WO2021177653A1 - Novel oxime ester carbazole derivative compound - Google Patents
Novel oxime ester carbazole derivative compound Download PDFInfo
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- WO2021177653A1 WO2021177653A1 PCT/KR2021/002358 KR2021002358W WO2021177653A1 WO 2021177653 A1 WO2021177653 A1 WO 2021177653A1 KR 2021002358 W KR2021002358 W KR 2021002358W WO 2021177653 A1 WO2021177653 A1 WO 2021177653A1
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- acrylate
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- LOCXTTRLSIDGPS-AZPGRJICSA-N CCCCCC/C(/C(c(cc1)ccc1Sc1ccccc1)=O)=N\OC(c1ccccc1)=O Chemical compound CCCCCC/C(/C(c(cc1)ccc1Sc1ccccc1)=O)=N\OC(c1ccccc1)=O LOCXTTRLSIDGPS-AZPGRJICSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
Definitions
- a photoinitiator is a substance that absorbs light and decomposes to generate chemically active atoms or molecules, and is widely used in photosensitive compositions and the like.
- Examples of chemically active substances include acids, bases, and radicals.
- the photoinitiator in which radicals are generated may be used together with an acryl group that causes a polymerization reaction with the radical to improve the strength of the coated film.
- a photoinitiator may be applied to the photosensitive resin composition for photoetching using inkjet ink or a transparent or colored protective film such as a car or mobile phone, and a phenomenon in which solubility is reduced according to a polymerization reaction by light. have.
- Representative examples include a photopolymerization type photosensitive resin composition used for manufacturing a color filter of a liquid crystal display device, a photosensitive composition for a resin black matrix, and the like.
- the photosensitive composition can be used to form a pattern by applying on a substrate to form a coating film, exposing a specific portion of the coating film by light irradiation using a photomask or the like, and then developing and removing the unexposed portion.
- photoinitiator used in the photosensitive resin composition include various types of acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, and acylphosphine oxide derivatives.
- One embodiment of the present invention provides an oxime ester carbazole derivative compound useful as a photoinitiator by having excellent radical generation efficiency with a small exposure dose, excellent sensitivity, and improved solubility to sufficiently increase the concentration of the photoinitiator.
- Another embodiment of the present invention provides a photosensitive resin comprising the novel oxime ester carbazole derivative compound as a photoinitiator.
- an oxime ester carbazole derivative compound represented by the following formula (1).
- R 1 and R 3 are each independently a C1-C12 aliphatic hydrocarbon
- R 2 is C1 ⁇ C12 alkyl or C6 ⁇ C12 aryl
- n 1 to 2
- n is an integer from 1 to 5;
- a photosensitive resin composition comprising the oxime ester carbazole derivative compound and a compound having an ethylenically unsaturated bond.
- the novel oxime ester carbazole compound is useful as a photoinitiator with improved solubility to sufficiently increase the concentration of the photoinitiator, the novel oxime ester carbazole compound has excellent radical generation efficiency with a small exposure dose, excellent sensitivity, and sufficient concentration of the photoinitiator.
- R 1 and R 3 are each independently a C1-C12 aliphatic hydrocarbon
- R 2 is C1 ⁇ C12 alkyl or C6 ⁇ C12 aryl
- n 1 to 2
- n is an integer from 1 to 5;
- R 1 and R 3 may further improve solubility as the number of carbon atoms increases.
- the number of carbon atoms of R 1 and R 3 may be appropriately selected in consideration of both solubility and sensitivity to be implemented.
- R 1 and R 3 may each independently be a C7 ⁇ C12 aliphatic hydrocarbon.
- solubility may be further improved as n is larger.
- n may be an integer of 2 to 5.
- n may be an integer of 3 to 5.
- R 1 and R 3 when R 1 and R 3 are branched chain alkyl rather than straight chain alkyl, solubility may be further improved.
- R 1 and R 3 since R 1 and R 3 may be disadvantageous in terms of sensitivity when they are branched-chain alkyl rather than straight-chain alkyl, consider whether to introduce branched-chain alkyl as R 1 or R 3 in consideration of solubility and sensitivity to be implemented. can be appropriately selected.
- R 1 and R 3 may each independently be a straight-chain alkyl.
- R 2 may improve sensitivity as the number of carbon atoms decreases.
- R 2 may be methyl.
- the oxime ester carbazole derivative compound may be any one of the following compounds.
- a photosensitive resin composition comprising the photoinitiator, and the photoinitiator comprises the oxime ester carbazole derivative compound.
- the oxime ester carbazole derivative compound absorbs ultraviolet light and shows almost no color, has high radical generation efficiency, has excellent compatibility and stability with other components mixed in the photosensitive resin composition, and improves photopolymerization initiation efficiency do.
- the sensitivity during the pattern exposure process of the photosensitive resin composition to which the oxime ester carbazole derivative compound is applied as a photoinitiator is high, the exposure amount may not be increased, and thus the production amount may be increased.
- the photoinitiator has excellent radical generation efficiency with a small exposure amount, has excellent sensitivity, and exhibits improved solubility to sufficiently increase the concentration of the photoinitiator.
- the photosensitive resin composition may be manufactured for use in forming liquid crystal display devices such as TVs and monitors, in addition to uses such as laptops and mobiles, in response to the increasing and diversifying uses of LCDs.
- the photosensitive resin composition can quickly respond to light and mechanically implement excellent physical properties, thereby improving the productivity and durability of the applied product.
- the photosensitive resin composition may form a pattern by, for example, a photo-lithography method, or an insulating protective film may be formed through exposure of the entire surface.
- a property of rapidly reacting to light ie, photosensitivity
- the photoinitiator has excellent photosensitivity, excellent quality may be realized by a process by a photolithography method.
- a column spacer serving as a support or an overcoat and passivation film serving as a protective film may be formed by the photosensitive resin composition.
- Such column spacers, overcoats and passivation films should have excellent mechanical properties.
- the photoinitiator since the photoinitiator has excellent photosensitivity, it can be suitably applied to applications requiring excellent mechanical properties.
- the photosensitive resin composition may include a binder resin.
- the binder resin may include one selected from the group consisting of an acrylic acid-containing acrylic copolymer, a novolak-based phenol resin, a polyhydroxystyrene resin, a copolymer of hydroxystyrene and acrylate, and combinations thereof.
- the compound having the ethylenically unsaturated bond is, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylic Alkyl esters of (meth)acrylic acid such as lactate, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate having 2 to 14 ethylene oxide groups, ethylene glycol di(meth)acrylate, ethylene oxide group Polyethylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate, bisphenol A diglycidyl ether Acrylic acid adduct, phthalic acid diester of ⁇ -hydroxyethyl (meth)acrylate, toluene diisocyan
- the photosensitive resin may include a photopolymerizable compound.
- the photopolymerizable compound is a component for supplementing light efficiency, and the type thereof is not particularly limited, but may include an acrylic binder resin having an ethylenically unsaturated bond.
- the acrylic binder resin having an ethylenically unsaturated bond is a photocurable acrylic oligomer configured to enable a UV curing reaction by a chemical reaction between an acrylic oligomer precursor and a monomer for introducing an ethylenically unsaturated bond.
- the acrylic oligomer precursor may be a copolymer of a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms and a polymerizable monomer.
- the method for preparing the acrylic oligomer precursor is not particularly limited, and it can be prepared using methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization commonly used in the art, and bulk polymerization is preferred.
- the alkyl group of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms includes an aliphatic alkyl group and an aromatic alkyl group, and these monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) Acrylate, ethylhexyl (meth) acrylate, ethylbutyl (meth) acrylate, n-oct
- polymerizable monomer for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, 2-hydroxypropylene glycol (meth)acrylate and 4-hydroxybutyl vinyl ether a monomer having a hydroxyl group; and monomers having a carboxyl group such as (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid.
- the polymerizable monomers may be used alone or in combination of two or more.
- the kind of monomer for introducing the said ethylenically unsaturated bond is not specifically limited.
- an isocyanate-based monomer having an isocyanate group and a double bond in one molecule is used, for example, 2-isocyanatoethyl (meth)acrylate.
- a method for producing a photocurable acrylic oligomer preferably used as the photopolymerizable compound is not particularly limited. Specifically, for example, after preparing the acrylic oligomer precursor, 0.5 to 20 parts by weight of the isocyanate-based monomer and 0.001 to 0.5 parts by weight of the catalyst are added and reacted with respect to 100 parts by weight of the prepared acrylic oligomer precursor.
- the type of the catalyst is not particularly limited as long as it can promote the reaction between the hydroxyl group or the carboxyl group and the isocyanate group contained in the acrylic oligomer precursor, and for example, an organotin-based compound, an organic silver-based compound, or a mixture thereof may be used.
- the photopolymerizable compound may have a weight average molecular weight (in terms of polystyrene, Mw) of 200,000 to 1,000,000 measured by gel permeation chromatography (GPC).
- the photopolymerization initiator is included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the solid content of the photopolymerizable compound. If the content is less than 0.01 parts by weight, the overall degree of curing of the photopolymerizable composition is lowered, and when it exceeds 10 parts by weight, the transmittance of ultraviolet rays is lowered and the degree of curing in the deep part is lowered.
- the photosensitive composition may be polymerized and cured by irradiating light.
- the photosensitive composition can be applied to applications that can utilize these properties.
- the photosensitive composition may be applied to 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.
- the photosensitive composition may further include a solvent.
- the solvent used in the conventional photopolymerizable composition is not particularly limited.
- ethers aromatic hydrocarbons, ketones, alcohols, esters or amides are preferable.
- the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; and alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate
- esters examples include esters such as ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; and cyclic esters such as ⁇ -butyrolactone.
- an organic solvent having a boiling point of 100°C to 200°C in terms of applicability and drying properties, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and ethyl lactate. , butalactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.
- the photosensitive composition may further include other components such as additives suitable for its specific use.
- the additive may be, for example, a silane coupling agent for improving glass adhesion, or a leveling agent for improving flatness.
- Step 2 Synthesis of compound 2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone (2-2)
- the reactant is naturally heated to room temperature (20-25 °C) and stirred for at least 8 hours. After completion of the reaction, cold water is added to the reaction mixture and extracted with MC (x 3). The extracted organic layer was dried over anhydrous MgSO 4 , concentrated under reduced pressure, and purified by column with ethyl acetate (EA)/hexane to obtain a pale yellow solid 2.2 (29.4 g, 82 % yield).
- EA ethyl acetate
- Step 3 Compound (Z)-2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone oxime (2-1) synthesis of
- Step 2 Compound 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-2-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)ethanone ( 3-2) synthesis
- Step 3 Compound (Z)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-2-(4-(2,4,4-trimethylpentan-2-yl)phenoxy ) Synthesis of ethanone oxime (3-1)
- Step 3 Synthesis of compound (Z)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-2-(mesityloxy)ethanone oxime (4-1)
- Step 2 Synthesis of compound 2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone (5-2)
- Step 3 Compound (Z)-2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone oxime (5-1) synthesis of
- Step 2 Compound 2-(4-(tert-butyl)-2-methylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone (6-2) synthesis
- Step 3 Compound (Z)-2-(4-(tert-butyl)-2-methylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone oxime ( 6-1) synthesis
- Step 2 Compound 2-(4-(tert-butyl)-2,6-dimethylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone (7-2 ) synthesis
- Step 3 Compound (Z)-2-(4-(tert-butyl)-2,6-dimethylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone Synthesis of oxime (7-1)
- PMEA Propylene glycol methyl ether acetate
- PHS polyhydroxystyrene resin
- DPHA dipentaerythritol hexaacrylate
- the coating was coated to have a film thickness of 5 ⁇ m, dried at 120° C. for 2 minutes to volatilize the solvent, and a fusion lamp Exposure, development in 0.045wt% KOH aqueous solution at 23 °C, and the thickness was evaluated based on the exposure amount maintaining 80% compared to the initial thickness using a non-contact thickness measuring instrument.
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Abstract
A novel oxime ester carbazole derivative compound is provided.
Description
신규한 옥심에스테르 카바졸 유도체 화합물 및 이를 포함하는 감광성 수지 조성물에 관한 것이다.It relates to a novel oxime ester carbazole derivative compound and a photosensitive resin composition comprising the same.
광개시제는 빛을 흡수하여 분해됨으로써 화학적으로 활성을 지닌 원자 또는 분자를 생성하는 물질이며, 감광성 조성물 등에 널리 사용된다.A photoinitiator is a substance that absorbs light and decomposes to generate chemically active atoms or molecules, and is widely used in photosensitive compositions and the like.
화학적 활성을 지닌 물질의 예로는 산이나 염기 그리고 라디칼 등이 있다. 특히, 라디칼이 생성되는 광개시제는 라디칼과 함께 중합 반응을 일으키는 아크릴기와 함께 사용되어 코팅된 막의 강도를 향상시키는 목적으로 사용될 수 있다.Examples of chemically active substances include acids, bases, and radicals. In particular, the photoinitiator in which radicals are generated may be used together with an acryl group that causes a polymerization reaction with the radical to improve the strength of the coated film.
이러한 용도의 감광성 조성물로는 잉크젯용 잉크 또는 자동차나 휴대폰 등의 투명하거나 착색된 보호막이 또한, 빛에 의한 중합 반응에 따른 용해도가 감소되는 현상을 이용하는 광식각법용 감광성 수지 조성물에 광개시제가 응용될 수 있다. As a photosensitive composition for this purpose, a photoinitiator may be applied to the photosensitive resin composition for photoetching using inkjet ink or a transparent or colored protective film such as a car or mobile phone, and a phenomenon in which solubility is reduced according to a polymerization reaction by light. have.
대표적인 예로는 액정표시소자의 컬러 필터 제조에 사용되는 광중합형 감광성 수지 조성물이나, 수지 블랙 매트릭스용 감광성 조성물 등이 있다.Representative examples include a photopolymerization type photosensitive resin composition used for manufacturing a color filter of a liquid crystal display device, a photosensitive composition for a resin black matrix, and the like.
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.The photosensitive composition can be used to form a pattern by applying on a substrate to form a coating film, exposing a specific portion of the coating film by light irradiation using a photomask or the like, and then developing and removing the unexposed portion.
감광성 수지 조성물에 사용되는 광 개시제의 일반적인 예는 아세토페논 유도체, 벤조페논 유도체, 트리아진 유도체, 비이미다졸 유도체, 아실포스핀 옥사이드 유도체 등 여러 종류가 알려져 있다.Common examples of the photoinitiator used in the photosensitive resin composition include various types of acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, and acylphosphine oxide derivatives.
본 발명의 일 구현예는 적은 노광량으로 라디칼 생성 효율이 우수하여, 감도가 우수하며, 광개시제의 농도를 충분히 높일 수 있도록 용해도가 향상되어 광개시제로서 유용한 옥심에스테르 카바졸 유도체 화합물을 제공한다.One embodiment of the present invention provides an oxime ester carbazole derivative compound useful as a photoinitiator by having excellent radical generation efficiency with a small exposure dose, excellent sensitivity, and improved solubility to sufficiently increase the concentration of the photoinitiator.
본 발명의 또 다른 구현예는 상기 신규한 옥심에스테르 카바졸 유도체 화합물을 광개시제로서 포함하는 감광성 수지를 제공한다.Another embodiment of the present invention provides a photosensitive resin comprising the novel oxime ester carbazole derivative compound as a photoinitiator.
본 발명의 일 구현예에서, 하기 화학식 1로 표시되는 옥심에스테르 카바졸 유도체 화합물을 제공한다.In one embodiment of the present invention, there is provided an oxime ester carbazole derivative compound represented by the following formula (1).
<화학식 1><Formula 1>
상기 식에서, In the above formula,
R
1 및 R
3은, 각각 독립적으로, C1~C12의 지방족 탄화수소이고,R 1 and R 3 are each independently a C1-C12 aliphatic hydrocarbon,
R
2는 C1~C12의 알킬 또는 C6~C12의 아릴이고,R 2 is C1~ C12 alkyl or C6~ C12 aryl;
m은 1~2의 정수이고,m is an integer of 1 to 2,
n은 1~5의 정수이다.n is an integer from 1 to 5;
본 발명의 다른 구현예에서, 상기 옥심에스테르 카바졸 유도체 화합물 및 에틸렌계 불포화 결합을 갖는 화합물을 포함하는 감광성 수지 조성물를 제공한다.In another embodiment of the present invention, there is provided a photosensitive resin composition comprising the oxime ester carbazole derivative compound and a compound having an ethylenically unsaturated bond.
상기 신규한 옥심에스테르 카바졸 화합물은 적은 노광량으로 라디칼 생성 효율이 우수하여, 감도가 우수하며, 광개시제의 농도를 충분히 높일 수 있도록 용해도가 향상된 광개시제로서 유용하다.The novel oxime ester carbazole compound is useful as a photoinitiator with improved solubility to sufficiently increase the concentration of the photoinitiator, the novel oxime ester carbazole compound has excellent radical generation efficiency with a small exposure dose, excellent sensitivity, and sufficient concentration of the photoinitiator.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구항의 범주에 의해 정의될 뿐이다. Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.
본 발명의 일 구현예에서, 신규한 하기 화학식 1로 표시되는 옥심에스테르 카바졸 유도체 화합물을 제공한다.In one embodiment of the present invention, there is provided a novel oxime ester carbazole derivative compound represented by the following formula (1).
<화학식 1><Formula 1>
상기 식에서, In the above formula,
R
1 및 R
3은, 각각 독립적으로, C1~C12의 지방족 탄화수소이고,R 1 and R 3 are each independently a C1-C12 aliphatic hydrocarbon,
R
2는 C1~C12의 알킬 또는 C6~C12의 아릴이고,R 2 is C1~ C12 alkyl or C6~ C12 aryl;
m은 1~2의 정수이고,m is an integer of 1 to 2,
n은 1~5의 정수이다.n is an integer from 1 to 5;
일 구현예에서, R
1 및 R
3은 탄소수가 커질수록 용해도를 더욱 향상시킬 수 있다. 다만, 탄소수가 커질 경우, 화합물의 분자량을 증가시키게 되고, 이는 감도 측면에서는 불리한 영향을 줄 수 있다. 따라서, 구현하고자 하는 용해도와 감도를 함께 고려하여 R
1 및 R
3의 탄소수를 적절히 선택할 수 있다. 예를 들어, 상기 R
1 및 R
3은, 각각 독립적으로, C7~C12의 지방족 탄화수소일 수 있다.In one embodiment, R 1 and R 3 may further improve solubility as the number of carbon atoms increases. However, when the number of carbon atoms increases, the molecular weight of the compound increases, which may adversely affect the sensitivity. Therefore, the number of carbon atoms of R 1 and R 3 may be appropriately selected in consideration of both solubility and sensitivity to be implemented. For example, R 1 and R 3 may each independently be a C7~C12 aliphatic hydrocarbon.
일 구현예에서, n이 클수록 용해도를 더욱 향상시킬 수 있다. 예를 들어, 상기 n은 2~5의 정수일 수 있다. 다른 예를 들어, 상기 n은 3~5의 정수일 수 있다.In one embodiment, solubility may be further improved as n is larger. For example, n may be an integer of 2 to 5. As another example, n may be an integer of 3 to 5.
일 구현예에서, R
1 및 R
3은 직쇄 알킬보다는 분지쇄 알킬일 때 용해도를 더욱 향상시킬 수 있다. 다만, R
1 및 R
3은 직쇄 알킬보다는 분지쇄 알킬일 때 감도 측면에서는 불리할 수 있기 때문에, 구현하고자 하는 용해도와 감도를 함께 고려하여 R
1 또는 R
3를 분지쇄 알킬을 도입할 지 여부를 적절히 선택할 수 있다. 예를 들어, 상기 R
1 및 R
3은, 각각 독립적으로, 직쇄 알킬일 수 있다.In one embodiment, when R 1 and R 3 are branched chain alkyl rather than straight chain alkyl, solubility may be further improved. However, since R 1 and R 3 may be disadvantageous in terms of sensitivity when they are branched-chain alkyl rather than straight-chain alkyl, consider whether to introduce branched-chain alkyl as R 1 or R 3 in consideration of solubility and sensitivity to be implemented. can be appropriately selected. For example, R 1 and R 3 may each independently be a straight-chain alkyl.
일 구현예에서, R
2는 탄소수가 작을수록 감도를 향상시킬 수 있다. 예를 들어, 상기 R
2는 메틸일 수 있다.In one embodiment, R 2 may improve sensitivity as the number of carbon atoms decreases. For example, R 2 may be methyl.
예를 들어, 상기 옥심에스테르 카바졸 유도체 화합물은 하기 화합물 중 어느 하나일 수 있다.For example, the oxime ester carbazole derivative compound may be any one of the following compounds.
본 발명의 일 구현예에서, 상기 광개시제를 포함하는 감광성 수지 조성물을 제공하고, 상기 광개시제는 상기 옥심에스테르 카바졸 유도체 화합물을 포함한다.In one embodiment of the present invention, there is provided a photosensitive resin composition comprising the photoinitiator, and the photoinitiator comprises the oxime ester carbazole derivative compound.
상기 옥심에스테르 카바졸 유도체 화합물은 광개시제로서 자외선을 흡수하여 색을 거의 나타내지 않고, 라디칼 발생 효율이 높으며, 감광성 수지 조성물에서 혼합되는 다른 성분들과의 상용성 및 안정성이 우수하면서도, 광중합 개시 효율이 향상된다. 또한, 상기 옥심에스테르 카바졸 유도체 화합물을 광개시제로 적용한 감광성 수지 조성물의 패턴 노광 공정 시 감도가 높기 때문에 노광량을 늘리지 않을 수 있고, 이로 인해 생산량을 높일 수 있다.As a photoinitiator, the oxime ester carbazole derivative compound absorbs ultraviolet light and shows almost no color, has high radical generation efficiency, has excellent compatibility and stability with other components mixed in the photosensitive resin composition, and improves photopolymerization initiation efficiency do. In addition, since the sensitivity during the pattern exposure process of the photosensitive resin composition to which the oxime ester carbazole derivative compound is applied as a photoinitiator is high, the exposure amount may not be increased, and thus the production amount may be increased.
상기 광개시제는 적은 노광량으로 라디칼 생성 효율이 우수하여, 감도가 우수하며, 광개시제의 농도를 충분히 높일 수 있도록 향상된 용해도를 나타낸다.The photoinitiator has excellent radical generation efficiency with a small exposure amount, has excellent sensitivity, and exhibits improved solubility to sufficiently increase the concentration of the photoinitiator.
상기 감광성 수지 조성물은 용도가 고급화되고, 다양화되는 LCD의 용도에 부응하여, 노트북, 모바일 등의 용도 이외에도, TV, 모니터 등의 액정표시소자를 구성하는 용도로 제작될 수 있다. 상기 감광성 수지 조성물은 빛에 빠르게 반응할 수 있고, 기계적으로 우수한 물성을 구현함에 따라서, 적용되는 제품의 생산성 및 내구성을 향상시킬 수 있다.The photosensitive resin composition may be manufactured for use in forming liquid crystal display devices such as TVs and monitors, in addition to uses such as laptops and mobiles, in response to the increasing and diversifying uses of LCDs. The photosensitive resin composition can quickly respond to light and mechanically implement excellent physical properties, thereby improving the productivity and durability of the applied product.
상기 감광성 수지 조성물은, 예를 들어, 포토리소그래피(Photo-lithography) 법에 의해 패턴을 형성시키거나, 전면 노광을 통해 절연 보호막을 형성할 수 있다. 이러한 포토리소그래피 법에 의한 공정에 의하는 경우, 상기 감광성 수지 조성물에 있어서, 빛에 빠르게 반응하는 특성, 즉 광감도는 매우 중요한 역할을 하는 요인이 된다. 상기 광개시제는 광감도가 우수하므로, 포토리소그래피 법에 의한 공정으로 우수한 품질을 구현할 수 있다.The photosensitive resin composition may form a pattern by, for example, a photo-lithography method, or an insulating protective film may be formed through exposure of the entire surface. In the case of the photolithography process, in the photosensitive resin composition, a property of rapidly reacting to light, ie, photosensitivity, is a factor that plays a very important role. Since the photoinitiator has excellent photosensitivity, excellent quality may be realized by a process by a photolithography method.
또한, 외부에서 가한 충격에 의해 액정표시소자가 파손되지 않고 원래의 성능을 발휘하게 하기 위해서 지지대 역할을 하는 컬럼 스페이서 또는 보호막의 역할을 하는 오버코트와 패시베이션 막 등이 상기 감광성 수지 조성물에 의해 형성될 수 있다. 이러한 컬럼 스페이서, 오버코트와 패시베이션 막 등은 기계적 물성이 우수해야 한다. 마찬가지로, 상기 광개시제는 광감도가 우수하므로, 우수한 기계적 물성을 요구하는 용도에 적합하게 적용될 수 있다.In addition, in order to ensure that the liquid crystal display device is not damaged by external impact and exhibits its original performance, a column spacer serving as a support or an overcoat and passivation film serving as a protective film may be formed by the photosensitive resin composition. have. Such column spacers, overcoats and passivation films should have excellent mechanical properties. Likewise, since the photoinitiator has excellent photosensitivity, it can be suitably applied to applications requiring excellent mechanical properties.
상기 옥심에스테르 카바졸 유도체 화합물에 대한 상세한 설명은 전술한 바와 같다.Detailed description of the oxime ester carbazole derivative compound is the same as described above.
상기 감광성 수지 조성물은 바인더 수지를 포함할 수 있다. 상기 바인더 수지는 아크릴산 함유 아크릴공중합체, 노볼락계 페놀 수지, 폴리히드록시스티렌 수지, 히드록시스티렌과 아크릴레이트의 공중합체 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다.The photosensitive resin composition may include a binder resin. The binder resin may include one selected from the group consisting of an acrylic acid-containing acrylic copolymer, a novolak-based phenol resin, a polyhydroxystyrene resin, a copolymer of hydroxystyrene and acrylate, and combinations thereof.
상기 에틸렌계 불포화 결합을 갖는 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, β-히드록시 에틸(메타)아크릴레이트의 프탈산디에스테르, β-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,β-불포화 카르복시산을 에스테르화하여 얻어지는 화합물, 트리메틸올프로판트리글리시딜에테르아크릴산 부가물과 같이 다가 글리시딜 화합물의 아크릴산 부가물 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상 함께 사용할 수 있다.The compound having the ethylenically unsaturated bond is, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylic Alkyl esters of (meth)acrylic acid such as lactate, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate having 2 to 14 ethylene oxide groups, ethylene glycol di(meth)acrylate, ethylene oxide group Polyethylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate, bisphenol A diglycidyl ether Acrylic acid adduct, phthalic acid diester of β-hydroxyethyl (meth)acrylate, toluene diisocyanate adduct of β-hydroxyethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri( Polyhydric alcohols and α, such as meth)acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol tri (meth) acrylate, and a compound obtained by esterifying a β-unsaturated carboxylic acid, an acrylic acid adduct of a polyvalent 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. .
상기 감광성 수지는 광중합성 화합물을 포함할 수 있다.The photosensitive resin may include a photopolymerizable compound.
상기 광중합성 화합물은 광효율을 보완하기 위한 성분으로서, 그 종류가 특별히 한정되지 않으나, 에틸렌성 불포화 결합을 갖는 아크릴계 바인더 수지를 포함할 수 있다.The photopolymerizable compound is a component for supplementing light efficiency, and the type thereof is not particularly limited, but may include an acrylic binder resin having an ethylenically unsaturated bond.
상기 에틸렌성 불포화 결합을 갖는 아크릴계 바인더 수지는 아크릴계 올리고머 전구체와 에틸렌성 불포화 결합을 도입하기 위한 단량체의 화학 반응에 의해 자외선 경화 반응이 가능하도록 구성된 광경화형 아크릴계 올리고머이다. 상기 아크릴계 올리고머 전구체는 탄소수 1 내지 14의 알킬기를 갖는 (메타)아크릴계 단량체와 중합성 단량체가 공중합된 것일 수 있다. 아크릴계 올리고머 전구체의 제조방법은 특별히 한정되지 않으며, 당 분야에서 통상적으로 사용되는 괴상중합, 용액중합, 유화중합 또는 현탁중합 등의 방법을 이용하여 제조할 수 있으며, 괴상중합이 바람직하다. 또한, 중합 시 통상 사용되는 용매를 사용하며, 아조계, 퍼옥사이드계, 아세탈계, 헤미아세탈계 및 레독스계 등의 중합 개시제를 사용할 수 있다. 상기 탄소수 1 내지 14의 알킬기를 갖는 (메타)아크릴계 단량체의 알킬기는 지방족 알킬기와 방향족 알킬기를 포함하며, 이러한 단량체로는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, n-부틸(메타)아크릴레이트, 2-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 에틸헥실(메타)아크릴레이트, 에틸부틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 이소노닐(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 이소데실(메타)아크릴레이트 및 라우릴(메타)아크릴레이트 등을 들 수 있다. 상기 단량체들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The acrylic binder resin having an ethylenically unsaturated bond is a photocurable acrylic oligomer configured to enable a UV curing reaction by a chemical reaction between an acrylic oligomer precursor and a monomer for introducing an ethylenically unsaturated bond. The acrylic oligomer precursor may be a copolymer of a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms and a polymerizable monomer. The method for preparing the acrylic oligomer precursor is not particularly limited, and it can be prepared using methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization commonly used in the art, and bulk polymerization is preferred. In addition, a solvent commonly used during polymerization is used, and polymerization initiators such as azo, peroxide, acetal, hemiacetal and redox initiators may be used. The alkyl group of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms includes an aliphatic alkyl group and an aromatic alkyl group, and these monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) Acrylate, ethylhexyl (meth) acrylate, ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate , isobornyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, and the like. The above monomers may be used alone or in combination of two or more.
상기 중합성 단량체로는 구체적으로 예를 들어, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 2-히드록시에틸렌글리콜(메타)아크릴레이트, 2-히드록시프로필렌글리콜(메타)아크릴레이트 및 4-히드록시부틸비닐에테르 등의 히드록시기를 갖는 단량체; (메타)아크릴산, 크로톤산, 말레인산, 이타콘산 및 푸마르산 등의 카르복시기를 갖는 단량체 등을 들 수 있다. 상기 중합성 단량체들은 단독 또는 2종 이상 혼합하여 사용할 수 있다. 상기 에틸렌성 불포화 결합을 도입하기 위한 단량체의 종류는 특별히 한정되지 않는다. 그러나 바람직하게는 1분자 내에 이소시아네이트기와 이중결합을 동시에 갖는 이소시아네이트계 단량체를 사용하며, 예를 들어 2-이소시아네이토에틸(메타)아크릴레이트를 들 수 있다. 상기 광중합성 화합물로 바람직하게 사용되는 광경화형 아크릴계 올리고머의 제조방법은 특별히 한정되지 않는다. 구체적으로 예를 들어, 아크릴계 올리고머 전구체를 제조한 후 제조된 아크릴계 올리고머 전구체 100 중량부에 대하여 이소시아네이트계 단량체 0.5 내지 20 중량부 및 촉매 0.001 내지 0.5 중량부를 첨가하고 반응시키는 방법으로 제조할 수 있다. 촉매는 아크릴계 올리고머 전구체에 함유된 히드록시기 또는 카르복시기와 이소시아네이트기의 반응을 촉진시킬 수 있는 것이라면 그 종류가 특별히 한정되지 않으며, 예컨대 유기 주석계 화합물, 유기 은계 화합물 또는 이들의 혼합물을 사용할 수 있다. 상기 광중합성 화합물은 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 중량평균분자량(폴리스티렌 환산, Mw)이 20만 내지 100만일 수 있다.Specifically as the polymerizable monomer, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, 2-hydroxypropylene glycol (meth)acrylate and 4-hydroxybutyl vinyl ether a monomer having a hydroxyl group; and monomers having a carboxyl group such as (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid. The polymerizable monomers may be used alone or in combination of two or more. The kind of monomer for introducing the said ethylenically unsaturated bond is not specifically limited. However, preferably, an isocyanate-based monomer having an isocyanate group and a double bond in one molecule is used, for example, 2-isocyanatoethyl (meth)acrylate. A method for producing a photocurable acrylic oligomer preferably used as the photopolymerizable compound is not particularly limited. Specifically, for example, after preparing the acrylic oligomer precursor, 0.5 to 20 parts by weight of the isocyanate-based monomer and 0.001 to 0.5 parts by weight of the catalyst are added and reacted with respect to 100 parts by weight of the prepared acrylic oligomer precursor. The type of the catalyst is not particularly limited as long as it can promote the reaction between the hydroxyl group or the carboxyl group and the isocyanate group contained in the acrylic oligomer precursor, and for example, an organotin-based compound, an organic silver-based compound, or a mixture thereof may be used. The photopolymerizable compound may have a weight average molecular weight (in terms of polystyrene, Mw) of 200,000 to 1,000,000 measured by gel permeation chromatography (GPC).
상기 광중합 개시제는 광중합성 화합물의 고형분 100 중량부에 대하여 0.01 내지 10 중량부로 포함된다. 상기 함량이 0.01 중량부 미만이면, 광중합성 조성물의 전체적인 경화도가 저하되며, 10 중량부를 초과하면, 자외선의 투과율이 저하되어 심부에서의 경화도가 저하된다는 문제점이 있다.The photopolymerization initiator is included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the solid content of the photopolymerizable compound. If the content is less than 0.01 parts by weight, the overall degree of curing of the photopolymerizable composition is lowered, and when it exceeds 10 parts by weight, the transmittance of ultraviolet rays is lowered and the degree of curing in the deep part is lowered.
상기 감광성 조성물은 광을 조사하여 중합하고 경화시킬 수 있다. 상기 감광성 조성물은 이러한 성질을 이용할 수 있는 용도에 응용될 수 있다. 예를 들어, 상기 감광성 조성물은 광경화성 잉크, 감광성 인쇄판, 각종 포토레지스트, LCD용 컬러 필터 포토레지스트, 수지 블랙 매트릭스용 포토레지스트 또는 투명 감광재 등에 적용될 수 있다.The photosensitive composition may be polymerized and cured by irradiating light. The photosensitive composition can be applied to applications that can utilize these properties. For example, the photosensitive composition may be applied to 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.
상기 감광성 조성물은 용매를 더 포함할 수 있다.The photosensitive composition may further include a solvent.
상기 용매는, 광중합성 조성물에 포함되는 다른 성분들을 용해시키는데 효과적인 것이면, 통상의 광중합성 조성물에서 사용되는 용제를 특별히 제한하지If the solvent is effective for dissolving other components included in the photopolymerizable composition, the solvent used in the conventional photopolymerizable composition is not particularly limited.
않고 사용할 수 있으며, 특히 에테르류, 방향족 탄화수소류, 케톤류, 알콜류, 에스테르류 또는 아미드류 등이 바람직하다. 상기 에테르류로는 예를 들어, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노부틸에테르등의 에틸렌글리콜모노알킬에테르류; 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜디프로필에테르, 디에틸렌글리콜디부틸에테르 등의 디에틸렌글리콜디알킬에테르류; 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트 등의 에틸렌글리콜알킬에테르아세테이트류; 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노프로필에테르아세테이트, 메톡시부틸아세테이트, 메톡시펜틸아세테이트 등의 알킬렌글리콜알킬에테르아세테이트류 등이 있다. 상기 에스테르류로는 에틸락테이트, 부틸락테이트, 3-에톡시프로피온산에틸, 3-메톡시프로피온산메틸 등의 에스테르류; 및 γ-부티롤락톤 등의 환상 에스테르류 등을 들 수 있다.In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are preferable. Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; and alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate. Examples of the esters include esters such as ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.
상기 용제 중에서도 도포성 및 건조성면에서 비점이 100℃ 내지 200℃인 유기 용제를 사용하는 것이 더욱 바람직하며 그 예로는 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 시클로헥사논, 에틸락테이트, 부탈락테이트, 3-에톡시프로피온산에틸 및 3-메톡시프로피온산메틸 등이 있다.Among the above solvents, it is more preferable to use an organic solvent having a boiling point of 100°C to 200°C in terms of applicability and drying properties, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and ethyl lactate. , butalactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.
상기 감광성 조성물은 그 구체적인 용도에 적합한 첨가제 등의 기타 성분을 더 포함할 수 있다.The photosensitive composition may further include other components such as additives suitable for its specific use.
상기 첨가제는, 예를 들어, 글라스 밀착력 향상을 위한 실란커플링제나, 평탄성을 향상하기 위한 레벨링제 등일 수 있다.The additive may be, for example, a silane coupling agent for improving glass adhesion, or a leveling agent for improving flatness.
이하 본 발명의 실시예 및 비교예를 기재한다. 그러한 하기한 실시예는 본 발명의 일 실시예일뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, Examples and Comparative Examples of the present invention will be described. The following examples are only examples of the present invention, and the present invention is not limited to the following examples.
(실시예)(Example)
[합성예 1] 화합물 2의 합성[Synthesis Example 1] Synthesis of compound 2
[반응식 1][Scheme 1]
1 단계 : 화합물 3-니트로-9-에틸카바졸 (2-3)의 합성Step 1: Synthesis of compound 3-nitro-9-ethylcarbazole (2-3)
반응 용기에 아세트산 (50 mL)를 넣고 9-에틸카바졸 (20 g, 102 mmol)를 넣고 교반하면서 65% HNO
3 (8 mL, 113 mmol, 1.1 eq)를 천천히 넣고 상온(20-25 ℃)에서 6 시간 동안 교반한다. 반응이 완결되면 반응물에 정제수 (60 mL)를 넣고 1 시간 이상 교반한다. 생성된 고체를 여과하여 수득하여 조생성물 2-3을 얻는다. 얻어진 고체 생성물을 아세트산(AcOH)으로 재결정하여 노란색 결정형 고체 2-3 (21.2 g, 86 % 수율)을 얻는다.Acetic acid (50 mL) was added to the reaction vessel, 9-ethylcarbazole (20 g, 102 mmol) was added, 65% HNO 3 (8 mL, 113 mmol, 1.1 eq) was slowly added while stirring, and room temperature (20-25 ℃) stirred for 6 hours. When the reaction is complete, add purified water (60 mL) to the reaction and stir for at least 1 hour. The resulting solid is obtained by filtration to obtain a crude product 2-3. The obtained solid product is recrystallized from acetic acid (AcOH) to obtain yellow crystalline solid 2-3 (21.2 g, 86 % yield).
2 단계 : 화합물 2-(4-(터트-부틸)페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 (2-2)의 합성Step 2: Synthesis of compound 2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone (2-2)
- 화합물 2-(4-(터트-부틸)페녹시)아세틸 클로라이드 (3)의 합성- Synthesis of compound 2-(4-(tert-butyl)phenoxy)acetyl chloride (3)
반응 용기에 디클로로에탄(DCE) (200 mL)를 넣고 4-터트-부틸페녹시아세트산 (24 g, 115 mmol)을 넣고 상온(20-25 ℃)에서 교반한다. 동일 온도에서 옥살일 클로라이드 (17 mL, 201 mmol, 1.5 eq.)를 천천히 (반응온도가 40 ℃를 넘지 않도록 조절함) 적가한다. 적가 완료 후 반응 온도 (40 ℃에서 4 시간 동안 교반한다 (반응 진행 시 N
2를 흘려 보내 생성되는 HCl 가스를 충분히 배출(vent-out)시킨다). 반응 완료 후 감압하에 40 ℃로 반응용매 및 잔류 HCl 가스를 제거해 준다. 농축액을 다음 반응에 곧바로 사용한다. Dichloroethane (DCE) (200 mL) was added to a reaction vessel, 4-tert-butylphenoxyacetic acid (24 g, 115 mmol) was added, and the mixture was stirred at room temperature (20-25 ° C). At the same temperature, oxalyl chloride (17 mL, 201 mmol, 1.5 eq.) is slowly added dropwise (controlled so that the reaction temperature does not exceed 40 °C). After completion of the dropwise addition, the reaction temperature (agitate at 40° C. for 4 hours (when the reaction proceeds, N 2 is flowed to sufficiently vent-out the HCl gas generated). After completion of the reaction, the reaction solvent and residual Remove the HCl gas and use the concentrate directly for the next reaction.
N
2 가스하에서 반응 용기에 메틸렌클로라이드(MC) (200 mL)를 넣고 화합물 2-3 (20 g, 83.2 mmol)을 넣고 교반한다. 반응물에 무수 AlCl
3 (15 g, 108.2 mmol, 1.3 eq.)를 한번에 넣는다. 질소 분위기 하에서 상온 (20-25 ℃)에서 30분 동안 교반한 다음 반응물을 얼음/물 배쓰(bath)를 이용하여 0~5 ℃로 냉각한다. 앞서 제조해 놓은 화합물 4-(
터트-부틸)벤조일 클로라이드 (3) (~25 g, 125 mmol, 1.5 eq.)를 30분 동안 반응온도가 10 ℃를 넘지 않게 천천히 적가한다. 반응물을 상온 (20-25 ℃)으로 자연승온 후 8 시간 이상 교반한다. 반응 완료 후 반응물에 냉수를 넣고 MC (x 3)로 추출한다. 추출된 유기층을 무수 MgSO
4로 건조하고 감압 농축한 다음 에틸아세테이트(EA)/헥산으로 컬럼 정제하여 옅은 노란색 고체 2.2 (29.4 g, 82 % 수율)를 얻는다.In a reaction vessel under N 2 gas, methylene chloride (MC) (200 mL) was added, and compound 2-3 (20 g, 83.2 mmol) was added and stirred. To the reaction was added anhydrous AlCl 3 (15 g, 108.2 mmol, 1.3 eq.) in one portion. After stirring for 30 minutes at room temperature (20-25 ℃) under a nitrogen atmosphere, the reactant is cooled to 0-5 ℃ using an ice/water bath. The previously prepared compound 4-( tert -butyl)benzoyl chloride (3) (~25 g, 125 mmol, 1.5 eq.) was slowly added dropwise so that the reaction temperature did not exceed 10 °C for 30 minutes. The reactant is naturally heated to room temperature (20-25 ℃) and stirred for at least 8 hours. After completion of the reaction, cold water is added to the reaction mixture and extracted with MC (x 3). The extracted organic layer was dried over anhydrous MgSO 4 , concentrated under reduced pressure, and purified by column with ethyl acetate (EA)/hexane to obtain a pale yellow solid 2.2 (29.4 g, 82 % yield).
3 단계 : 화합물 (Z)-2-(4-(터트-부틸)페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 옥심 (2-1)의 합성Step 3: Compound (Z)-2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone oxime (2-1) synthesis of
반응 용기에 피리딘 (70 mL)를 넣은 다음 앞 단계에서 합성한 화합물 2-2 (25 g, 62.4 mmol) 넣고 교반한다. 상온 (20-25 ℃)에서 2-메톡시에탄올 (15 mL, 187.3 mmol, 3 eq.)과 포타슘-터트-부톡사이드(KO
t-Bu) (11 g, 94 mmol, 1.5 eq.)을 넣는다. 반응물을 80 ℃로 승온 후 4 시간 동안 교반한다. 그 후 반응물에 H
2N-OH.HCl (13 g, 187.3 mmol, 3 eq)를 넣은 다음 100 ℃에서 밤샘 교반한다. 반응물을 상온 (20-25 ℃)으로 냉각한 다음 정제수 (1000 mL)를 넣어 고체 생성물을 석출시킨다. 고체를 여과하고 메탄올(MeOH)로 세척하고 건조하여 흰색 고체 생성물 2-1 (18.1 g, 70 % 수율)을 얻는다.After putting pyridine (70 mL) in a reaction vessel, the compound 2-2 (25 g, 62.4 mmol) synthesized in the previous step was added and stirred. Add 2-methoxyethanol (15 mL, 187.3 mmol, 3 eq.) and potassium-tert-butoxide (KO t -Bu) (11 g, 94 mmol, 1.5 eq.) at room temperature (20-25 ° C) . The reaction mixture was heated to 80 °C and stirred for 4 hours. Thereafter, H 2 N-OH.HCl (13 g, 187.3 mmol, 3 eq) was added to the reaction mixture, followed by stirring at 100° C. overnight. The reactant was cooled to room temperature (20-25 °C), and then purified water (1000 mL) was added to precipitate a solid product. The solid is filtered, washed with methanol (MeOH) and dried to give a white solid product 2-1 (18.1 g, 70 % yield).
최종 단계 : 화합물 (Z)-2-(4-(터트-부틸)페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 O-아세틸 옥심 (2)의 합성Final step: compound (Z)-2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone O-acetyl oxime (2 ) synthesis
반응 용기에 아세톤 (100 mL)를 넣고 앞 단계 생성물 2-1 (15 g, 36 mmol)을 넣고 교반하면서 얼음/물 배쓰를 이용하여 0-5℃로 냉각한다. 냉각된 반응물에 트리에틸아민(TEA) (10 mL, 72 mmol, 2 eq.)와 아세트산무수물(Ac
2O) (7 mL, 72 mmol, 2 eq.)를 첨가하였다. 반응물을 상온 (20-25 ℃)에서 2 시간 동안 교반하여 반응을 완결한다. 반응물에 물을 넣고 EA로 추출한다. 추출된 유기층을 정제수, 포화소금물로 세척하고 무수 MgSO
4로 건조한 다음 감압농축하여 조(Crude) 고체 생성물을 얻는다. 얻어진 고체 생성물을 메틸터셔리부틸에테르(MTBE)로 재결정하여 흰색 고체 생성물인 2 화합물 (12 g, 73 % 수율)을 수득하였다.Acetone (100 mL) is added to the reaction vessel, the product of the previous step 2-1 (15 g, 36 mmol) is added, and the mixture is cooled to 0-5° C. using an ice/water bath while stirring. To the cooled reaction was added triethylamine (TEA) (10 mL, 72 mmol, 2 eq.) and acetic anhydride (Ac 2 O) (7 mL, 72 mmol, 2 eq.). The reaction is completed by stirring the reactant at room temperature (20-25 °C) for 2 hours. Add water to the reaction mixture and extract with EA. The extracted organic layer is washed with purified water and saturated brine, dried over anhydrous MgSO 4 and concentrated under reduced pressure to obtain a crude solid product. The obtained solid product was recrystallized from methyl tertiary butyl ether (MTBE) to obtain compound 2 (12 g, 73 % yield) as a white solid product.
CDCl
3 에서 H-NMR : 8.48 (d, 1H), 8.01 (d, 1H), 7.82 (s, 1H), 7.80 (d, 1H), 7.66 (d, 1H), 7.41 (d, 1H), 7.18 (d, 2H), 6.69 (d, 2H), 5.37 (s, 2H), 3.89 (q, 2H), 2.08 (s, 3H), 1.51 (t, 3H), 1.34 (s, 9H)H-NMR in CDCl 3 : 8.48 (d, 1H), 8.01 (d, 1H), 7.82 (s, 1H), 7.80 (d, 1H), 7.66 (d, 1H), 7.41 (d, 1H), 7.18 (d, 2H), 6.69 (d, 2H), 5.37 (s, 2H), 3.89 (q, 2H), 2.08 (s, 3H), 1.51 (t, 3H), 1.34 (s, 9H)
[합성예 2] 화합물 3의 합성[Synthesis Example 2] Synthesis of compound 3
[반응식 2][Scheme 2]
1 단계 : 화합물 3-니트로-9-에틸카바졸 (3-3)의 합성Step 1: Synthesis of compound 3-nitro-9-ethylcarbazole (3-3)
상기 합성예는 [화합물 2-3]의 합성예와 동일하게 진행하여 [화합물 3-3]을 얻었다.The synthesis example proceeded in the same manner as in the synthesis example of [Compound 2-3] to obtain [Compound 3-3].
(21.2 g, 86 % 수율) (21.2 g, 86% yield)
2 단계 : 화합물 1-(9-에틸-6-니트로-9H-카바졸-3-일)-2-(4-(2,4,4-트리메틸펜탄-2-일)페녹시)에탄온 (3-2)의 합성Step 2: Compound 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-2-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)ethanone ( 3-2) synthesis
상기 합성예 2-(2)에서 사용한 [화합물 3] 대신 [화합물 4]를 사용한 것을 제외하고는 동일한 방법으로 합성하여 [화합물 3-2]를 얻었다. (33.2 g, 82 % 수율) [Compound 3-2] was obtained by synthesizing in the same manner except that [Compound 4] was used instead of [Compound 3] used in Synthesis Example 2-(2). (33.2 g, 82% yield)
3 단계 : 화합물 (Z)-1-(9-에틸-6-니트로-9H-카바졸-3-일)-2-(4-(2,4,4-트리메틸펜탄-2-일)페녹시)에탄온 옥심 (3-1)의 합성Step 3: Compound (Z)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-2-(4-(2,4,4-trimethylpentan-2-yl)phenoxy ) Synthesis of ethanone oxime (3-1)
상기 합성예 2-(1)에서 사용한 동일한 방법으로 합성하여 [화합물 3-1]를 얻었다. It was synthesized by the same method used in Synthesis Example 2-(1) to obtain [Compound 3-1].
(21.6 g, 70 % 수율)(21.6 g, 70% yield)
최종 단계 : 화합물 (Z)-1-(9-에틸-6-니트로-9H-카바졸-3-일)-2-(4-(2,4,4-트리메틸펜탄-2-일)페녹시)에탄온 O-아세틸 옥심 (3)의 합성Final step: compound (Z)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-2-(4-(2,4,4-trimethylpentan-2-yl)phenoxy ) Synthesis of ethanone O-acetyl oxime (3)
상기 합성예 2에서 사용한 동일한 방법으로 합성하여 [화합물 3]를 얻었다. It was synthesized by the same method used in Synthesis Example 2 to obtain [Compound 3].
(16.0 g, 74 % 수율)(16.0 g, 74% yield)
CDCl
3 에서 H-NMR : 8.48 (d, 1H), 8.01 (d, 1H), 7.82 (s, 1H), 7.80 (d, 1H), 7.66 (d, 1H), 7.41 (d, 1H), 7.20 (d, 2H), 7.00 (d, 2H), 5.37 (s, 2H), 3.89 (q, 2H), 2.08 (s, 3H), 1.51 (t, 3H), 1.46 (s, 2H), 1.39 (s, 6H), 1.06 (s, 9H)H-NMR in CDCl 3 : 8.48 (d, 1H), 8.01 (d, 1H), 7.82 (s, 1H), 7.80 (d, 1H), 7.66 (d, 1H), 7.41 (d, 1H), 7.20 (d, 2H), 7.00 (d, 2H), 5.37 (s, 2H), 3.89 (q, 2H), 2.08 (s, 3H), 1.51 (t, 3H), 1.46 (s, 2H), 1.39 ( s, 6H), 1.06 (s, 9H)
[합성예 3] 화합물 4의 합성[Synthesis Example 3] Synthesis of compound 4
[반응식 3][Scheme 3]
1 단계 : 화합물 3-니트로-9-에틸카바졸 (4-3)의 합성Step 1: Synthesis of compound 3-nitro-9-ethylcarbazole (4-3)
상기 합성예는 [화합물 2-3]의 합성예와 동일하게 진행하여 [화합물 4-3]을 얻었다.The synthesis example proceeded in the same manner as in the synthesis example of [Compound 2-3] to obtain [Compound 4-3].
(21.2 g, 86 % 수율) (21.2 g, 86% yield)
2 단계 : 화합물 1-(9-에틸-6-니트로-9H-카바졸-3-일)-2-(메시틸옥시)에탄온 (4-2)의 합성Step 2: Synthesis of compound 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-2-(mesityloxy)ethanone (4-2)
상기 합성예 2-(2)에서 사용한 [화합물 3] 대신 [화합물 5]를 사용한 것을 제외하고는 동일한 방법으로 합성하여 [화합물 4-2]를 얻었다. (29.4 g, 85 % 수율) [Compound 4-2] was obtained by synthesizing in the same manner except that [Compound 5] was used instead of [Compound 3] used in Synthesis Example 2-(2). (29.4 g, 85% yield)
3 단계 : 화합물 (Z)-1-(9-에틸-6-니트로-9H-카바졸-3-일)-2-(메시틸옥시)에탄온 옥심 (4-1)의 합성Step 3: Synthesis of compound (Z)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-2-(mesityloxy)ethanone oxime (4-1)
상기 합성예 2-(1)에서 사용한 동일한 방법으로 합성하여 [화합물 4-1]를 얻었다. It was synthesized by the same method used in Synthesis Example 2-(1) to obtain [Compound 4-1].
(18.6 g, 72 % 수율)(18.6 g, 72% yield)
최종 단계 : 화합물 (Z)-1-(9-에틸-6-니트로-9H-카바졸-3-일)-2-(메시틸옥시)에탄온 O-아세틸 옥심 (4)의 합성Final step: synthesis of compound (Z)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-2-(mesityloxy)ethanone O-acetyl oxime (4)
상기 합성예 2에서 사용한 동일한 방법으로 합성하여 [화합물 4]를 얻었다. It was synthesized by the same method used in Synthesis Example 2 to obtain [Compound 4].
(14.2 g, 72 % 수율)(14.2 g, 72% yield)
CDCl
3 에서 H-NMR : 8.48 (d, 1H), 8.01 (d, 1H), 7.82 (s, 1H), 7.80 (d, 1H), 7.66 (d, 1H), 7.41 (d, 1H), 6.56 (s, 2H), 5.37 (s, 2H), 3.89 (q, 2H), 2.08 (s, 3H), 2.37 (s, 6H), 2.33 (s, 3H), 1.51 (t, 3H)H-NMR in CDCl 3 : 8.48 (d, 1H), 8.01 (d, 1H), 7.82 (s, 1H), 7.80 (d, 1H), 7.66 (d, 1H), 7.41 (d, 1H), 6.56 (s, 2H), 5.37 (s, 2H), 3.89 (q, 2H), 2.08 (s, 3H), 2.37 (s, 6H), 2.33 (s, 3H), 1.51 (t, 3H)
[합성예 4] 화합물 5의 합성[Synthesis Example 4] Synthesis of compound 5
[반응식 4][Scheme 4]
1 단계 : 화합물 3-니트로-9-에틸카바졸 (5-3)의 합성Step 1: Synthesis of compound 3-nitro-9-ethylcarbazole (5-3)
상기 합성예는 [화합물 2-3]의 합성예와 동일하게 진행하여 [화합물 5-3]을 얻었다.The synthesis example proceeded in the same manner as in the synthesis example of [Compound 2-3] to obtain [Compound 5-3].
(21.2 g, 86 % 수율) (21.2 g, 86% yield)
2 단계 : 화합물 2-(4-(터트-부틸)페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 (5-2)의 합성Step 2: Synthesis of compound 2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone (5-2)
상기 합성예 2-(2)에서 사용한 [화합물 3] 대신 [화합물 6]를 사용한 것을 제외하고는 동일한 방법으로 합성하여 [화합물 5-2]를 얻었다. (30.1 g, 84 % 수율) [Compound 5-2] was obtained by synthesizing in the same manner except that [Compound 6] was used instead of [Compound 3] used in Synthesis Example 2-(2). (30.1 g, 84% yield)
3 단계 : 화합물 (Z)-2-(4-(터트-부틸)페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 옥심 (5-1)의 합성Step 3: Compound (Z)-2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone oxime (5-1) synthesis of
상기 합성예 2-(1)에서 사용한 동일한 방법으로 합성하여 [화합물 5-1]를 얻었다. It was synthesized by the same method used in Synthesis Example 2-(1) to obtain [Compound 5-1].
(22.0 g, 71 % 수율)(22.0 g, 71% yield)
최종 단계 : 화합물 (Z)-2-(4-(터트-부틸)페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 O-벤조일 옥심 (5)의 합성Final step: compound (Z)-2-(4-(tert-butyl)phenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone O-benzoyl oxime (5 ) synthesis
상기 합성예 2에서 사용한 동일한 방법으로 합성하여 [화합물 5]를 얻었다. It was synthesized by the same method used in Synthesis Example 2 to obtain [Compound 5].
(19.8 g, 73 % 수율)(19.8 g, 73% yield)
CDCl
3 에서 H-NMR : 8.48 (d, 1H), 8.13 (d, 2H), 8.01 (d, 1H), 7.82 (s, 1H), 7.80 (d, 1H), 7.66 (d, 1H), 7.60 (t, 1H), 7.47 (t, 2H), 7.41 (d, 1H), 7.18 (d, 2H), 6.69 (d, 2H), 5.37 (s, 2H), 3.89 (q, 2H), 1.51 (t, 3H), 1.34 (s, 9H)H-NMR in CDCl 3 : 8.48 (d, 1H), 8.13 (d, 2H), 8.01 (d, 1H), 7.82 (s, 1H), 7.80 (d, 1H), 7.66 (d, 1H), 7.60 (t, 1H), 7.47 (t, 2H), 7.41 (d, 1H), 7.18 (d, 2H), 6.69 (d, 2H), 5.37 (s, 2H), 3.89 (q, 2H), 1.51 ( t, 3H), 1.34 (s, 9H)
[합성예 5] 화합물 6의 합성[Synthesis Example 5] Synthesis of compound 6
[반응식 5][Scheme 5]
1 단계 : 화합물 3-니트로-9-에틸카바졸 (6-3)의 합성Step 1: Synthesis of compound 3-nitro-9-ethylcarbazole (6-3)
상기 합성예는 [화합물 2-3]의 합성예와 동일하게 진행하여 [화합물 6-3]을 얻었다.The synthesis example proceeded in the same manner as in the synthesis example of [Compound 2-3] to obtain [Compound 6-3].
(21.2 g, 86 % 수율) (21.2 g, 86% yield)
2 단계 : 화합물 2-(4-(터트-부틸)-2-메틸페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 (6-2)의 합성Step 2: Compound 2-(4-(tert-butyl)-2-methylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone (6-2) synthesis
상기 합성예 2-(2)에서 사용한 [화합물 3] 대신 [화합물 7]를 사용한 것을 제외하고는 동일한 방법으로 합성하여 [화합물 6-2]를 얻었다. (32.1 g, 82 % 수율) [Compound 6-2] was obtained by synthesizing in the same manner except that [Compound 7] was used instead of [Compound 3] used in Synthesis Example 2-(2). (32.1 g, 82% yield)
3 단계 : 화합물 (Z)-2-(4-(터트-부틸)-2-메틸페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 옥심 (6-1)의 합성Step 3: Compound (Z)-2-(4-(tert-butyl)-2-methylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone oxime ( 6-1) synthesis
상기 합성예 2-(1)에서 사용한 동일한 방법으로 합성하여 [화합물 6-1]를 얻었다. It was synthesized by the same method used in Synthesis Example 2-(1) to obtain [Compound 6-1].
(24.5 g, 74 % 수율)(24.5 g, 74% yield)
최종 단계 : 화합물 (Z)-2-(4-(터트-부틸)-2-메틸페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 O-아세틸 옥심 (6)의 합성Final step: compound (Z)-2-(4-(tert-butyl)-2-methylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone O- Synthesis of acetyl oxime (6)
상기 합성예 2에서 사용한 동일한 방법으로 합성하여 [화합물 6]를 얻었다. It was synthesized by the same method used in Synthesis Example 2 to obtain [Compound 6].
(19.0 g, 71 % 수율)(19.0 g, 71% yield)
CDCl
3 에서 H-NMR : 8.99 (s, 1H), 8.94 (s, 1H), 8.17 (m, 2H), 7.97 (d, 2H), 7.34 (s, 1H), 7.29 (d, 1H), 6.79 (d, 1H), 5.37 (s, 2H), 4.53 (q, 2H), 2.28 (s, 3H), 2.15 (s, 3H), 1.35 (s, 9H), 1.29 (t, 3H)H-NMR in CDCl 3 : 8.99 (s, 1H), 8.94 (s, 1H), 8.17 (m, 2H), 7.97 (d, 2H), 7.34 (s, 1H), 7.29 (d, 1H), 6.79 (d, 1H), 5.37 (s, 2H), 4.53 (q, 2H), 2.28 (s, 3H), 2.15 (s, 3H), 1.35 (s, 9H), 1.29 (t, 3H)
[합성예 6] 화합물 7의 합성[Synthesis Example 6] Synthesis of compound 7
[반응식 6][Scheme 6]
1 단계 : 화합물 3-니트로-9-에틸카바졸 (7-3)의 합성Step 1: Synthesis of compound 3-nitro-9-ethylcarbazole (7-3)
상기 합성예는 [화합물 2-3]의 합성예와 동일하게 진행하여 [화합물 7-3]을 얻었다.The synthesis example proceeded in the same manner as in the synthesis example of [Compound 2-3] to obtain [Compound 7-3].
(21.2 g, 86 % 수율) (21.2 g, 86% yield)
2 단계 : 화합물 2-(4-(터트-부틸)-2,6-디메틸페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 (7-2)의 합성Step 2: Compound 2-(4-(tert-butyl)-2,6-dimethylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone (7-2 ) synthesis
상기 합성예 2-(2)에서 사용한 [화합물 3] 대신 [화합물 8]를 사용한 것을 제외하고는 동일한 방법으로 합성하여 [화합물 7-2]를 얻었다. (32.4 g, 80 % 수율) [Compound 7-2] was obtained by synthesizing in the same manner except that [Compound 8] was used instead of [Compound 3] used in Synthesis Example 2-(2). (32.4 g, 80% yield)
3 단계 : 화합물 (Z)-2-(4-(터트-부틸)-2,6-디메틸페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 옥심 (7-1)의 합성Step 3: Compound (Z)-2-(4-(tert-butyl)-2,6-dimethylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone Synthesis of oxime (7-1)
상기 합성예 2-(1)에서 사용한 동일한 방법으로 합성하여 [화합물 7-1]를 얻었다. It was synthesized by the same method used in Synthesis Example 2-(1) to obtain [Compound 7-1].
(24.1 g, 72 % 수율)(24.1 g, 72% yield)
최종 단계 : 화합물 (Z)-2-(4-(터트-부틸)-2,6-디메틸페녹시)-1-(9-에틸-6-니트로-9H-카바졸-3-일)에탄온 O-아세틸 옥심 (7)의 합성Final step: compound (Z)-2-(4-(tert-butyl)-2,6-dimethylphenoxy)-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)ethanone Synthesis of O-acetyl oxime (7)
상기 합성예 2에서 사용한 동일한 방법으로 합성하여 [화합물 7]를 얻었다. It was synthesized by the same method used in Synthesis Example 2 to obtain [Compound 7].
(18.9 g, 72 % 수율)(18.9 g, 72% yield)
CDCl
3 에서 H-NMR : 8.99 (s, 1H), 8.94 (s, 1H), 8.17 (m, 2H), 7.97 (d, 2H), 7.15 (s, 2H), 5.37 (s, 2H), 4.53 (q, 2H), 2.28 (s, 3H), 2.15 (s, 6H), 1.35 (s, 9H), 1.29 (t, 3H)H-NMR in CDCl 3 : 8.99 (s, 1H), 8.94 (s, 1H), 8.17 (m, 2H), 7.97 (d, 2H), 7.15 (s, 2H), 5.37 (s, 2H), 4.53 (q, 2H), 2.28 (s, 3H), 2.15 (s, 6H), 1.35 (s, 9H), 1.29 (t, 3H)
[실시예 1~6 및 비교예 1~5] 감광성 수지 조성물의 제조[Examples 1 to 6 and Comparative Examples 1 to 5] Preparation of photosensitive resin composition
교반기가 설치되어 있는 반응 혼합조에 하기 표 1에 기재된 성분과 함량에 따라 프로필렌글리콜메틸에테르아세테이트 (PGMEA, Propyrene Glycol Methyl Ether Acetate), 폴리히드록시스티렌수지(PHS), 디펜타에리트리톨헥사아크릴레이트(DPHA) 및 광개시제를 순차적으로 첨가하고, 상온에서 교반하여 감광성 수지 조성물을 제조하였다. 표 1에 기재된 화합물의 화학식을 표 2에 기재하였다.Propylene glycol methyl ether acetate (PGMEA, Propyrene Glycol Methyl Ether Acetate), polyhydroxystyrene resin (PHS), dipentaerythritol hexaacrylate ( DPHA) and a photoinitiator were sequentially added and stirred at room temperature to prepare a photosensitive resin composition. Chemical formulas of the compounds listed in Table 1 are shown in Table 2.
구분division | PHS(g)PHS(g) | DPHA(g)DPHA(g) | 광개시제 (g)Photoinitiator (g) | PGMEA(g)PGMEA(g) |
실시예 1Example 1 | 2020 | 1010 | 화합물 2 (1)compound 2 (1) | 6969 |
실시예 2Example 2 | 2020 | 1010 | 화합물 3 (1)compound 3 (1) | 6969 |
실시예 3Example 3 | 2020 | 1010 | 화합물 4 (1)compound 4 (1) | 6969 |
실시예 4Example 4 | 2020 | 1010 | 화합물 5 (1)compound 5 (1) | 6969 |
실시예 5Example 5 | 2020 | 1010 | 화합물 6 (1)compound 6 (1) | 6969 |
실시예 6Example 6 | 2020 | 1010 | 화합물 7 (1)compound 7 (1) | 6969 |
비교예 1Comparative Example 1 | 2020 | 1010 | OXE-01 (1)OXE-01 (1) | 6969 |
비교예 2Comparative Example 2 | 2020 | 1010 | OXE-02 (1)OXE-02 (1) | 6969 |
비교예 3Comparative Example 3 | 2020 | 1010 | I-184 (1)I-184 (1) | 6969 |
비교예 4Comparative Example 4 | 2020 | 1010 | 화합물 10 (1)compound 10 (1) | 6969 |
비교예 5Comparative Example 5 | 2020 | 1010 | 화합물 11 (1)compound 11 (1) | 6969 |
PHSPHS |
알드리치사 (폴리 4-히드록시페놀), Mw=25,000 Aldrich (poly 4-hydroxyphenol), Mw=25,000 |
DPHADPHA |
알드리치사,
디펜타에리트리톨 헥사아크릴레이트 Aldrichsa, Dipentaerythritol Hexaacrylate |
OXE-01OXE-01 | |
OXE-02OXE-02 | |
I-184I-184 | |
화합물 10compound 10 | |
화합물 11compound 11 | |
PGMEAPGMEA | 프로필렌글리콜메틸에테르아세트산 (Propylene Glycol Methyl Ether Acetate)Propylene Glycol Methyl Ether Acetate |
실험예 1: 감도 평가Experimental Example 1: Sensitivity evaluation
실시예 1~6 및 비교예 1~5에서 제조한 감광성 수지 조성물의 평가는, 유리기판 위에 건조 후 막두께가 5um가 되도록 코팅하고, 120℃에서 2분간 건조하여 용제를 휘발시키고, 퓨전램프로 노광하고, 23℃의 0.045wt% KOH 수용액에서 현상하고, 두께를 비접촉식 두께 측정기를 이용하여 초기 두께 대비 80%를 유지하는 노광량을 기준으로 감도를 평가하였다.In the evaluation of the photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 5, after drying on a glass substrate, the coating was coated to have a film thickness of 5 μm, dried at 120° C. for 2 minutes to volatilize the solvent, and a fusion lamp Exposure, development in 0.045wt% KOH aqueous solution at 23 ℃, and the thickness was evaluated based on the exposure amount maintaining 80% compared to the initial thickness using a non-contact thickness measuring instrument.
실험예 2: PGMEA 용해도 평가Experimental Example 2: PGMEA solubility evaluation
실시예 1~6 및 비교예 1~5의 감광성 수지 조성물의 제조에서, 개시제 1g 대신에 10g로하여, 상온에서 1시간 교반 후 용액의 투명도 즉, 헤이즈를 육안으로 확인하여 용해도를 확인하여, 투명한 경우 O, 헤이즈가 관찰된 경우 X로 판정하였다.In the preparation of the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5, 10 g instead of 1 g of the initiator, after stirring at room temperature for 1 hour, the transparency of the solution, that is, the haze, was visually checked to confirm the solubility, and the transparent The case was judged as O, and when haze was observed, it was judged as X.
실험예 1 및 2의 결과를 하기 표 3에 기재하였다.The results of Experimental Examples 1 and 2 are shown in Table 3 below.
감도
(mJ/cm 2)Sensitivity (mJ/cm 2 ) |
용해도
Solubility |
|
실시예 1Example 1 | 3030 | OO |
실시예 2Example 2 | 3131 | OO |
실시예 3Example 3 | 2929 | OO |
실시예 4Example 4 | 3535 | OO |
실시예 5Example 5 | 3131 | OO |
실시예 6Example 6 | 2828 | OO |
비교예 1Comparative Example 1 | 8080 | OO |
비교예 2Comparative Example 2 | 5555 | OO |
비교예 3Comparative Example 3 | 150150 | OO |
비교예 4Comparative Example 4 | 115115 | OO |
비교예 5Comparative Example 5 | 3030 | XX |
표 3에서, 비교예 1~5에 대비하여, 실시예 1~6은 감도 및 용해도 결과가 모두 우수함을 확인할 수 있다. In Table 3, as compared to Comparative Examples 1 to 5, it can be seen that Examples 1 to 6 have excellent sensitivity and solubility results.
이상에서 본 발명의 바람직한 실시예들에 대하여 상세하게 설명하였지만 본 발명의 권리 범위는 이에 한정되는 것은 아니고 다음의 청구 범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리 범위에 속하는 것이다.Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It belongs to the scope of the invention.
Claims (4)
- 하기 화학식 1로 표시되는 옥심에스테르 카바졸 유도체 화합물:An oxime ester carbazole derivative compound represented by the following formula (1):<화학식 1><Formula 1>상기 식에서, In the above formula,R 1 및 R 3은, 각각 독립적으로, C1~C12의 지방족 탄화수소이고,R 1 and R 3 are each independently a C1-C12 aliphatic hydrocarbon,R 2는 C1~C12의 알킬 또는 C6~C12의 아릴이고,R 2 is C1~ C12 alkyl or C6~ C12 aryl;m은 1~2의 정수이고,m is an integer of 1 to 2,n은 1~5의 정수이다.n is an integer from 1 to 5;
- 제1항에 있어서,According to claim 1,n이 2~5의 정수인where n is an integer from 2 to 5옥심에스테르 카바졸 유도체 화합물.Oxime ester carbazole derivative compound.
- 광개시제를 포함하는 감광성 수지 조성물이고,A photosensitive resin composition comprising a photoinitiator,상기 광개시제는 제1항 내지 제3항 중 어느 한 항에 따른 옥심에스테르 카바졸 유도체 화합물을 포함하는 감광성 수지 조성물.The photoinitiator is a photosensitive resin composition comprising an oxime ester carbazole derivative compound according to any one of claims 1 to 3.
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US20170235224A1 (en) * | 2014-10-15 | 2017-08-17 | Chi Mei Corporation | Photosensitive resin composition, color filter, and liquid crystal display element thereof |
WO2018235664A1 (en) * | 2017-06-20 | 2018-12-27 | 株式会社Adeka | Polymerizable composition, photosensitive composition for black matrixes, and photosensitive composition for black column spacers |
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US20170235224A1 (en) * | 2014-10-15 | 2017-08-17 | Chi Mei Corporation | Photosensitive resin composition, color filter, and liquid crystal display element thereof |
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