtained by esterifying an unsaturated carboxylic acid, an acrylic acid adduct of a polyhydric glycidyl compound such as a trimethylolpropane triglycidyl ether acrylic acid adduct, and the like, and these may be used alone or in combination of two or more.

본 발명에 의한 현상성 바인더 수지는, 아크릴산함유 아크릴공중합체, 노볼락계 페놀수지, 폴리히드록시스트렌수지, 히드록시스티렌과 아크릴레이트의 공중합체 및 이들의 혼합일수 있다.The developable binder resin according to the present invention may be an acrylic acid-containing acrylic copolymer, a novolac-based phenol resin, a polyhydroxystyrene resin, a hydroxystyrene-acrylate copolymer, and a mixture thereof.

바람직한 구현 예에서, 상기 화학식 1로 표현되는 화합물은 하기 화학식 1-1 내지 1-16으로 표현되는 옥심에스테르 벤조알파카바졸 화합물들 중에서 선택될 수 있다.In a preferred embodiment, the compound represented by Formula 1 may be selected from oxime ester benzoalphacarbazole compounds represented by Formulas 1-1 to 1-16 below.

상기 화학식 1의 바람직한 구체적인 예들은 다음의 화학식으로 표현될 수 있다.Preferred specific examples of Formula 1 may be represented by the following formula.

상기 화학식 1의 바람직한 구체적인 예들은 다음의 화학식으로 표현될 수 있다.Preferred specific examples of Formula 1 may be represented by the following formula.

Figure pat00005
Figure pat00005

화학식 1-1 화학식 1-2 화학식 1-3 화학식 1-4Formula 1-1 Formula 1-2 Formula 1-3 Formula 1-4

Figure pat00006
Figure pat00006

화학식 1-5 화학식 1-6 화학식 1-7 화학식 1-8Formula 1-5 Formula 1-6 Formula 1-7 Formula 1-8

Figure pat00007
Figure pat00007

화학식 1-9 화학식 1-10 화학식 1-11 화학식 1-12Formula 1-9 Formula 1-10 Formula 1-11 Formula 1-12

Figure pat00008
Figure pat00008

화학식 1-13 화학식 1-14 화학식 1-15 화학식 1-16Formula 1-13 Formula 1-14 Formula 1-15 Formula 1-16

본 발명의 화학식 1-1 내지 1-16의 화합물을 제조하는 방법은 예를 들면 하기 반응식 1로 설명되는 합성과정에 의해 제조될 수 있다. The method of preparing the compounds of Formulas 1-1 to 1-16 of the present invention can be prepared by, for example, a synthetic procedure described by Scheme 1 below.

Figure pat00009
Figure pat00009

상기 반응식 1에 따르면, 염기 존재 하에 벤조알파카바졸과 다이할로 에틸에테르의 SN2 반응으로부터 준비된 2-할로 에틸에테르 벤조알파카바졸과 아실 클로라이드를 Lewis acid 존재 하에 Fridel-Craft 반응을 통해 상응하는 케톤 화합물을 얻는다. 상기 케톤 화합물을 아세트산무수물과 염산 하이드록실아민을 이용한 옥심 반응을 거쳐 상응하는 옥심 화합물을 얻는다. 상기 옥심 화합물을 상응하는 무수초산과 반응시켜 상기 화학식 1-1 내지 1-16으로 표현되는 옥심 에스테르 벤조알파카바졸 유도체 화합물들을 수득할 수 있다. According to Reaction Scheme 1, 2-halo ethyl ether benzoalphacarbazole and acyl chloride prepared from S N 2 reaction of benzoalphacarbazole and dihalo ethyl ether in the presence of a base were matched through Fridel-Craft reaction in the presence of Lewis acid. To obtain a ketone compound. The ketone compound is subjected to an oxime reaction using acetic anhydride and hydroxylamine hydrochloride to obtain a corresponding oxime compound. By reacting the oxime compound with corresponding acetic anhydride, oxime ester benzoalphacarbazole derivative compounds represented by Formulas 1-1 to 1-16 can be obtained.

이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 실시예를 들어 상세하게 설명한다.Hereinafter, for a detailed understanding of the present invention, representative compounds of the present invention will be described in detail with examples.

실시예 1에 기재된 합성법을 적용 시, 화학식 1-2 내지 1-8의 구조에 상응하는 Ar1, Ar2 및 R1 를 도입하면 화학식 1-2 내지 1-8 화합물의 제조가 가능하다. When applying the synthesis method described in Example 1, by introducing Ar 1 , Ar 2 and R 1 corresponding to the structures of Formulas 1-2 to 1-8, it is possible to prepare compounds of Formulas 1-2 to 1-8.

[실시예 1: 화학식 1-1 화합물의 합성][Example 1: Synthesis of Compound 1-1]

Figure pat00010
Figure pat00010

1 단계: 11-(2-(2-chloroethoxy)ethyl)-11H-benzo[α]carbazole 의 합성Step 1: Synthesis of 11-(2-(2-chloroethoxy)ethyl)-11H-benzo[α]carbazole

질소분위기 하에서 DMF (200 mL) 에 11H-benzo[α]carbazole (21.7 g, 0.1 mol) 을 가하고 0 ℃ 에서 sodium hydride (4.8 g, 0.2 mol) 을 투입한 다음 30 분간 교반한다. 반응액에 1-chloro-2-(2-chloroethoxy)ethane (28.4 g, 0.2 mol) 을 가하고 2 시간 교반한다. TLC로 반응 종결을 확인한 후 반응액을 상온으로 승온한다. DCM (200 mL) 를 투입한 후 brine (400 mL) 으로 세척하여 추출한다. 추출된 유기층에 대해서 3 회에 걸쳐 증류수 (200 mL X 3 회) 를 투입하여 세척한다. 유기층을 MgSO4로 처리하고 감압 농축한 후 농축액은 실리카젤 컬럼 크로마토그래피 (n-Hex./E.A. = 2/1) 을 이용한 정제 과정을 거쳐 목적화합물 (29.7 g) 을 92 % 수율로 획득한다. In a nitrogen atmosphere, 11H-benzo[α]carbazole (21.7 g, 0.1 mol) was added to DMF (200 mL), sodium hydride (4.8 g, 0.2 mol) was added at 0 ℃, followed by stirring for 30 minutes. 1-chloro-2-(2-chloroethoxy)ethane (28.4 g, 0.2 mol) was added to the reaction solution and stirred for 2 hours. After confirming the completion of the reaction by TLC, the reaction solution was heated to room temperature. After adding DCM (200 mL), extract by washing with brine (400 mL). Distilled water (200 mL X 3 times) was added to the extracted organic layer 3 times and washed. The organic layer was treated with MgSO 4 and concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-Hex./EA = 2/1) to obtain the target compound (29.7 g) in 92% yield.

1H-NMR (δ, ppm), CDCl3: 8.56 (d/d, 1H), 8.16 (d, 1H), 8.14 (d, 1H), 8.03 (d, 1H), 7.65 (d, 1H), 7.42-7.30 (m, 4H), 7.28 (m, 1H), 4.45 (t, 2H), 3.83 (t, 2H), 3.69-3.57 (m, 4H). 1 H-NMR (δ, ppm), CDCl 3 : 8.56 (d/d, 1H), 8.16 (d, 1H), 8.14 (d, 1H), 8.03 (d, 1H), 7.65 (d, 1H), 7.42-7.30 (m, 4H), 7.28 (m, 1H), 4.45 (t, 2H), 3.83 (t, 2H), 3.69-3.57 (m, 4H).

2 단계: (11-(2-(2-chloroethoxy)ethyl)-5-(2-methylbenzoyl)-11H-benzoStep 2: (11-(2-(2-chloroethoxy)ethyl)-5-(2-methylbenzoyl)-11H-benzo

[α]carbazol-8-yl)(4-methoxyphenyl)methanone 합성Synthesis of [α]carbazol-8-yl)(4-methoxyphenyl)methanone

질소분위기 하에서 DCM (100 mL) 에 상기 1단계 화합물 (16.2 g, 50 mmol) 을 녹인 용액에 대해 2-methylbenzoyl chloride (8.5 g, 55 mmol) 와 aluminum chloride (6.7 g, 55 mmol) 을 0

Figure pat00011
에서 적가한다. 반응액을 실온에서 교반하면서 TLC로 반응이 완료된 것을 확인한 후, 반응액을 0
Figure pat00012
로 냉각하고 4-methoxybenzoyl chloride (9.4 g, 55 mmol) 와 aluminum chloride (6.7 g, 55 mmol) 을 적가한다. 반응액을 실온에서 교반하면서 TLC로 반응이 완료된 것을 확인한 후, 강교반하면서 ice-water (400 mL) 에 반응액을 서서히 적가한다. DCM (200 mL) 가한 후 유기층을 brine (200 mL) 으로 세척하여 추출한다. 추출된 유기층에 대해서 증류수 (100 mL X 3 회) 를 투입하여 세척한다. 유기층을 MgSO4로 처리하고 감압 농축한 후 농축액은 실리카젤 컬럼 크로마토그래피 (n-Hex./E.A. = 1/1)을 이용한 정제 과정을 거쳐 목적화합물 (22.6 g) 을 79 % 수율로 획득한다. 2-methylbenzoyl chloride (8.5 g, 55 mmol) and aluminum chloride (6.7 g, 55 mmol) were added to the solution of the first step compound (16.2 g, 50 mmol) in DCM (100 mL) under a nitrogen atmosphere.
Figure pat00011
Dropwise from After confirming that the reaction was completed by TLC while stirring the reaction solution at room temperature,
Figure pat00012
After cooling with 4-methoxybenzoyl chloride (9.4 g, 55 mmol) and aluminum chloride (6.7 g, 55 mmol) is added dropwise. After confirming that the reaction is complete by TLC while stirring the reaction solution at room temperature, the reaction solution is slowly added dropwise to ice-water (400 mL) while stirring strongly. After DCM (200 mL) was added, the organic layer was washed with brine (200 mL) and extracted. Distilled water (100 mL X 3 times) was added to the extracted organic layer and washed. The organic layer was treated with MgSO 4 , concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-Hex./EA = 1/1) to obtain the target compound (22.6 g) in 79% yield.

1H-NMR (δ, ppm), CDCl3: 9.58 (d, 1H), 8.82 (d, 1H), 8.37 (d, 1H), 8.30 (d, 1H), 7.87 (d, 1H), 7.85-7.49 (m, 5H), 7.45-7.19 (m, 6H), 4.48 (t, 2H), 3.87 (t, 2H), 3.82 (s, 3H), 3.73-3.60 (m, 4H), 2.35 (s, 3H). 1 H-NMR (δ, ppm), CDCl 3 : 9.58 (d, 1H), 8.82 (d, 1H), 8.37 (d, 1H), 8.30 (d, 1H), 7.87 (d, 1H), 7.85- 7.49 (m, 5H), 7.45-7.19 (m, 6H), 4.48 (t, 2H), 3.87 (t, 2H), 3.82 (s, 3H), 3.73-3.60 (m, 4H), 2.35 (s, 3H).

3단계: (11-(2-(2-chloroethoxy)ethyl)-8-((hydroxyimino)(4-methoxyStep 3: (11-(2-(2-chloroethoxy)ethyl)-8-((hydroxyimino)(4-methoxy

phenyl)methyl)-11H-benzo[a]carbazol-5-yl)(o-tolyl)methanone 합성Synthesis of phenyl)methyl)-11H-benzo[a]carbazol-5-yl)(o-tolyl)methanone

질소분위기 하에서 DMF (100 mL) 에 상기 2단계 화합물 (11.5 g, 20 mmol) 을 녹인 후, sodium acetate trihydrate (3.0 g, 22 mmol) 과 hydroxylamine HCl salt (1.5 g, 22 mmol) 을 넣고 100

Figure pat00013
로 승온한다. TLC 로 반응이 완료된 것을 확인한 후, 반응액을 실온으로 냉각하고 증류수 (100 mL) 를 투입하여 quenching 한다. DCM (100 mL) 을 투입하여 추출한 유기층을 brine (100 mL) 과 증류수 (100 mL) 로 3 회 세척한다. 유기층을 MgSO4로 처리하고 감압 농축한 후 농축액은 실리카젤 컬럼 크로마토그래피 (n-Hex./E.A. = 1/1) 을 이용한 정제 과정을 거쳐 목적화합물 (9.7 g) 을 82 % 수율로 획득한다. After dissolving the second-stage compound (11.5 g, 20 mmol) in DMF (100 mL) under a nitrogen atmosphere, sodium acetate trihydrate (3.0 g, 22 mmol) and hydroxylamine HCl salt (1.5 g, 22 mmol) were added to 100
Figure pat00013
To increase the temperature. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature, and distilled water (100 mL) was added thereto for quenching. DCM (100 mL) was added and the extracted organic layer was washed 3 times with brine (100 mL) and distilled water (100 mL). The organic layer was treated with MgSO 4 , concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-Hex./EA = 1/1) to obtain the target compound (9.7 g) in 82% yield.

1H-NMR (δ, ppm), CDCl3: 9.56 (d, 1H), 8.80 (d, 1H), 8.34 (d, 1H), 8.29 (d, 1H), 7.85 (d, 1H), 7.83-7.47 (m, 5H), 7.44-7.21 (m, 6H), 4.46 (t, 2H), 3.85 (t, 2H), 3.79 (s, 3H), 3.72-3.58 (m, 4H), 2.33 (s, 3H). 1 H-NMR (δ, ppm), CDCl 3 : 9.56 (d, 1H), 8.80 (d, 1H), 8.34 (d, 1H), 8.29 (d, 1H), 7.85 (d, 1H), 7.83- 7.47 (m, 5H), 7.44-7.21 (m, 6H), 4.46 (t, 2H), 3.85 (t, 2H), 3.79 (s, 3H), 3.72-3.58 (m, 4H), 2.33 (s, 3H).

4단계: ((((11-(2-(2-chloroethoxy)ethyl)-5-(2-methylbenzoyl)-11H-benzo[a]carbazol-8-yl)(4-methoxyphenyl)methylene)amino)oxy)ethanone 합성Step 4: ((((11-(2-(2-chloroethoxy)ethyl)-5-(2-methylbenzoyl)-11H-benzo[a]carbazol-8-yl)(4-methoxyphenyl)methylene)amino)oxy )ethanone synthesis

질소 분위기하에서 상기 3단계 화합물 (5.9 g, 10 mmol) 을 DCM (40 mL) 에 녹인 후, acetic anhydride (1.5 g, 15 mmol) 을 서서히 적하한다. 적하 완료 후 반응 용기를 알루미늄 호일을 이용하여 빛을 차단하고 12 시간 동안 실온에서 교반한다. 반응 종결을 TLC 로 확인한 후, 반응액에 증류수 (100 mL)와 DCM (60 mL)을 투입한다. 수득된 유기층을 증류수 (100 mL) 로 3 회 수세한 후, 감압 조건에서 농축한다. 농축액은 실리카젤 컬럼 크로마토그래피 (n-Hex./E.A. = 1/1) 을 이용한 정제 과정을 거쳐 목적화합물 (5.5 g) 을 87 % 수율로 획득한다. After dissolving the third-step compound (5.9 g, 10 mmol) in DCM (40 mL) under a nitrogen atmosphere, acetic anhydride (1.5 g, 15 mmol) was slowly added dropwise. After completion of the dropping, the reaction vessel was blocked from light using aluminum foil, and stirred at room temperature for 12 hours. After confirming the completion of the reaction by TLC, distilled water (100 mL) and DCM (60 mL) were added to the reaction solution. The obtained organic layer was washed 3 times with distilled water (100 mL), and then concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography (n-Hex./E.A. = 1/1) to obtain the target compound (5.5 g) in 87% yield.

1H-NMR (δ, ppm), CDCl3: 9.57 (d, 1H), 8.82 (d, 1H), 8.35 (d, 1H), 8.31 (d, 1H), 7.86 (d, 1H), 7.85-7.47 (m, 5H), 7.47-7.21 (m, 6H), 4.47 (t, 2H), 3.86 (t, 2H), 3.81 (s, 3H), 3.74-3.58 (m, 4H), 2.35 (s, 3H), 2.31 (s, 3H). 1 H-NMR (δ, ppm), CDCl 3 : 9.57 (d, 1H), 8.82 (d, 1H), 8.35 (d, 1H), 8.31 (d, 1H), 7.86 (d, 1H), 7.85- 7.47 (m, 5H), 7.47-7.21 (m, 6H), 4.47 (t, 2H), 3.86 (t, 2H), 3.81 (s, 3H), 3.74-3.58 (m, 4H), 2.35 (s, 3H), 2.31 (s, 3H).

화학식 1-2 내지 1-8 로 표현되는 옥심 에스테르 벤조알파카바졸 유도체 화합물들은 염기 존재 하에서 벤조알파카바졸 고리 내 질소 원자와 1-chloro-2-(2-chloroethoxy)ethane과의 SN2 반응으로부터 준비된 11-(2-(2-chloroethoxy)ethyl)-11H-benzo[α]carbazole 을 출발물질로 하여 실시예　1의 제조방법에 준하여 표 1과 같이 합성한다.Oxime ester represented by the formula 1-2 to 1-8 benzo alpha carbazole derivative compounds in the presence of a base benzo alpha carbazole ring nitrogen atom and 1-chloro-2- (2- chloroethoxy) ethane and the S N 2 reaction Using 11-(2-(2-chloroethoxy)ethyl)-11H-benzo[α]carbazole prepared from as a starting material, it was synthesized as shown in Table 1 according to the preparation method of Example 1.

화학식 No.Chemical formula No. Ar1 Ar 1 Ar2 Ar 2 R1 R 1 1H-NMR (δ, ppm) 1 H-NMR (δ, ppm) 1-21-2

Figure pat00014
Figure pat00014
Figure pat00015
Figure pat00015
 CH3 CH 3 9.52 (d, 1H), 8.61 (d, 1H), 8.36 (d, 1H), 8.32 (d, 1H), 7.87 (d, 1H), 7.81-7.47 (m, 5H), 7.40-7.16 (m, 6H), 4.48 (t, 2H), 3.88 (t, 2H), 3.73-3.60 (m, 4H), 2.35 (s, 3H), 2.30 (s, 3H).9.52 (d, 1H), 8.61 (d, 1H), 8.36 (d, 1H), 8.32 (d, 1H), 7.87 (d, 1H), 7.81-7.47 (m, 5H), 7.40-7.16 (m, 6H), 4.48 (t, 2H), 3.88 (t, 2H), 3.73-3.60 (m, 4H), 2.35 (s, 3H), 2.30 (s, 3H). 1-31-3
Figure pat00016
Figure pat00016
Figure pat00017
Figure pat00017
 CH3 CH 3 9.53 (d, 1H), 8.60 (d, 1H), 8.35 (d, 1H), 8.30 (d, 1H), 7.89 (d, 1H), 7.83-7.49 (m, 6H), 7.42-7.18 (m, 6H), 4.47 (t, 2H), 3.86 (t, 2H), 3.73-3.58 (m, 4H), 2.33 (s, 3H), 2.27 (s, 3H).9.53 (d, 1H), 8.60 (d, 1H), 8.35 (d, 1H), 8.30 (d, 1H), 7.89 (d, 1H), 7.83-7.49 (m, 6H), 7.42-7.18 (m, 6H), 4.47 (t, 2H), 3.86 (t, 2H), 3.73-3.58 (m, 4H), 2.33 (s, 3H), 2.27 (s, 3H). 1-41-4
Figure pat00018
Figure pat00018
Figure pat00019
Figure pat00019
 C5H5 C 5 H 5 9.52 (d, 1H), 8.59 (d, 1H), 8.33 (d, 1H), 8.28 (d, 1H), 7.88 (d, 1H), 7.76-7.12 (m, 17H), 4.46 (t, 2H), 3.84 (t, 2H), 3.81 (s, 3H), 3.71-3.57 (m, 4H), 2.32 (s, 3H), 2.29 (s, 3H).9.52 (d, 1H), 8.59 (d, 1H), 8.33 (d, 1H), 8.28 (d, 1H), 7.88 (d, 1H), 7.76-7.12 (m, 17H), 4.46 (t, 2H) , 3.84 (t, 2H), 3.81 (s, 3H), 3.71-3.57 (m, 4H), 2.32 (s, 3H), 2.29 (s, 3H). 1-51-5
Figure pat00020
Figure pat00020
Figure pat00021
Figure pat00021
 CH3 CH 3 9.52 (d, 1H), 8.63 (d, 1H), 8.37 (d, 1H), 8.32 (d, 1H), 7.88 (d, 1H), 7.79-7.47 (m, 5H), 7.40-7.16 (m, 6H), 4.46 (t, 2H), 3.85 (t, 2H), 3.82 (s, 3H), 3.73-3.60 (m, 4H), 2.49 (s, 3H), 2.38 (s, 3H), 2.28 (s, 3H), 2.28 (s, 6H).9.52 (d, 1H), 8.63 (d, 1H), 8.37 (d, 1H), 8.32 (d, 1H), 7.88 (d, 1H), 7.79-7.47 (m, 5H), 7.40-7.16 (m, 6H), 4.46 (t, 2H), 3.85 (t, 2H), 3.82 (s, 3H), 3.73-3.60 (m, 4H), 2.49 (s, 3H), 2.38 (s, 3H), 2.28 (s , 3H), 2.28 (s, 6H). 1-61-6
Figure pat00022
Figure pat00022
Figure pat00023
Figure pat00023
 CH3 CH 3 9.52 (d, 1H), 8.62 (d, 1H), 8.37 (d, 1H), 8.31 (d, 1H), 7.88 (d, 1H), 7.82-7.48 (m, 5H), 7.42-7.15 (m, 6H), 4.49 (t, 2H), 3.87 (t, 2H), 3.75-3.62 (m, 4H), 2.34 (s, 3H), 2.29 (s, 3H), 2.27 (s, 6H).9.52 (d, 1H), 8.62 (d, 1H), 8.37 (d, 1H), 8.31 (d, 1H), 7.88 (d, 1H), 7.82-7.48 (m, 5H), 7.42-7.15 (m, 6H), 4.49 (t, 2H), 3.87 (t, 2H), 3.75-3.62 (m, 4H), 2.34 (s, 3H), 2.29 (s, 3H), 2.27 (s, 6H). 1-71-7
Figure pat00024
Figure pat00024
Figure pat00025
Figure pat00025
 CH3 CH 3 9.53 (d, 1H), 8.59 (d, 1H), 8.34 (d, 1H), 8.30 (d, 1H), 7.88 (d, 1H), 7.83-7.49 (m, 6H), 7.42-7.18 (m, 6H), 4.46 (t, 2H), 3.85 (t, 2H), 3.79 (s, 3H), 3.72-3.58 (m, 4H), 2.34 (s, 3H), 2.30 (s, 3H), 2.28 (s, 6H).9.53 (d, 1H), 8.59 (d, 1H), 8.34 (d, 1H), 8.30 (d, 1H), 7.88 (d, 1H), 7.83-7.49 (m, 6H), 7.42-7.18 (m, 6H), 4.46 (t, 2H), 3.85 (t, 2H), 3.79 (s, 3H), 3.72-3.58 (m, 4H), 2.34 (s, 3H), 2.30 (s, 3H), 2.28 (s , 6H). 1-81-8
Figure pat00026
Figure pat00026
Figure pat00027
Figure pat00027
 C5H5 C 5 H 5 9.51 (d, 1H), 8.59 (d, 1H), 8.32 (d, 1H), 8.28 (d, 1H), 7.88 (d, 1H), 7.75-7.12 (m, 17H), 4.47 (t, 2H), 3.85 (t, 2H), 3.81 (s, 3H), 3.71-3.55 (m, 4H), 2.31 (s, 3H), 2.28 (s, 3H).9.51 (d, 1H), 8.59 (d, 1H), 8.32 (d, 1H), 8.28 (d, 1H), 7.88 (d, 1H), 7.75-7.12 (m, 17H), 4.47 (t, 2H) , 3.85 (t, 2H), 3.81 (s, 3H), 3.71-3.55 (m, 4H), 2.31 (s, 3H), 2.28 (s, 3H).

실시예 2 에 기재된 합성법을 적용 시, 화학식 1-10 내지 1-16 의 구조When applying the synthesis method described in Example 2, the structure of formulas 1-10 to 1-16

에 상응하는 Ar1, Ar2 및 R1 를 도입하면 화학식 1-10 내지 1-16 화합물의 제조가 가능하다. Introducing the corresponding Ar 1 , Ar 2 and R 1 to prepare compounds of Formulas 1-10 to 1-16.

[실시예 2: 화학식 1-9 화합물의 합성][Example 2: Synthesis of Compound 1-9]

Figure pat00028
Figure pat00028

1 단계: 11-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-11H-benzo[α]carbazole 의 합성Step 1: Synthesis of 11-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-11H-benzo[α]carbazole

질소분위기 하에서 DMF (150 mL) 에 11H-benzo[α]carbazole (14.1 g, 65 mmol) 을 가하고 0 ℃ 에서 sodium hydride (3.1 g, 130 mmol) 을 투입한 다음 30 분간 교반한다. 반응액에 1,2-bis(2-chloroethoxy)ethane (24.2 g, 130 mmol) 을 가하고 2 시간 교반한다. TLC로 반응 종결을 확인한 후 반응액을 상온으로 승온하고 DCM (150 mL) 를 투입한 후 brine (200 mL) 으로 세척하여 추출한다. 추출된 유기층에 대해서 3 회에 걸쳐 증류수 (150 mL X 3 회) 를 투입하여 세척한다. 유기층을 MgSO4로 처리하고 감압 농축한 후 농축액은 실리카젤 컬럼 크로마토그래피 (n-Hex./E.A. = 2/1)을 이용한 정제 과정을 거쳐 목적화합물 (21.2 g) 을 89 % 수율로 획득한다. In a nitrogen atmosphere, 11H-benzo[α]carbazole (14.1 g, 65 mmol) was added to DMF (150 mL), sodium hydride (3.1 g, 130 mmol) was added at 0 ℃, followed by stirring for 30 minutes. 1,2-bis(2-chloroethoxy)ethane (24.2 g, 130 mmol) was added to the reaction solution and stirred for 2 hours. After confirming the completion of the reaction by TLC, the reaction solution was heated to room temperature, DCM (150 mL) was added, and then washed with brine (200 mL) and extracted. Distilled water (150 mL X 3 times) was added to the extracted organic layer 3 times and washed. The organic layer was treated with MgSO 4 and concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-Hex./EA = 2/1) to obtain the target compound (21.2 g) in 89% yield.

1H-NMR (δ, ppm), CDCl3: 8.55 (d/d, 1H), 8.14 (d, 1H), 8.11 (d, 1H), 8.00 (d, 1H), 7.63 (d, 1H), 7.44-7.29 (m, 4H), 7.24 (m, 1H), 4.48 (t, 2H), 3.85 (t, 2H), 3.75-3.60 (m, 8H). 1 H-NMR (δ, ppm), CDCl 3 : 8.55 (d/d, 1H), 8.14 (d, 1H), 8.11 (d, 1H), 8.00 (d, 1H), 7.63 (d, 1H), 7.44-7.29 (m, 4H), 7.24 (m, 1H), 4.48 (t, 2H), 3.85 (t, 2H), 3.75-3.60 (m, 8H).

2 단계: (11-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-5-(2-methylbenzoyl)-11H-benzo[a]carbazol-8-yl)(4-methoxyphenyl)methanone 합성Step 2: Synthesis of (11-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-5-(2-methylbenzoyl)-11H-benzo[a]carbazol-8-yl)(4-methoxyphenyl)methanone

질소분위기 하에서 DCM (100 mL) 에 상기 1단계 화합물 (18.4 g, 50 mmol) 을 녹인 용액에 대해 2-methylbenzoyl chloride (8.5 g, 55 mmol) 와 aluminum chloride (6.7 g, 55 mmol) 을 0

Figure pat00029
에서 적가한다. 반응액을 실온에서 교반하면서 TLC로 반응이 완료된 것을 확인한 후, 반응액을 0
Figure pat00030
로 냉각하고 4-methoxybenzoyl chloride (9.4 g, 55 mmol) 와 aluminum chloride (6.7 g, 55 mmol) 을 적가한다. 반응액을 실온에서 교반하면서 TLC로 반응이 완료된 것을 확인한 후, 강교반하면서 ice-water (400 mL) 에 반응액을 서서히 적가한다. DCM (200 mL) 가한 후 유기층을 brine (200 mL) 으로 세척하여 추출한다. 추출된 유기층에 대해서 증류수 (100 mL X 3 회) 를 투입하여 세척한다. 유기층을 MgSO4로 처리하고 감압 농축한 후 농축액은 실리카젤 컬럼 크로마토그래피 (n-Hex./E.A. = 1/1)을 이용한 정제 과정을 거쳐 목적화합물 (25.4 g) 을 82 % 수율로 획득한다. 2-methylbenzoyl chloride (8.5 g, 55 mmol) and aluminum chloride (6.7 g, 55 mmol) were added to the solution in which the first step compound (18.4 g, 50 mmol) was dissolved in DCM (100 mL) under a nitrogen atmosphere.
Figure pat00029
Dropwise from After confirming that the reaction was completed by TLC while stirring the reaction solution at room temperature,
Figure pat00030
After cooling with 4-methoxybenzoyl chloride (9.4 g, 55 mmol) and aluminum chloride (6.7 g, 55 mmol) is added dropwise. After confirming that the reaction is complete by TLC while stirring the reaction solution at room temperature, the reaction solution is slowly added dropwise to ice-water (400 mL) while stirring strongly. After DCM (200 mL) was added, the organic layer was washed with brine (200 mL) and extracted. Distilled water (100 mL X 3 times) was added to the extracted organic layer and washed. The organic layer was treated with MgSO 4 , concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-Hex./EA = 1/1) to obtain the target compound (25.4 g) in 82% yield.

1H-NMR (δ, ppm), CDCl3: 9.57 (d, 1H), 8.83 (d, 1H), 8.36 (d, 1H), 8.31 (d, 1H), 7.88 (d, 1H), 7.86-7.48 (m, 5H), 7.44-7.17 (m, 6H), 4.47 (t, 2H), 3.84 (t, 2H), 3.76 (s, 3H), 3.72-3.60 (m, 8H), 2.35 (s, 3H). 1 H-NMR (δ, ppm), CDCl 3 : 9.57 (d, 1H), 8.83 (d, 1H), 8.36 (d, 1H), 8.31 (d, 1H), 7.88 (d, 1H), 7.86- 7.48 (m, 5H), 7.44-7.17 (m, 6H), 4.47 (t, 2H), 3.84 (t, 2H), 3.76 (s, 3H), 3.72-3.60 (m, 8H), 2.35 (s, 3H).

3단계: (11-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-8-((hydroxyimino)(4-methoxyphenyl)methyl)-11H-benzo[a]carbazol-5-yl)(o-tolyl)methanone 합성Step 3: (11-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-8-((hydroxyimino)(4-methoxyphenyl)methyl)-11H-benzo[a]carbazol-5-yl)(o -tolyl)methanone synthesis

질소분위기 하에서 DMF (100 mL) 에 상기 2단계 화합물 (12.4 g, 20 mmol) 을 녹인 후, sodium acetate trihydrate (3.0 g, 22 mmol) 과 hydroxylamine HCl salt (1.5 g, 22 mmol) 을 넣고 100

Figure pat00031
로 승온한다. TLC 로 반응이 완료된 것을 확인한 후, 반응액을 실온으로 냉각하고 증류수 (100 mL)를 투입하여 quenching 한다. DCM (100 mL)을 투입하여 추출한 유기층을 brine (100 mL) 과 증류수 (100 mL)로 3 회 세척한다. 유기층을 MgSO4로 처리하고 감압 농축한 후 농축액은 실리카젤 컬럼 크로마토그래피 (n-Hex./E.A. = 1/1) 을 이용한 정제 과정을 거쳐 목적화합물 (10.8 g) 을 85 % 수율로 획득한다. After dissolving the second-stage compound (12.4 g, 20 mmol) in DMF (100 mL) under a nitrogen atmosphere, sodium acetate trihydrate (3.0 g, 22 mmol) and hydroxylamine HCl salt (1.5 g, 22 mmol) were added.
Figure pat00031
To increase the temperature. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature, and distilled water (100 mL) was added to perform quenching. Add DCM (100 mL) and wash the extracted organic layer 3 times with brine (100 mL) and distilled water (100 mL). The organic layer was treated with MgSO 4 and concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-Hex./EA = 1/1) to obtain the target compound (10.8 g) in 85% yield.

1H-NMR (δ, ppm), CDCl3: 9.56 (d, 1H), 8.81 (d, 1H), 8.37 (d, 1H), 8.29 (d, 1H), 7.85 (d, 1H), 7.84-7.42 (m, 5H), 7.41-7.10 (m, 6H), 4.48 (t, 2H), 3.85 (t, 2H), 3.74 (s, 3H), 3.71-3.60 (m, 8H), 2.34 (s, 3H). 1 H-NMR (δ, ppm), CDCl 3 : 9.56 (d, 1H), 8.81 (d, 1H), 8.37 (d, 1H), 8.29 (d, 1H), 7.85 (d, 1H), 7.84- 7.42 (m, 5H), 7.41-7.10 (m, 6H), 4.48 (t, 2H), 3.85 (t, 2H), 3.74 (s, 3H), 3.71-3.60 (m, 8H), 2.34 (s, 3H).

4단계: ((((11-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-5-(2-methylbenzoyl)Step 4: ((((11-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-5-(2-methylbenzoyl)

-11H-benzo[a]carbazol-8-yl)(4 methoxyphenyl)methylene)amino)oxy)-11H-benzo[a]carbazol-8-yl)(4 methoxyphenyl)methylene)amino)oxy)

ethanone 합성ethanone synthesis

질소 분위기하에서 상기 3단계 화합물 (6.3 g, 10 mmol) 을 DCM (40 mL) 에 녹인 후, acetic anhydride (1.5 g, 15 mmol) 을 서서히 적하한다. 적하 완료 후 반응 용기를 알루미늄 호일을 이용하여 빛을 차단하고 12 시간 동안 실온에서 교반한다. 반응 종결을 TLC 로 확인한 후, 반응액에 증류수 (100 mL) 와 DCM (60 mL) 을 투입한다. 수득된 유기층을 증류수 (100 mL) 로 3 회 수세한 후, 감압 조건에서 농축한다. 농축액은 실리카젤 컬럼 크로마토그래피 (n-Hex./E.A. = 1/1) 을 이용한 정제 과정을 거쳐 목적화합물 (5.5 g) 을 82 % 수율로 획득한다. After dissolving the third-step compound (6.3 g, 10 mmol) in DCM (40 mL) under a nitrogen atmosphere, acetic anhydride (1.5 g, 15 mmol) was slowly added dropwise. After completion of the dropping, the reaction vessel was blocked from light using aluminum foil, and stirred at room temperature for 12 hours. After confirming the completion of the reaction by TLC, distilled water (100 mL) and DCM (60 mL) were added to the reaction solution. The obtained organic layer was washed 3 times with distilled water (100 mL) and then concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography (n-Hex./E.A. = 1/1) to obtain the target compound (5.5 g) in 82% yield.

1H-NMR (δ, ppm), CDCl3: 9.58 (d, 1H), 8.83 (d, 1H), 8.38 (d, 1H), 8.30 (d, 1H), 7.86 (d, 1H), 7.86-7.41 (m, 5H), 7.43-7.10 (m, 6H), 4.49 (t, 2H), 3.86 (t, 2H), 3.74 (s, 3H), 3.72-3.59 (m, 8H), 2.36 (s, 3H), 2.27 (s, 3H). 1 H-NMR (δ, ppm), CDCl 3 : 9.58 (d, 1H), 8.83 (d, 1H), 8.38 (d, 1H), 8.30 (d, 1H), 7.86 (d, 1H), 7.86- 7.41 (m, 5H), 7.43-7.10 (m, 6H), 4.49 (t, 2H), 3.86 (t, 2H), 3.74 (s, 3H), 3.72-3.59 (m, 8H), 2.36 (s, 3H), 2.27 (s, 3H).

화학식 1-10 내지 1-16 으로 표현되는 옥심 에스테르 벤조알파카바졸 유도체 화합물들은 염기 존재 하에서 벤조알파카바졸 고리 내 질소 원자와 1,2-bis(2-chloroethoxy)ethane 과의 SN2 반응으로부터 준비된 11-(2-(2-(2-chloro ethoxy)ethoxy)ethyl)-11H-benzo[α]carbazole 을 출발물질로 하여 실시예　2의 제조방법에 준하여 표 2와 같이 합성한다.Benzoin oxime ester represented by the formula 1-10 to 1-16 alpha carbazole derivative compounds in the presence of a base benzo alpha carbazole ring nitrogen atoms and 1,2-bis (2-chloroethoxy) from S N 2 reaction with ethane Using the prepared 11-(2-(2-(2-chloro ethoxy)ethoxy)ethyl)-11H-benzo[α]carbazole as a starting material, it was synthesized as shown in Table 2 according to the preparation method of Example 2.

화학식 No.Chemical formula No. Ar1 Ar 1 Ar2 Ar 2 R1 R 1 1H-NMR (δ, ppm) 1 H-NMR (δ, ppm) 1-101-10

Figure pat00032
Figure pat00032
Figure pat00033
Figure pat00033
 CH3 CH 3 9.54 (d, 1H), 8.60 (d, 1H), 8.37 (d, 1H), 8.31 (d, 1H), 7.85 (d, 1H), 7.80-7.45 (m, 5H), 7.42-7.16 (m, 6H), 4.49 (t, 2H), 3.87 (t, 2H), 3.75 (s, 3H), 3.71-3.58 (m, 8H), 2.35 (s, 3H), 2.27 (s, 3H).9.54 (d, 1H), 8.60 (d, 1H), 8.37 (d, 1H), 8.31 (d, 1H), 7.85 (d, 1H), 7.80-7.45 (m, 5H), 7.42-7.16 (m, 6H), 4.49 (t, 2H), 3.87 (t, 2H), 3.75 (s, 3H), 3.71-3.58 (m, 8H), 2.35 (s, 3H), 2.27 (s, 3H). 1-111-11
Figure pat00034
Figure pat00034
Figure pat00035
Figure pat00035
 CH3 CH 3 9.53 (d, 1H), 8.61 (d, 1H), 8.34 (d, 1H), 8.31 (d, 1H), 7.88 (d, 1H), 7.82-7.49 (m, 6H), 7.42-7.18 (m, 6H), 4.47 (t, 2H), 3.84 (t, 2H), 3.75 (s, 3H), 3.71-3.59 (m, 8H), 2.34 (s, 3H), 2.25 (s, 3H).9.53 (d, 1H), 8.61 (d, 1H), 8.34 (d, 1H), 8.31 (d, 1H), 7.88 (d, 1H), 7.82-7.49 (m, 6H), 7.42-7.18 (m, 6H), 4.47 (t, 2H), 3.84 (t, 2H), 3.75 (s, 3H), 3.71-3.59 (m, 8H), 2.34 (s, 3H), 2.25 (s, 3H). 1-121-12
Figure pat00036
Figure pat00036
Figure pat00037
Figure pat00037
 C5H5 C 5 H 5 9.51 (d, 1H), 8.59 (d, 1H), 8.33 (d, 1H), 8.27 (d, 1H), 7.87 (d, 1H), 7.72-7.10 (m, 17H), 4.46 (t, 2H), 3.84 (t, 2H), 3.73 (s, 3H), 3.71-3.58 (m, 8H), 2.34 (s, 3H), 2.30 (s, 3H).9.51 (d, 1H), 8.59 (d, 1H), 8.33 (d, 1H), 8.27 (d, 1H), 7.87 (d, 1H), 7.72-7.10 (m, 17H), 4.46 (t, 2H) , 3.84 (t, 2H), 3.73 (s, 3H), 3.71-3.58 (m, 8H), 2.34 (s, 3H), 2.30 (s, 3H). 1-131-13
Figure pat00038
Figure pat00038
Figure pat00039
Figure pat00039
 CH3 CH 3 9.50 (d, 1H), 8.61 (d, 1H), 8.37 (d, 1H), 8.32 (d, 1H), 7.88 (d, 1H), 7.79-7.49 (m, 5H), 7.40-7.13 (m, 6H), 4.48 (t, 2H), 3.84 (t, 2H), 3.71-3.60 (m, 8H), 2.35 (s, 3H), 2.30 (s, 3H), 2.28 (s, 6H).9.50 (d, 1H), 8.61 (d, 1H), 8.37 (d, 1H), 8.32 (d, 1H), 7.88 (d, 1H), 7.79-7.49 (m, 5H), 7.40-7.13 (m, 6H), 4.48 (t, 2H), 3.84 (t, 2H), 3.71-3.60 (m, 8H), 2.35 (s, 3H), 2.30 (s, 3H), 2.28 (s, 6H). 1-141-14
Figure pat00040
Figure pat00040
Figure pat00041
Figure pat00041
 CH3 CH 3 9.52 (d, 1H), 8.62 (d, 1H), 8.37 (d, 1H), 8.31 (d, 1H), 7.88 (d, 1H), 7.82-7.48 (m, 5H), 7.42-7.15 (m, 6H), 4.50 (t, 2H), 3.86 (t, 2H), 3.74-3.61 (m, 8H), 2.34 (s, 3H), 2.31 (s, 3H), 2.28 (s, 6H), 2.26 (s, 3H).9.52 (d, 1H), 8.62 (d, 1H), 8.37 (d, 1H), 8.31 (d, 1H), 7.88 (d, 1H), 7.82-7.48 (m, 5H), 7.42-7.15 (m, 6H), 4.50 (t, 2H), 3.86 (t, 2H), 3.74-3.61 (m, 8H), 2.34 (s, 3H), 2.31 (s, 3H), 2.28 (s, 6H), 2.26 (s , 3H). 1-151-15
Figure pat00042
Figure pat00042
Figure pat00043
Figure pat00043
 CH3 CH 3 9.51 (d, 1H), 8.59 (d, 1H), 8.34 (d, 1H), 8.30 (d, 1H), 7.88 (d, 1H), 7.83-7.49 (m, 6H), 7.42-7.18 (m, 6H), 4.48 (t, 2H), 3.84 (t, 2H), 3.75 (s, 3H), 3.71-3.60 (m, 8H), 2.35 (s, 3H), 2.30 (s, 3H), 2.28 (s, 6H).9.51 (d, 1H), 8.59 (d, 1H), 8.34 (d, 1H), 8.30 (d, 1H), 7.88 (d, 1H), 7.83-7.49 (m, 6H), 7.42-7.18 (m, 6H), 4.48 (t, 2H), 3.84 (t, 2H), 3.75 (s, 3H), 3.71-3.60 (m, 8H), 2.35 (s, 3H), 2.30 (s, 3H), 2.28 (s , 6H). 1-161-16
Figure pat00044
Figure pat00044
Figure pat00045
Figure pat00045
 C5H5 C 5 H 5 9.50 (d, 1H), 8.57 (d, 1H), 8.31 (d, 1H), 8.29 (d, 1H), 7.87 (d, 1H), 7.75-7.10 (m, 17H), 4.45 (t, 2H), 3.83 (t, 2H), 3.74 (s, 3H), 3.70-3.58 (m, 8H), 2.33 (s, 3H), 2.29 (s, 3H), 2.26 (s, 6H).9.50 (d, 1H), 8.57 (d, 1H), 8.31 (d, 1H), 8.29 (d, 1H), 7.87 (d, 1H), 7.75-7.10 (m, 17H), 4.45 (t, 2H) , 3.83 (t, 2H), 3.74 (s, 3H), 3.70-3.58 (m, 8H), 2.33 (s, 3H), 2.29 (s, 3H), 2.26 (s, 6H).

본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있는 것으로, 본 발명을 이에 한정하는 것은 아니다.The embodiments according to the present invention may be modified in various different forms, and the present invention is not limited thereto.

참고로, 비교예 1의 경우 BASF사의 OXE-01이며 비교예　2의 경우 BASF사의 OXE-02이다.For reference, Comparative Example 1 is BASF's OXE-01, and Comparative Example 2 is BASF's OXE-02.

Figure pat00046
Figure pat00046

비교예 1（OXE-01)Comparative Example 1 (OXE-01)

비교예 2（OXE-02)Comparative Example 2 (OXE-02)

앞서 반응식 1의 제조법을 통해서 준비된 옥심 에스테르 벤조알파카바졸 화합물, 1-1 내지 1-16을 광중합 개시제로 사용하여 아래와 같은 감광성 조성물을 조제한다. 또 한 비교예 1 (BASF사 OXE-01) 및 비교예 2 (BASF사 OXE-02)를 동일한 조성물에 대한 광중합 개시제로 사용한다.Using the oxime ester benzoalphacarbazole compounds, 1-1 to 1-16, prepared through the preparation method of Scheme 1 as a photopolymerization initiator, a photosensitive composition as follows is prepared. In addition, Comparative Example 1 (OXE-01 by BASF) and Comparative Example 2 (OXE-02 by BASF) were used as photopolymerization initiators for the same composition.

[화학식 1-1 내지 1-16을 포함하는 감광성 수지 조성물과 비교예 1과 2를 포함하는 감광성 수지 조성물의 제조][Preparation of a photosensitive resin composition comprising Formulas 1-1 to 1-16 and a photosensitive resin composition comprising Comparative Examples 1 and 2]

교반기가 설치되어 있는 반응 혼합조에 하기 표 3에 기재된 성분과 함량에 따라 프로필렌글리콜메틸에테르아세테이트(PGMEA ; Propyrene Glycol Methyl Ether Acetate) 및 폴리히드록시스티렌수지(PHS); 디펜타에리트리톨헥사아크릴레이트(DPHA); 광개시제를 순차적으로 첨가하고, 상온에서 교반하여 감광성 수지 조성물을 제조한다.Propylene glycol methyl ether acetate (PGMEA; Propyrene Glycol Methyl Ether Acetate) and polyhydroxystyrene resin (PHS) according to the components and contents shown in Table 3 in a reaction mixing tank equipped with a stirrer; Dipentaerythritol hexaacrylate (DPHA); A photoinitiator is sequentially added and stirred at room temperature to prepare a photosensitive resin composition.

PHS : 알드리치사 (폴리 4-히드록시페놀), Mw=25,000PHS: Aldrich (poly 4-hydroxyphenol), Mw=25,000

DPHA : 알드리치사 디펜타에리트리톨헥사아크릴레이DPHA: Aldrich Dipentaerythritol Hexaacrylate

광개시제(g)Photoinitiator (g) PHS(g)PHS(g) DPHA(g)DPHA(g) PGMEA(g)PGMEA(g) 화학식 1-1Formula 1-1 2020 1010 6969 화학식 1-2Formula 1-2 2020 1010 6969 화학식 1-3Formula 1-3 2020 1010 6969 화학식 1-4Formula 1-4 2020 1010 6969 화학식 1-5Formula 1-5 2020 1010 6969 화학식 1-6Formula 1-6 2020 1010 6969 화학식 1-7Formula 1-7 2020 1010 6969 화학식 1-8Formula 1-8 2020 1010 6969 화학식 1-9Formula 1-9 2020 1010 6969 화학식 1-10Formula 1-10 2020 1010 6969 화학식 1-11Formula 1-11 2020 1010 6969 화학식 1-12Formula 1-12 2020 1010 6969 화학식 1-13Formula 1-13 2020 1010 6969 화학식 1-14Formula 1-14 2020 1010 6969 화학식 1-15Formula 1-15 2020 1010 6969 화학식 1-16Formula 1-16 2020 1010 6969 비교예 1Comparative Example 1 2020 1010 6969 비교예 2Comparative Example 2 2020 1010 6969

[시험예] [Test Example]

감도 평가Sensitivity evaluation

상기 제조된 옥심 에스테르계 광개시제와 비교예 1 내지 2에서 제조한 감광성 수지 조성물의 평가는 유리기판 위에 건조 후 막 두께가 5 um이 되도록 코팅하고, 120 ℃에서 2 분간 건조하여 용제를 휘발시킨다. 퓨전램프로 노광하고 23 ℃에서 0.045 % KOH 수용액에 현상한 후 두께를 비접촉식 두께 측정기를 이용하여 초기 두께 대비 80 %를 유지하는 노광량을 기준으로 감도를 측정한다 (표 4). Evaluation of the prepared oxime ester photoinitiator and the photosensitive resin composition prepared in Comparative Examples 1 to 2 was coated on a glass substrate so that the film thickness was 5 um after drying, and dried at 120° C. for 2 minutes to volatilize the solvent. After exposure with a fusion lamp and developing in 0.045% KOH aqueous solution at 23°C, the sensitivity is measured based on the exposure amount maintaining 80% of the initial thickness using a non-contact thickness gauge (Table 4).

광개시제(g)Photoinitiator (g) 감도 (mJ/cm2)Sensitivity (mJ/cm2) 화학식 1-1Formula 1-1 2020 화학식 1-2Formula 1-2 2020 화학식 1-3Formula 1-3 2020 화학식 1-4Formula 1-4 2525 화학식 1-5Formula 1-5 2020 화학식 1-6Formula 1-6 2020 화학식 1-7Formula 1-7 2020 화학식 1-8Formula 1-8 2525 화학식 1-9Formula 1-9 2525 화학식 1-10Formula 1-10 2525 화학식 1-11Formula 1-11 2525 화학식 1-12Formula 1-12 3030 화학식 1-13Formula 1-13 2525 화학식 1-14Formula 1-14 2525 화학식 1-15Formula 1-15 2525 화학식 1-16Formula 1-16 3030 비교예 1 Comparative Example 1 8080 비교예 2 Comparative Example 2 6060

Claims (7)

하기 화학식 1로 표시되는 옥심에스테르 벤조알파카바졸 유도체 화합물로써,
[화학식 1]

Figure pat00047


상기 화학식에서 X는 Cl 또는 Br이며, n은 1 단위체 내지 3 단위체 할로에틸에테르이다. Ar1 또는 Ar2 는 C6-C30 아릴에테르, C6-C30 할로아릴, C6-C30 아릴, C7-C30 아르알킬, C5-C30 헤테로아릴이며 R1 는 C1-C3 알킬 또는 페닐이다.
As an oxime ester benzoalphacarbazole derivative compound represented by the following formula (1),
[Formula 1]

Figure pat00047


In the above formula, X is Cl or Br, and n is 1 to 3 unit haloethyl ether. Ar 1 or Ar 2 is C 6 -C 30 aryl ether, C 6 -C 30 haloaryl, C 6 -C 30 aryl, C 7 -C 30 aralkyl, C 5 -C 30 heteroaryl and R 1 is C 1 -C 3 alkyl or phenyl.
 제 1항에 있어서, X는 Cl 또는 Br이며 보다 바람직하게는 Cl 이다. n은 1 단위체 내지 3 단위체 할로 에틸에테르이며 보다 바람직하게는 n은 1 단위체 내지 2 단위체 할로 에틸에테르이다. Ar1 또는 Ar2 는 C6-C12 아릴에테르, C6-C12 할로아릴, C6-C12 아릴, C7-C15 아르알킬이며R1 는 C1-C3 알킬 또는 페닐이며 보다 바람직하게는 메틸 및 페닐이다.
According to claim 1, X is Cl or Br, more preferably Cl. n is 1 to 3 unit halo ethyl ether, and more preferably n is 1 to 2 unit halo ethyl ether. Ar 1 or Ar 2 is C 6 -C 12 aryl ether, C 6 -C 12 haloaryl, C 6 -C 12 aryl, C 7 -C 15 aralkyl, and R 1 is C 1 -C 3 alkyl or phenyl. Preferably methyl and phenyl.
 Ar1 또는 Ar2 는 C6-C12 아릴에테르, C6-C12 할로아릴, C6-C12 아릴, C7-C15 아르알킬이며R1 는 C1-C3 알킬 또는 페닐이며 보다 바람직하게는 Ar1 또는 Ar2 는 오르소 또는 오르소와 메틸 및 파라 위치에 알킬기로 치환된 C6-C20 아릴이며 Ar1 또는 Ar2 는 C6-C20 아릴이나 오르소 또는 오르소와 메틸 및 파라 위치에 할로겐 및 에테르기로 치환된 C6-C20 아릴이다.
Ar 1 or Ar 2 is C 6 -C 12 aryl ether, C 6 -C 12 haloaryl, C 6 -C 12 aryl, C 7 -C 15 aralkyl, and R 1 is C 1 -C 3 alkyl or phenyl. Preferably, Ar 1 or Ar 2 is ortho or ortho and C 6 -C 20 aryl substituted with an alkyl group at the methyl and para position, and Ar 1 or Ar 2 is C 6 -C 20 aryl or ortho or ortho and It is a C 6 -C 20 aryl substituted with halogen and ether groups in the methyl and para positions.
 Ar1 또는 Ar2 는 오르소 위치에 메틸기로 치환된 페닐이나 오르소, 메타 및 파라 위치에 메틸기로 치환된 페닐이며 Ar1 또는 Ar2 는 오르소 위치에 Cl 또는 F 기로 치환된 페닐이나 파라 위치에 메틸, 에틸, 프로필, 이소프로필, 부틸, 펜틸, 이소펜틸기를 갖는 에테르 작용기를 포함한다.
Ar 1 or Ar 2 is phenyl substituted with a methyl group at the ortho position or phenyl substituted with a methyl group at the ortho, meta and para positions, and Ar 1 or Ar 2 is a phenyl or para position substituted with a Cl or F group at the ortho position And ether functional groups having methyl, ethyl, propyl, isopropyl, butyl, pentyl, and isopentyl groups.
 제 1항에 있어서, 상기 옥심에스테르 벤조알파카바졸 유도체 화합물을 광중합용 개시제로 사용하며 에틸렌계 불포화 결합을 가지는 화합물을 포함하는 감광성 수지 조성물.The photosensitive resin composition according to claim 1, wherein the oxime ester benzoalphacarbazole derivative compound is used as an initiator for photopolymerization and includes a compound having an ethylenically unsaturated bond. 제 1항에 있어서, 상기 옥심에스테르계 광개시제, 에틸렌계 불포화 결합을 가지는 화합물 및 현상성 바인더수지를 포함하는 감광성 수지 조성물.
The photosensitive resin composition according to claim 1, comprising the oxime ester photoinitiator, a compound having an ethylenically unsaturated bond, and a developable binder resin.
 제 1항에 있어서, 옥심에스테르 벤조알파카바졸 유도체 화합물이 하기 화학식 1-1 내지 1-16으로 표현되는 광개시제.
The photoinitiator of claim 1, wherein the oxime ester benzoalphacarbazole derivative compound is represented by the following formulas 1-1 to 1-16.
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