KR20210152189A - Oxime ester carbazole compound,and photosensitive resin composition containing thereof - Google Patents

Abstract

The present invention provides an oxime ester carbazole compound represented by chemical formula 1 or chemical formula 2, wherein in the chemical formulas: X is Cl or Br; R_1 and R_3 are each independently C_1 to C_20 alkyl, C_5 to C_10 cycloalkyl, C_6 to C_30 aryloxy, C_1 to C_20 alkylthio, C_6 to C_30 aryl, C_7 to C_30 aralkyl, or C_5 to C_30 heteroaryl; R_2 is C_1 to C_3 alkyl or phenyl; and n is an integer from 1 to 3.

Description

Oxime ester carbazole compound and photosensitive resin comprising the same

The present invention relates to an oxime ester carbazole compound and a photosensitive resin composition comprising the same. More specifically, it relates to an oxime ester carbazole compound having excellent solubility in organic solvents, and a photosensitive resin composition comprising the same.

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. 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.

The photosensitive composition for this purpose includes ink for inkjet ink or a transparent or colored protective film for automobiles or mobile phones, etc., and a photoinitiator can be applied to the photosensitive resin composition for photolithography using a phenomenon in which solubility is reduced due to polymerization 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 may be applied on a substrate to form a coating film, exposed by light irradiation using a photomask or the like on a specific portion of the coating film, and then developed and removed to form a pattern.

The photosensitive resin composition typically includes a polymeric resin compound, a polymerizable compound containing an ethylenically unsaturated bond, a solvent, and a photoinitiator.

The photosensitive resin composition is being manufactured for the purpose of composing liquid crystal display devices such as TVs and monitors in addition to the conventional use of laptops and mobiles as the uses of LCDs are advanced and diversified, and reacts quickly to light to improve productivity and durability. And, the demand for mechanically excellent physical properties is increasing.

On the other hand, when a pattern is formed by a photo-lithography method or an insulating protective film is formed through full exposure, the property of quickly responding to light, that is, photosensitivity, is a very important factor. In addition, in order to ensure that the liquid crystal display device is not damaged by an external impact and exhibits its original performance, the column spacer serving as a support or an overcoat and passivation film serving as a protective film must have excellent mechanical properties. Accordingly, these problems can be solved by using a photopolymerization initiator having excellent photosensitivity.

Common examples of photoinitiators used in the photosensitive resin composition include acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives, and oxime ester derivatives. It absorbs and exhibits almost no color, has a high radical generation efficiency, and has excellent compatibility and stability with the materials of the photosensitive resin composition.

However, the initially developed oxime ester derivative compound has a low photopolymerization initiation efficiency, and, in particular, has a low sensitivity during a pattern exposure process, so that an exposure amount needs to be increased, thereby reducing production.

Recently, as the demand for large-area high-definition displays increases 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.

Korean Patent Laid-Open Publication No. 10-2008-0109833 discloses a photosensitive composition using an oxime ester derivative and a specific sensitizer, which relates to a photosensitive composition, a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed board. It is difficult to expect sufficient productivity improvement due to low solubility and low sensitivity.

It is an object of the present invention to provide an oxime ester carbazole compound with increased photosensitivity due to increased solubility in organic solvents and increased photopolymerization initiation efficiency, and a photosensitive resin composition comprising the same.

The above and other objects of the present invention can all be achieved by the present invention described below.

1. One aspect of the present invention relates to an oximeester carbazole compound.

The oxime ester carbazole compound is represented by Formula 1 or Formula 2:

[Formula 1]

[Formula 2]

wherein X is Cl or Br, R ₁ and R ₃ are each independently C ₁ to C ₂₀ alkyl, C ₅ to C ₁₀ cycloalkyl, C ₆ to C ₃₀ aryloxy, C ₁ to C ₂₀ alkylthio, C ₆ to C ₃₀ aryl, C ₇ to C ₃₀ aralkyl, or C ₅ to C ₃₀ heteroaryl, R ₂ is C ₁ to C ₃ alkyl or phenyl;

n is an integer from 1 to 3.

2. In the above 1 embodiment, X is Cl, R ₁ and R ₃ are each independently linear or branched C ₁ to C ₂₀ alkyl, C ₅ to C ₁₀ cycloalkyl, C ₆ to C ₃₀ aryl, R ₂ may be methyl or phenyl.

3. In embodiments 1 or 2, the compound of Formula 1 may be any one selected from Formulas 1-1 to 1-30.

4. In embodiments 1 to 3, the compound of Formula 2 may be any one selected from the following Formulas 2-1 to 2-24.

5. Another aspect of the present invention is the oxime ester carbazole compound; And it provides a photosensitive resin composition comprising a compound having an ethylenically unsaturated bond.

6. In the 5th embodiment, the photosensitive resin composition may further include a developable binder resin.

7. In the above 5 or 6 embodiments, the developable binder resin is any one selected from the group consisting of acrylic acid-containing acrylic copolymer, novolak-based phenol resin, polyhydroxystyrene resin, hydroxystyrene and copolymer of acrylate. It may be one or a mixture of two or more.

The present invention can prepare a photosensitive resin composition having high sensitivity by providing a photoinitiator having excellent radical generation efficiency even with a small exposure amount.

Even when an excess of solvent is added to the photosensitive resin composition, solubility is increased and precipitation does not occur, so the efficiency of a large LCD manufacturing process can be greatly increased.

In addition, in the photosensitive resin composition, an ethyl ether group is introduced into a nitrogen atom in the carbazole ring substituted with a nitro group, and the solubility in a solvent is increased by being substituted with alkyl or aryl at one end, as well as pattern stability, chemical resistance and adhesion.

1 is a graph showing the sensitivity evaluation of a photosensitive resin composition according to an embodiment of the present invention.

Like reference numerals refer to like elements throughout. In addition, in describing the present invention, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

When 'including', 'having', 'consisting', etc. mentioned in this specification are used, other parts may be added unless 'only' is used. When a component is expressed in the singular, cases including the plural are included unless otherwise explicitly stated.

In interpreting the components, it is construed as including an error range even if there is no separate explicit description.

One aspect of the present invention provides an oxime ester carbazole compound represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

[Formula 2]

wherein X is Cl or Br, R ₁ and R ₃ are each independently C ₁ to C ₂₀ alkyl, C ₅ to C ₁₀ cycloalkyl, C ₆ to C ₃₀ aryloxy, C ₁ to C ₂₀ alkylthio, C ₆ to C ₃₀ aryl, C ₇ to C ₃₀ aralkyl, or C ₅ to C ₃₀ heteroaryl, R ₂ is C ₁ to C ₃ alkyl or phenyl;

n is an integer from 1 to 3.

More specifically, X is C ₁ , R ₁ and R ₃ are each independently linear or branched C ₁ to C ₂₀ alkyl, C ₅ to C ₁₀ cycloalkyl, C ₆ to C ₃₀ aryl, and R ₂ is methyl or phenyl.

When R ₁ and R ₃ are alkyl or aryl, and R ₂ is methyl or phenyl, pattern stability, chemical resistance, and adhesion may be improved in the photosensitive resin composition.

The oxime ester carbazole compound represented by Formula 1 or Formula 2 introduces a 2-halo ethyl ether group containing an ethyl ester that is 1 to 3 units to a nitrogen atom in the carbazole ring. Propylene glycol methyl useful as a solvent for a photosensitive composition The solubility in ether acetate (PGMEA) is greatly increased.

On the other hand, when R ₁ , R ₂ or R ₃ is each independently alkyl, the alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t -amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl , allyl, butenyl, ethynyl, and may be any one selected from the group consisting of propynyl.

In addition, when R ₁ , or R ₃ is each independently aryl, phenyl, p-methoxyphenyl, o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphenyl, p-fluorophenyl, p- Chlorophenyl, p-bromophenyl, pentafluorophenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 9-phenantholyl, 1-pyrenyl, 9-fluorenyl, terphenyl group , o-tolyl, m-tolyl, p-tolyl, and preferably any one selected from the group consisting of xenyl.

When R ₁ , or R ₃ is each independently aralkyl, preferably any one selected from the group consisting of benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and phenylethenyl do.

When R ₁ , or R ₃ is each independently a heteroaryl group, from the group consisting of furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, and pyrrolidyl It is preferable that any one selected.

When R ₂ is an alkyl, it is methyl, ethyl, or propyl, and in the case of an aryl group, it is preferably phenyl.

More specifically, the compound of Formula 1 is any one selected from the following Formulas 1-1 to 1-30.

In addition, the compound of Formula 2 is any one selected from the following Formulas 2-1 to 2-24.

Another aspect of the present invention, the oxime ester carbazole compound; And it provides a photosensitive resin composition comprising a compound having an ethylenically unsaturated bond.

In one embodiment of the present invention, the photosensitive resin composition comprises 0.001 to 10 wt% of an oxime ester carbazole compound, 10 to 50 wt% of a developable binder, 5 to 30 wt% of a compound having an ethylenically unsaturated bond, and 50 to 80 wt% of a solvent Including %.

The compound having the ethylenically unsaturated bond is (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate ( Alkyl ester of meth) acrylic acid, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate having 2 to 14 ethylene oxide groups, ethylene glycol di (meth) acrylate, ethylene oxide group 2 to 14 polyethylene glycol di (meth) acrylate, 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 (meth) acrylate , pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol tri (meth) acrylate with polyhydric alcohols such as α, β-unsaturated carboxylic acids Any one or two or more selected from the group consisting of a compound obtained by esterifying a compound and an acrylic acid adduct of a polyvalent glycidyl compound such as trimethylolpropane triglycidyl ether acrylic acid adduct may be used together.

The polymerizable compound having an ethylenically unsaturated bond of the above type is suitable for use as a photoinitiator when mixed with the oxime ester compound.

When the polymerizable compound is included, increased heat resistance and film strength may be obtained, and developability of the photosensitive resin composition may be increased.

When two or more types of the above-mentioned polymerizable compound are mixed and used, it is preferable to use them as a copolymer by copolymerization.

The photosensitive resin composition further includes a developable binder resin.

The developable binder resin is any one or two selected from the group consisting of acrylic acid-containing acrylic copolymer, novolak-based phenol resin, polyhydroxystyrene resin, polysiloxane resin, polyimide resin, hydroxystyrene, and a copolymer of acrylate. It may be a mixture of the above.

The developable binder resin may increase the developability of the photosensitive resin composition with an unsaturated monobasic acid.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are only illustrative of the present invention and the scope of the present invention is not limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

[Scheme 1]

According to Scheme 1, compounds of Formulas 1-1 to 1-30 were synthesized.

2-halo ethyl ether carbazole and acyl chloride prepared from the S _N 2 reaction of carbazole and dihalo ethyl ether in the presence of a base were subjected to Fridel-Craft reaction in the presence of Lewis acid to obtain the corresponding ketone compound.

The ketone compound was reacted with nitric acid to introduce a nitro group to the carbazole ring, and the nitro ketone compound was subjected to an oxime reaction with hydroxylamine hydrochloride to obtain the corresponding oxime compound. The oxime compound was reacted with an acyl halide or a corresponding anhydride to obtain oxime ester carbazole derivative compounds represented by Chemical Formulas 1-1 to 1-30.

[Scheme 2]

According to Scheme 2, compounds of Formulas 2-1 to 2-24 were synthesized.

First, 2-halo ethyl ether carbazole prepared according to Scheme 1 was subjected to Fridel-Craft reaction with acyl chloride according to Scheme 2 in the presence of Lewis acid to obtain a corresponding ketone compound.

The ketone compound was reacted with nitric acid to introduce a nitro group into the carbazole ring and reacted with alkyl nitrite in the presence of a strong base to obtain the corresponding α-keto oxime compound.

The α-keto oxime compound was reacted with an acyl halide or a corresponding anhydride to obtain a derivative of the α-ketooxime ester carbazole compound represented by Chemical Formulas 2-1 to 2-24.

A more specific example will be described below.

<Example 1> Synthesis of compounds of Formula 1-17

[Formula 1-17]

Step 1: Synthesis of 9-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-9H-carbazole

Carbazole (16.7 g, 0.1 mol) was added to a reactor containing DMF (160 mL) under a nitrogen atmosphere and stirred. After confirming that the carbazole is dissolved, NaOH (8.0 g, 0.2 mol) is added, and 1,2-bis(2-chloroethoxy)ethane (37.2 g, 0.2 mol) is added dropwise over 10 minutes while stirring at room temperature. After confirming that carbazole was consumed by TLC, the reaction solution was added dropwise to distilled water (200 mL), and DCM (200 mL) was further added. The extracted organic layer was washed by adding distilled water (200 mL X 3 times) three times. After the organic layer was concentrated under reduced pressure, the concentrate was purified by silica gel column chromatography (n-Hex./E.A. = 3/1) to obtain 27.6 g of an off-white solid in 87% yield.

¹ H-NMR confirmed the product.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.07 (d/d, 2H), 7.44 (m, 4H), 7.22 (m, 2H), 4.48 (t, 2H), 3.85 (t, 2H), 3.75-3.60 (m, 8H).

Step 2: 1-(9-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-9H-carbazol

Synthesis of -3-yl)octan-1-one

The compound from Step 1 (20.0 g, 63 mmol) was added to AlCl3 (9.2 g, 69 mmol) precipitated in DCM (80 mL) under a nitrogen atmosphere, and then the reaction solution was cooled using an ice-bath. After dissolving octanoyl chloride (11.2 g, 69 mmol) in DCM (20 mL), it is slowly added dropwise to the reaction solution over 30 minutes. After completion of the dropping, the ice-bath was removed and the mixture was stirred at room temperature for 2 hours.

After confirming the completion of the reaction by TLC, the reaction solution is slowly added dropwise to a sufficiently cooled 10% HCl (200 mL) aqueous solution. The organic layer in the reaction solution was extracted using DCM (100 mL), washed with 5% NaOH (200 mL) and distilled water (200 mL), and then concentrated under reduced pressure.

The concentrate was purified by silica gel column chromatography (n-Hex./E.A. = 2/1) to obtain 25.4 g of a pale yellow solid in 91% yield.

¹ H-NMR confirmed the product.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.57 (s, 1H), 8.22 (d, 1H), 8.19 (d, 1H), 7.67-7.32 (m, 4H), 4.49 (t, 2H), 3.89 (t, 2H), 3.54-3.42 (m, 8H), 2.97 (t, 2H), 1.57 (m, 2H), 1.43-1.24 (m, 8H), 0.89 (t, 3H).

Step 3: 1-(9-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-6-nitro-9H-

Synthesis of carbazol-3-yl)octan-1-one

The compound from Step 2 (22 g, 50 mmol) was added to an acetic acid solution (150 mL) under a nitrogen atmosphere, followed by stirring. Nitric acid (9.4 g, 100 mmol) was slowly added dropwise to the stirred reaction solution over 30 minutes while maintaining the temperature at 30 °C or less, followed by stirring for 2 hours.

After confirming the completion of the reaction by TLC, the reaction solution was added dropwise to distilled water (200 mL) and stirred for additional 30 minutes. After DCM (200 mL) was added to separate the organic layer, distilled water (200 mL X 3 times) was added to wash the organic layer, and the mixture was concentrated under reduced pressure. The concentrate was recrystallized using polar and non-polar solvents to obtain 20.5 g of a yellow solid in 84% yield.

¹ H-NMR confirmed the product.

1H-NMR (δ, ppm), CDCl ₃ : 9.04 (s, 1H), 8.51 (s, 1H), 8.37 (d/d, 1H), 7.97 (d/d, 1H), 7.54 (m, 2H) , 4.55 (t, 2H), 3.93 (t, 2H), 3.57-3.47 (m, 8H), 2.98 (t, 2H), 1.59 (m, 2H), 1.43-1.26 (m, 8H), 0.88 (t) , 3H).

Step 4: 1-(9-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-6-nitro-9H-

Synthesis of carbazol-3-yl)octan-1-one oxime

The compound from Step 3 (18.0 g, 37 mmol) was placed in ethanol (120 mL) under a nitrogen atmosphere. Hydroxylamine hydrochloride (2.8 g, 41 mmol) and sodium acetate trihydrate (5.6 g, 41 mmol) were added to the reaction solution, and the temperature was raised to reflux, followed by stirring for 4 hours.

After confirming the completion of the reaction by TLC, the reaction solution is cooled to room temperature, and distilled water (200 mL) is added to perform quenching. The organic layer extracted by adding DCM (200 mL) was washed with distilled water (200 mL) three times, and then concentrated under reduced pressure. 17.9 g of the yellow solid obtained after concentration was used for the next reaction without further purification.

¹ H-NMR confirmed the product.

¹ H-NMR (δ, ppm), CDCl ₃ : 9.02 (s, 1H), 8.45 (s, 1H), 8.38 (d/d, 1H), 7.99 (d/d, 1H), 7.53 (m, 2H) ), 4.56 (t, 2H), 3.92 (t, 2H), 3.57-3.47 (m, 8H), 2.92 (t, 2H), 1.60 (m, 2H), 1.43-1.26 (m, 8H), 0.88 ( t, 3H).

Step 5: 1-(9-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-6-nitro-9H-

Synthesis of carbazol-3-yl)octan-1-one O-acetyl oxime

The compound from Step 4 (15.0 g, 30 mmol) was dissolved in DCM (80 mL) under a nitrogen atmosphere, and then acetic anhydride (3.4 g, 33 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 4 hours.

After confirming the completion of the reaction by TLC, distilled water (200 mL) and DCM (120 mL) are added to the reaction solution. The obtained organic layer was washed 3 times with distilled water (200 mL), and then concentrated under reduced pressure. The concentrate was subjected to recrystallization using polar and non-polar solvents to obtain a final product in 82% yield of 13.4 g of a yellow solid.

¹ H-NMR confirmed the synthesis of the carbazole derivative.

¹ H-NMR (δ, ppm), CDCl ₃ : 9.03 (s, 1H), 8.45 (s, 1H), 8.38 (d/d, 1H), 7.99 (d/d, 1H), 7.53 (m, 2H) ), 4.56 (t, 2H), 3.92 (t, 2H), 3.57-3.47 (m, 8H), 2.98 (t, 2H), 2.29 (s, 3H), 1.63 (m, 2H), 1.44-1.26 ( m, 8H), 0.87 (t, 3H).

The oxime ester carbazole derivative compounds represented by Formulas 1-1 to 1-10 are 9- prepared from _{the S N} 2 reaction of 1-chloro-2-(2-chloroethoxy)ethane with a nitrogen atom in the carbazole ring in the presence of a base. (2-(2-chloroethoxy)ethyl)-9H-carbazole was synthesized as shown in Table 1 according to the preparation method of Example 1 as a starting material.

Formula No. R ₁ R ₂ ¹ H-NMR (δ, ppm) 1-1 CH ₃ CH ₃ 9.04 (s, 1H), 8.43 (s, 1H), 8.37 (d/d, 1H), 8.01 (d/d, 1H), 7.52 (m, 2H), 4.54 (t, 2H), 3.96 (t, 2H), 3.59 (t, 2H), 3.46 (t, 2H), 2.92 (s, 3H), 2.32 (s, 3H). 1-2 C ₂ H ₅ CH ₃ 9.04 (s, 1H), 8.42 (s, 1H), 8.36 (d/d, 1H), 7.99 (d/d, 1H), 7.53 (m, 2H), 4.54 (t, 2H), 3.95 (t, 2H), 3.58 (t, 2H), 3.47 (t, 2H), 2.90 (q, 2H), 2.32 (s, 3H), 1.12 (t, 3H). 1-3 C ₃ H ₇ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.38 (d/d, 1H), 7.98 (d/d, 1H), 7.52 (m, 2H), 4.54 (t, 2H), 3.96 (t, 2H), 3.59 (t, 2H), 3.45 (t, 2H), 2.87 (t, 2H), 2.31 (s, 3H), 1.69 (m, 2H), 1.02 (t, 3H). 1-4 C ₄ H ₉ CH ₃ 9.03 (s, 1H), 8.43 (s, 1H), 8.36 (d/d, 1H), 7.99 (d/d, 1H), 7.52 (m, 2H), 4.53 (t, 2H), 3.95 (t, 2H), 3.60 (t, 2H), 3.45 (t, 2H), 2.86 (t, 2H), 2.31 (s, 3H), 1.62-1.43 (m, 4H), 0.96 (t, 3H). 1-5 C ₅ H ₁₁ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.38 (d/d, 1H), 7.97 (d/d, 1H), 7.53 (m, 2H), 4.53 (t, 2H), 3.95 (t, 2H), 3.60 (t, 2H), 3.44 (t, 2H), 2.84 (t, 2H), 2.30 (s, 3H), 1.59-1.37 (m, 6H), 0.93 (t, 3H). 1-6 C ₆ H ₁₃ CH ₃ 9.03 (s, 1H), 8.43 (s, 1H), 8.36 (d/d, 1H), 7.98 (d/d, 1H), 7.52 (m, 2H), 4.52 (t, 2H), 3.93 (t, 2H), 3.59 (t, 2H), 3.45 (t, 2H), 2.82 (t, 2H), 2.30 (s, 3H), 1.55-1.33 (m, 8H), 0.89 (t, 3H). 1-7 C ₇ H ₁₅ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.37 (d/d, 1H), 7.97 (d/d, 1H), 7.51 (m, 2H), 4.51 (t, 2H), 3.93 (t, 2H), 3.58 (t, 2H), 3.45 (t, 2H), 2.80 (t, 2H), 2.29 (s, 3H), 1.48-1.30 (m, 10H), 0.87 (t, 3H). 1-8 C ₆ H ₁₁ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.38 (d/d, 1H), 7.98 (d/d, 1H), 7.53 (m, 2H), 4.54 (t, 2H), 3.96 (t, 2H), 3.60 (t, 2H), 3.45 (t, 2H), 2.71 (m, 1H), 2.27 (s, 3H), 1.80-1.29 (m, 10H). 1-9 C ₇ H ₇ CH ₃ 9.03 (s, 1H), 8.45 (s, 1H), 8.38 (d/d, 1H), 7.99 (d/d, 1H), 7.63 (d, 1H), 7.53 (m, 2H), 7.48-7.12 ( m, 3H), 4.54 (t, 2H), 3.96 (t, 2H), 3.61 (t, 2H), 3.46 (t, 2H), 2.43 (s, 3H), 2.29 (s, 3H). 1-10 C ₇ H ₁₅ C ₆ H ₅ 9.02 (s, 1H), 8.42 (s, 1H), 8.39 (d/d, 1H), 8.19 (d/d, 1H), 8.01 (d/d, 1H), 7.98 (d/d, 1H), 7.72-7.59 (m, 3H), 7.54 (m, 2H), 4.54 (t, 2H), 3.96 (t, 2H), 3.61 (t, 2H), 3.46 (t, 2H), 2.82 (t, 2H) , 1.48-1.30 (m, 10H), 0.87 (t, 3H).

Oxime ester carbazole derivative compounds represented by Chemical Formulas 1-11 to 1-16 and 1-18 to 1-20 were synthesized as shown in Table 2 according to the preparation method of Example 1.

Formula No. R ₁ R ₂ ¹ H-NMR (δ, ppm) 1-11 CH ₃ CH ₃ 9.04 (s, 1H), 8.43 (s, 1H), 8.37 (d/d, 1H), 8.01 (d/d, 1H), 7.52 (m, 2H), 4.57 (t, 2H), 3.91 (t, 2H), 3.58-3.45 (m, 8H), 2.92 (s, 3H), 2.32 (s, 3H). 1-12 C ₂ H ₅ CH ₃ 9.04 (s, 1H), 8.43 (s, 1H), 8.37 (d/d, 1H), 7.99 (d/d, 1H), 7.53 (m, 2H), 4.56 (t, 2H), 3.92 (t, 2H), 3.57-3.45 (m, 8H), 2.90 (q, 2H), 2.32 (s, 3H), 1.09 (t, 3H). 1-13 C ₃ H ₇ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.38 (d/d, 1H), 7.98 (d/d, 1H), 7.52 (m, 2H), 4.56 (t, 2H), 3.91 (t, 2H), 3.56-3.43 (m, 8H), 2.87 (t, 2H), 2.31 (s, 3H), 1.68 (m, 2H), 1.03 (t, 3H). 1-14 C ₄ H ₉ CH ₃ 9.03 (s, 1H), 8.43 (s, 1H), 8.37 (d/d, 1H), 7.99 (d/d, 1H), 7.52 (m, 2H), 4.55 (t, 2H), 3.92 (t, 2H), 3.56-3.42 (m, 8H), 2.86 (t, 2H), 2.31 (s, 3H), 1.62-1.43 (m, 4H), 0.96 (t, 3H). 1-15 C ₅ H ₁₁ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.38 (d/d, 1H), 7.98 (d/d, 1H), 7.51 (m, 2H), 4.54 (t, 2H), 3.93 (t, 2H), 3.56-3.43 (m, 8H), 2.83 (t, 2H), 2.29 (s, 3H), 1.58-1.37 (m, 6H), 0.93 (t, 3H). 1-16 C ₆ H ₁₃ CH ₃ 9.03 (s, 1H), 8.43 (s, 1H), 8.36 (d/d, 1H), 7.96 (d/d, 1H), 7.50 (m, 2H), 4.55 (t, 2H), 3.92 (t, 2H), 3.56-3.42 (m, 8H), 2.83 (t, 2H), 2.28 (s, 3H), 1.56-1.33 (m, 8H), 0.89 (t, 3H). 1-18 C ₆ H ₁₁ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.38 (d/d, 1H), 7.98 (d/d, 1H), 7.52 (m, 2H), 4.56 (t, 2H), 3.92 (t, 2H), 3.55-3.42 (m, 8H), 2.69 (m, 1H), 2.25 (s, 3H), 1.88-1.25 (m, 10H). 1-19 C ₇ H ₇ CH ₃ 9.03 (s, 1H), 8.45 (s, 1H), 8.38 (d/d, 1H), 7.99 (d/d, 1H), 7.63 (d, 1H), 7.53 (m, 2H), 7.48-7.12 ( m, 3H), 4.55 (t, 2H), 3.91 (t, 2H), 3.58-3.45 (m, 8H), 2.35 (s, 3H), 2.29 (s, 3H). 1-20 C ₇ H ₁₅ C ₆ H ₅ 9.02 (s, 1H), 8.42 (s, 1H), 8.39 (d/d, 1H), 8.19 (d/d, 1H), 8.01 (d/d, 1H), 7.98 (d/d, 1H), 7.72-7.58 (m, 3H), 7.55 (m, 2H), 4.54 (t, 2H), 3.94 (t, 2H), 3.59-3.46 (m, 8H), 3.01 (t, 2H), 2.26 (s, 3H), 1.63 (m, 2H), 1.46-1.23 (m, 8H), 0.88 (t, 3H).

The oxime ester carbazole derivative compounds represented by Formulas 1-21 to 1-30 have a nitrogen atom in the carbazole ring and 1-chloro-2-(2-(2-(2-chloroethoxy)ethoxy)ethoxy)ethane in the presence of a base. 9-(2-(2-(3-(2-chloroethoxy)propoxy)ethoxy)ethyl)-9H-carbazole prepared from the S _{N 2 reaction of} synthesized.

Formula No. R ₁ R ₂ ¹ H-NMR (δ, ppm) 1-21 CH ₃ CH ₃ 9.05 (s, 1H), 8.44 (s, 1H), 8.36 (d/d, 1H), 8.01 (d/d, 1H), 7.52 (m, 2H), 4.57 (t, 2H), 3.93 (t, 2H), 3.61-3.49 (m, 12H), 2.92 (s, 3H), 2.32 (s, 3H). 1-22 C ₂ H ₅ CH ₃ 9.04 (s, 1H), 8.43 (s, 1H), 8.36 (d/d, 1H), 8.01 (d/d, 1H), 7.53 (m, 2H), 4.57 (t, 2H), 3.93 (t, 2H), 3.61-3.50 (m, 12H), 2.90 (q, 2H), 2.32 (s, 3H), 1.12 (t, 3H). 1-23 C ₃ H ₇ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.38 (d/d, 1H), 7.98 (d/d, 1H), 7.52 (m, 2H), 4.57 (t, 2H), 3.93 (t, 2H), 3.60-3.48 (m, 12H), 2.87 (t, 2H), 2.31 (s, 3H), 1.68 (m, 2H), 1.02 (t, 3H). 1-24 C ₄ H ₉ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.38 (d/d, 1H), 7.99 (d/d, 1H), 7.51 (m, 2H), 4.56 (t, 2H), 3.94 (t, 2H), 3.59-3.45 (m, 12H), 2.85 (t, 2H), 2.29 (s, 3H), 1.60-1.40 (m, 4H), 0.96 (t, 3H). 1-25 C ₅ H ₁₁ CH ₃ 9.03 (s, 1H), 8.43 (s, 1H), 8.38 (d/d, 1H), 7.98 (d/d, 1H), 7.53 (m, 2H), 4.56 (t, 2H), 3.93 (t, 2H), 3.60-3.45 (m, 12H), 2.82 (t, 2H), 2.30 (s, 3H), 1.60-1.37 (m, 6H), 0.93 (t, 3H). 1-26 C ₆ H ₁₃ CH ₃ 9.03 (s, 1H), 8.43 (s, 1H), 8.38 (d/d, 1H), 7.99 (d/d, 1H), 7.52 (m, 2H), 4.56 (t, 2H), 3.92 (t, 2H), 3.61-3.42 (m, 12H), 2.85 (t, 2H), 2.29 (s, 3H), 1.55-1.33 (m, 8H), 0.89 (t, 3H). 1-27 C ₇ H ₁₅ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.38 (d/d, 1H), 7.98 (d/d, 1H), 7.52 (m, 2H), 4.55 (t, 2H), 3.92 (t, 2H), 3.60-3.42 (m, 12H), 2.84 (t, 2H), 2.28 (s, 3H), 1.48-1.30 (m, 10H), 0.87 (t, 3H). 1-28 C ₆ H ₁₁ CH ₃ 9.03 (s, 1H), 8.44 (s, 1H), 8.36 (d/d, 1H), 7.97 (d/d, 1H), 7.53 (m, 2H), 4.54 (t, 2H), 3.96 (t, 2H), 3.60 (t, 2H), 3.45 (t, 2H), 2.65 (m, 1H), 2.27 (s, 3H), 1.80-1.21 (m, 10H). 1-29 C ₇ H ₇ CH ₃ 9.03 (s, 1H), 8.45 (s, 1H), 8.38 (d/d, 1H), 7.99 (d/d, 1H), 7.63 (d, 1H), 7.53 (m, 2H), 7.48-7.12 ( m, 3H), 4.57 (t, 2H), 3.94 (t, 2H), 3.59-3.44 (m, 12H), 2.43 (s, 3H), 2.29 (s, 3H). 1-30 C ₇ H ₁₅ C ₆ H ₅ 9.02 (s, 1H), 8.42 (s, 1H), 8.39 (d/d, 1H), 8.19 (d/d, 1H), 8.01 (d/d, 1H), 7.98 (d/d, 1H), 7.72-7.59 (m, 3H), 7.54 (m, 2H), 4.56 (t, 2H), 3.91 (t, 2H), 3.62-3.45 (m, 12H), 2.82 (t, 2H), 1.48-1.30 ( m, 10H), 0.87 (t, 3H).

Compounds of Formulas 1-1 to 1-30 were prepared by introducing _{R 1} , R ₂ and n units corresponding to each structure by the synthesis method described in Example 1.

<Example 2> Synthesis of compound of formula 2-14

[Formula 2-14]

Step 1: (1-(9-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-6-nitro-9H-

Synthesis of carbazol-3-yl)-2-(hydroxyimino)octan-1-one

In a nitrogen atmosphere, the compound of step 3 of Example 1 (15 g, 30 mmol) and sodium methoxide (1.7, 32 mmol) were added to a mixture of DCM (50 mL) and methanol (50 mL) (volume ratio 1:1), and The reaction solution was cooled to 0 °C using an ice-bath.

Amyl nitrite (3.7 g, 32 mmol) was gradually added dropwise to the reaction solution over about 30 minutes. After completion of the dropping, the ice-bath was removed and the mixture was stirred at room temperature for 2 hours.

After confirming the completion of the reaction by TLC, the reaction solution was slowly added dropwise to a 10% HCl (100 mL) aqueous solution to quench (quenching). The organic layer in the reaction solution was extracted using DCM (100 mL), and the obtained organic layer was washed with distilled water (150 mL) three times, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./E.A. = 2/1) to obtain 13.7 g of an off-white solid in 88% yield.

¹ H-NMR confirmed the product.

¹ H-NMR (δ, ppm), CDCl ₃ : 9.00 (s, 1H), 8.63 (s, 1H), 8.31 (d/d, 1H), 8.05 (d/d, 1H), 7.52-7.39 (m) , 2H), 4.55 (t, 2H), 3.93 (t, 2H), 3.57-3.47 (m, 8H), 2.64 (t, 2H), 1.52 (m, 2H), 1.39-1.20 (m, 8H), 0.90 (t, 3H).

Step 2: 2-(acetoxyimino)-1-(9-(2-(2-(2-chloroethoxy)ethoxy)

Synthesis of ethyl)-6-nitro-9H-carbazol-3-yl)octan-1-one

The compound from Step 4 (12.0 g, 23 mmol) was dissolved in DCM (60 mL) under a nitrogen atmosphere, and then acetic anhydride (2.6 g, 25 mmol) was slowly added dropwise. After completion of the dropping, the reaction vessel is blocked from light using aluminum foil and stirred at room temperature for 4 hours. After confirming the completion of the reaction by TLC, distilled water (150 mL) and DCM (100 mL) were added to the reaction solution. The obtained organic layer was washed 3 times with distilled water (150 mL), and then concentrated under reduced pressure. The concentrate was recrystallized using polar and non-polar solvents to obtain 11.7 g of a yellow solid in 91% yield.

¹ H-NMR confirmed the product.

¹ H-NMR (δ, ppm), CDCl ₃ : 9.00 (s, 1H), 8.62 (s, 1H), 8.32 (d/d, 1H), 8.03 (d/d, 1H), 7.52-7.36 (m) , 2H), 4.55 (t, 2H), 3.93 (t, 2H), 3.57-3.45 (m, 8H), 2.69 (t, 2H), 2.23 (s, 3H), 1.54 (m, 2H), 1.41- 1.23 (m, 8H), 0.89 (t, 3H).

The α-ketooxime ester carbazole derivative compounds represented by Chemical Formulas 2-1 to 2-8 were synthesized as shown in Table 4 below according to the preparation method of Example 2 using the corresponding carbazole ketone compound as a starting material.

Formula No. R ₂ R ₃ ¹ H-NMR (δ, ppm) 2-1 CH ₃ CH ₃ 9.05 (s, 1H), 8.65 (s, 1H), 8.34 (d/d, 1H), 8.06 (d/d, 1H), 7.56-7.32 (m, 2H), 4.56 (t, 2H), 3.97 ( t, 2H), 3.58 (t, 2H), 3.47 (t, 2H), 2.77 (s, 3H), 2.26 (s, 3H). 2-2 CH ₃ C ₂ H ₅ 9.05 (s, 1H), 8.64 (s, 1H), 8.34 (d/d, 1H), 8.05 (d/d, 1H), 7.55-7.32 (m, 2H), 4.55 (t, 2H), 3.97 ( t, 2H), 3.57 (t, 2H), 3.46 (t, 2H), 2.74 (q, 2H), 2.26 (s, 3H), 1.12 (t, 3H). 2-3 CH ₃ C ₃ H ₇ 9.04 (s, 1H), 8.64 (s, 1H), 8.34 (d/d, 1H), 8.05 (d/d, 1H), 7.55-7.30 (m, 2H), 4.55 (t, 2H), 3.97 ( t, 2H), 3.57 (t, 2H), 3.46 (t, 2H), 2.71 (t, 2H), 2.26 (s, 3H), 1.52 (m, 2H), 1.10 (t, 3H). 2-4 CH ₃ C ₄ H ₉ 9.04 (s, 1H), 8.62 (s, 1H), 8.32 (d/d, 1H), 8.03 (d/d, 1H), 7.53-7.28 (m, 2H), 4.54 (t, 2H), 3.96 ( t, 2H), 3.55 (t, 2H), 3.44 (t, 2H), 2.69 (t, 2H), 2.26 (s, 3H), 1.59-1.43 (m, 4H), 1.07 (t, 3H). 2-5 CH ₃ C ₅ H ₁₁ 9.02 (s, 1H), 8.60 (s, 1H), 8.29 (d/d, 1H), 8.04 (d/d, 1H), 7.54-7.26 (m, 2H), 4.56 (t, 2H), 3.96 ( t, 2H), 3.54 (t, 2H), 3.45 (t, 2H), 2.67 (t, 2H), 2.25 (s, 3H), 1.55-1.42 (m, 6H), 1.05 (t, 3H). 2-6 CH ₃ C ₆ H ₁₃ 9.01 (s, 1H), 8.60 (s, 1H), 8.30 (d/d, 1H), 8.02 (d/d, 1H), 7.53-7.21 (m, 2H), 4.55 (t, 2H), 3.97 ( t, 2H), 3.55 (t, 2H), 3.44 (t, 2H), 2.65 (t, 2H), 2.23 (s, 3H), 1.52-1.39 (m, 8H), 1.01 (t, 3H). 2-7 C ₆ H ₅ C ₆ H ₁₃ 9.04 (s, 1H), 8.65 (s, 1H), 8.34 (d/d, 1H), 8.19 (d/d, 1H), 8.05 (d/d, 1H), 7.98 (d/d, 1H), 7.72-7.59 (m, 3H), 7.55-7.30 (m, 2H), 4.55 (t, 2H), 3.97 (t, 2H), 3.57 (t, 2H), 3.46 (t, 2H), 2.83 (t, 2H), 1.49-1.32 (m, 8H), 0.87 (t, 3H). 2-8 CH ₃ C ₇ H ₇ 9.04 (s, 1H), 8.62 (s, 1H), 8.38 (d/d, 1H), 8.02 (d/d, 1H), 7.63 (d, 1H), 7.53 (m, 2H), 7.49-7.22 ( m, 3H), 4.56 (t, 2H), 3.94 (t, 2H), 3.57-3.42 (m, 12H), 2.40 (s, 3H), 2.28 (s, 3H).

The α-ketooxime ester carbazole derivative compounds represented by Formulas 2-9 to 2-13 and 2-15 and 2-16 were synthesized as shown in Table 5 according to the preparation method of Example 2.

Formula No. R ₂ R ₃ ¹ H-NMR (δ, ppm) 2-9 CH ₃ CH ₃ 9.03 (s, 1H), 8.62 (s, 1H), 8.34 (d/d, 1H), 8.05 (d/d, 1H), 7.54-7.31 (m, 2H), 4.56 (t, 2H), 3.91 ( t, 2H), 3.58-3.43 (m, 8H), 2.72 (s, 3H), 2.26 (s, 3H). 2-10 CH ₃ C ₂ H ₅ 9.04 (s, 1H), 8.61 (s, 1H), 8.34 (d/d, 1H), 8.04 (d/d, 1H), 7.55-7.30 (m, 2H), 4.56 (t, 2H), 3.92 ( t, 2H), 3.57-3.44 (m, 8H), 2.71 (q, 2H), 2.25 (s, 3H), 1.11 (t, 3H). 2-11 CH ₃ C ₃ H ₇ 9.03 (s, 1H), 8.61 (s, 1H), 8.32 (d/d, 1H), 8.03 (d/d, 1H), 7.55-7.28 (m, 2H), 4.56 (t, 2H), 3.90 ( t, 2H), 3.58-3.43 (m, 8H), 2.69 (t, 2H), 2.25 (s, 3H), 1.69 (m, 2H), 1.09 (t, 3H). 2-12 CH ₃ C ₄ H ₉ 9.03 (s, 1H), 8.62 (s, 1H), 8.32 (d/d, 1H), 8.02 (d/d, 1H), 7.53-7.28 (m, 2H), 4.56 (t, 2H), 3.92 ( t, 2H), 3.56-3.42 (m, 8H), 2.67 (t, 2H), 2.24 (s, 3H), 1.57-1.43 (m, 4H), 1.06 (t, 3H). 2-13 CH ₃ C ₅ H ₁₁ 9.02 (s, 1H), 8.59 (s, 1H), 8.29 (d/d, 1H), 8.01 (d/d, 1H), 7.55-7.26 (m, 2H), 4.55 (t, 2H), 3.93 ( t, 2H), 3.56-3.43 (m, 8H), 2.65 (t, 2H), 2.23 (s, 3H), 1.65-1.44 (m, 6H), 1.05 (t, 3H). 2-15 C ₆ H ₅ C ₆ H ₁₃ 9.04 (s, 1H), 8.65 (s, 1H), 8.34 (d/d, 1H), 8.19 (d/d, 1H), 8.05 (d/d, 1H), 7.98 (d/d, 1H), 7.72-7.59 (m, 3H), 7.55-7.30 (m, 2H), 4.54 (t, 2H), 3.94 (t, 2H), 3.59-3.46 (m, 8H), 2.83 (t, 2H), 1.49- 1.32 (m, 8H), 0.87 (t, 3H). 2-16 CH ₃ C ₇ H ₇ 9.04 (s, 1H), 8.62 (s, 1H), 8.38 (d/d, 1H), 8.02 (d/d, 1H), 7.63 (d, 1H), 7.53 (m, 2H), 7.49-7.22 ( m, 3H), 4.57 (t, 2H), 3.94 (t, 2H), 3.59-3.44 (m, 8H), 2.40 (s, 3H), 2.28 (s, 3H).

The α-ketooxime ester carbazole derivative compounds represented by Formulas 2-17 to 2-24 were synthesized as shown in Table 6 below according to the preparation method of Example 2 using the corresponding carbazole ketone compound as a starting material.

Formula No. R ₂ R ₃ ¹ H-NMR (δ, ppm) 2-17 CH ₃ CH ₃ 9.04 (s, 1H), 8.64 (s, 1H), 8.34 (d/d, 1H), 8.06 (d/d, 1H), 7.56-7.32 (m, 2H), 4.57 (t, 2H), 3.93 ( t, 2H), 3.61-3.49 (m, 12H), 2.72 (t, 2H), 2.26 (s, 3H). 2-18 CH ₃ C ₂ H ₅ 9.04 (s, 1H), 8.63 (s, 1H), 8.34 (d/d, 1H), 8.05 (d/d, 1H), 7.55-7.32 (m, 2H), 4.57 (t, 2H), 3.93 ( t, 2H), 3.61-3.50 (m, 12H), 2.71 (q, 2H), 2.25 (s, 3H), 1.12 (t, 3H). 2-19 CH ₃ C ₃ H ₇ 9.03 (s, 1H), 8.63 (s, 1H), 8.32 (d/d, 1H), 8.05 (d/d, 1H), 7.55-7.30 (m, 2H), 4.57 (t, 2H), 3.93 ( t, 2H), 3.60-3.48 (m, 12H), 2.70 (t, 2H), 2.25 (s, 3H), 1.09 (t, 3H). 2-20 CH ₃ C ₄ H ₉ 9.04 (s, 1H), 8.62 (s, 1H), 8.32 (d/d, 1H), 8.03 (d/d, 1H), 7.53-7.28 (m, 2H), 4.56 (t, 2H), 3.94 ( t, 2H), 3.59-3.45 (m, 12H), 2.69 (t, 2H), 2.24 (s, 3H), 1.58-1.43 (m, 4H), 1.07 (t, 3H). 2-21 CH ₃ C ₅ H ₁₁ 9.02 (s, 1H), 8.60 (s, 1H), 8.29 (d/d, 1H), 8.04 (d/d, 1H), 7.54-7.26 (m, 2H), 4.56 (t, 2H), 3.93 ( t, 2H), 3.60-3.45 (m, 12H), 2.67 (t, 2H), 2.25 (s, 3H), 1.55-1.42 (m, 6H), 1.05 (t, 3H). 2-22 CH ₃ C ₆ H ₁₃ 9.00 (s, 1H), 8.62 (s, 1H), 8.32 (d/d, 1H), 8.03 (d/d, 1H), 7.52-7.36 (m, 2H), 4.55 (t, 2H), 3.92 ( t, 2H), 3.60-3.42 (m, 12H), 2.69 (t, 2H), 2.23 (s, 3H), 1.54 (m, 2H), 1.41-1.23 (m, 8H), 0.89 (t, 3H) . 2-23 C ₆ H ₅ C ₆ H ₁₃ 9.03 (s, 1H), 8.64 (s, 1H), 8.34 (d/d, 1H), 8.19 (d/d, 1H), 8.05 (d/d, 1H), 7.98 (d/d, 1H), 7.72-7.59 (m, 3H), 7.55-7.30 (m, 2H), 4.56 (t, 2H), 3.91 (t, 2H), 3.62-3.45 (m, 12H), 2.83 (t, 2H), 1.49- 1.32 (m, 8H), 0.87 (t, 3H). 2-24 CH ₃ C ₇ H ₇ 9.04 (s, 1H), 8.62 (s, 1H), 8.38 (d/d, 1H), 8.02 (d/d, 1H), 7.63 (d, 1H), 7.53 (m, 2H), 7.49-7.22 ( m, 3H), 4.55 (t, 2H), 3.91 (t, 2H), 3.58-3.44 (m, 12H), 2.40 (s, 3H), 2.28 (s, 3H).

<Preparation Example> Preparation of photosensitive resin composition

Propylene glycol methyl ether acetate (PGMEA; Propylene Glycol Methyl Ether Acetate) solvent, polyhydroxystyrene resin (PHS), dipentaerythritol hexaacrylic A photosensitive resin composition was prepared by sequentially adding the rate (DPHA, Aldrich) and the photoinitiator according to the examples, and stirring at room temperature.

[Formula 3]

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

[Formula 4]

DPHA: Aldrich, dipentaerythritol hexaacrylate

In order to compare the sensitivity of the photosensitive resin composition, the samples of Comparative Examples 1 to 4 were prepared by mixing the compounds represented by the following Chemical Formulas 5 to 8.

[Formula 5]

The compound represented by Formula 5 was prepared through an oxime reaction and acetylation, excluding nitration from the ketone compound synthesized in Example 1.

[Formula 6]

The compound represented by Formula 6 was prepared through oxime reaction and acetylation, excluding nitration from the ketone compound synthesized in Example 2.

[Formula 7]

The compound represented by Formula 7 is OXE-01 manufactured by BASF.

[Formula 8]

The compound represented by Formula 8 is OXE-02 manufactured by BASF.

Photoinitiator (g) PHS(g) DPHA(g) PGMEA(g) Formula 1-11 (1) 20 10 69 Formula 1-13 (1) 20 10 69 Formula 1-15 (1) 20 10 69 Formula 1-17 (1) 20 10 69 Formula 1-19 (1) 20 10 69 Formula 1-20 (1) 20 10 69 Formula 2-12 (1) 20 10 69 Formula 2-14 (1) 20 10 69 Formula 2-15 (1) 20 10 69 Formula 2-16 (1) 20 10 69 Comparative Example 1 (Formula 5) (1) 20 10 69 Comparative Example 2 (Formula 6) (1) 20 10 69 Comparative Example 3 (Formula 7) (1) 20 10 69 Comparative Example 4 (Formula 8) (1) 20 10 69

<Experimental Example> Sensitivity evaluation of the photosensitive resin composition

The photosensitivity of the oxime ester-based photoinitiator prepared above, the α-ketooxime ester-based photoinitiator and the photosensitive resin composition prepared in Comparative Examples 1 to 4 was evaluated.

After drying on a glass substrate, it is coated to a film thickness of 5 μm, and dried at 120° C. for 2 minutes at 110° C. for 90 seconds to volatilize the solvent.

After exposure with a fusion lamp and development in 0.45% KOH aqueous solution at 23°C, the thickness was measured using a non-contact thickness measuring device based on the exposure amount maintaining 80% of the initial thickness.

Here, the lower the exposure value, the better the sensitivity.

Sensitivity
(mJ/cm ² ) Formula 1-11 30 Formula 1-13 30 Formula 1-15 30 Formula 1-17 30 Formula 1-19 30 Formula 1-20 35 Formula 2-12 25 Formula 2-14 25 Formula 2-15 30 Formula 2-16 25 Comparative Example 1 (Formula 3) 100 Comparative Example 2 (Formula 4) 80 Comparative Example 3 (OXE-01) 80 Comparative Example 4 (OXE-02) 60

The sensitivity measurement results are shown in FIG. 1 and Table 8.

1 and Table 8, it was confirmed that the high sensitivity of the photosensitive resin composition according to the embodiment of the present invention, in particular, compared to Comparative Examples 1 and 2, when substituted with a nitro group, it was confirmed that the sensitivity is greatly increased.

Since it is highly sensitive compared to commercial photoinitiators (Comparative Examples 3 and 4), it is possible to increase the efficiency of the photoresist process and the like.

As described above, the configuration and operation of the present invention has been described based on a preferred embodiment according to the present invention, but the present invention is not limited to a specific embodiment, and those of ordinary skill in the art will use a patent to be described later. Various modifications and changes can be made to the present invention without departing from the spirit and scope of the present invention described in the claims.

Claims (7)

An oxime ester carbazole compound represented by the following Chemical Formula 1 or Chemical Formula 2:
[Formula 1]

[Formula 2]

wherein X is Cl or Br, R ₁ and R ₃ are each independently C ₁ to C ₂₀ alkyl, C ₅ to C ₁₀ cycloalkyl, C ₆ to C ₃₀ aryloxy, C ₁ to C ₂₀ alkylthio, C ₆ to C ₃₀ aryl, C ₇ to C ₃₀ aralkyl, or C ₅ to C ₃₀ heteroaryl, R ₂ is C ₁ to C ₃ alkyl or phenyl;
n is an integer from 1 to 3.
The method according to claim 1, wherein X is Cl, R ₁ and R ₃ are each independently linear or branched C ₁ to C ₂₀ alkyl, C ₅ to C ₁₀ cycloalkyl, C ₆ to C ₃₀ aryl, and R ₂ is methyl or phenyl oxime ester carbazole compound.
The oxime ester carbazole compound according to claim 1, wherein the compound of Formula 1 is any one selected from the following Formulas 1-1 to 1-30:

The oxime ester carbazole compound according to claim 1, wherein the compound of Formula 2 is any one selected from the following Formulas 2-1 to 2-24:

The oxime ester carbazole compound of any one of Claims 1-5; and a compound having an ethylenically unsaturated bond.
The photosensitive resin composition according to claim 5, further comprising a developable binder resin.
7. The group of claim 6, wherein the developable binder resin is an acrylic acid-containing acrylic copolymer, a novolak-based phenol resin, a polyhydroxystyrene resin, a polysiloxane resin, a polyimide resin, a hydroxystyrene, and a copolymer of acrylate. Photosensitive resin composition, characterized in that any one or a mixture of two or more selected from.

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