KR20190090963A - Highly sensitive oxime ester photopolymerization initiator and photopolymerizable composition including the same - Google Patents

Abstract

The present invention relates to an oxime ester compound consisting of carbazoles containing hetero rings useful as a photopolymerization initiator in photocrosslinking reaction. More specifically, a carbon atom double-bonded with a nitrogen atom of an oxime ester structure is bonded to a heterocarbazole group and has a structure in which an alkyl group (C_1-C_20) or an allyl group (C_6-C_20) is also directly bonded wherein the heterocarbazole group has a structure substituted with at least one nitro group. In the compound and a photopolymerization composition comprising the same according to the present invention, the solubility is increased, the photosensitivity is excellent, and the remaining film ratio, pattern stability, and adhesion of a resist are excellent, thereby being useful for an LCD black resist, a color resist, overcoat, a column spacer, an organic insulating film, and the like.

Description

High sensitivity oxime ester photoinitiator and photopolymerization composition comprising same {HIGHLY SENSITIVE OXIME ESTER PHOTOPOLYMERIZATION INITIATOR AND PHOTOPOLYMERIZABLE COMPOSITION INCLUDING THE SAME}

The present invention relates to a high sensitivity oxime ester photopolymerization initiator and a photopolymerization composition comprising the same.

The photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized and cured by irradiating mixed light of 365 nm, 405 nm, and 436 nm to the photosensitive composition, so that the photocurable ink, photosensitive printing plate, and various photo It is used as a resist. Photosensitive compositions having sensitivity to short wavelength light sources require photopolymerization initiators having excellent sensitivity in consideration of beautiful printing.

As a photopolymerization initiator used in such a photosensitive composition, International Patent Publication No. WO02 / 100903A1 describes a photoinitiator having an oxime ester group, and details of the structure and synthesis of various oxime ester compounds which can be used as the photoinitiator are disclosed herein. have. However, known oxime ester compounds, including the oxime ester compounds shown in these documents, when used as a photopolymerization initiator, decomposed products due to light adhere to the mask during exposure, resulting in pattern defects in the printing process and lowering of yields.

Moreover, the decomposition temperature is 240 degrees C or less, and the adhesiveness of the photosensitive composition is reduced by decomposing a photoinitiator in the thermosetting process after image development processing. For this reason, there is a demand for a photopolymerization initiator having excellent sensitivity and pattern stability, adhesion, and the like.

Accordingly, an object of the present invention is to provide a photopolymerization initiator containing an oxime ester structure having a high sensitivity as a photoinitiator, which does not adhere to a mask when exposed to light, and which has excellent adhesion, pattern stability and excellent sensitivity.

It is another object of the present invention to provide a photoinitiator compound and a photosensitive compound comprising the same that can achieve appropriate solubility in a solvent used in the photopolymerization composition.

A further object of the present invention is a photosensitive composition comprising such an oxime ester compound as a photoinitiator, in particular a resist, organic insulating film or overcoat for formation of a black matrix, color filter, black column matrix or column spacer pattern with improved thin film properties. It is to provide a photosensitive composition for.

According to an aspect of the present invention, as an oxime ester compound used as a photoinitiator in a photocrosslinking reaction,

A structure in which a carbon atom double bond with a nitrogen atom of the oxime ester structure is bonded to a carbazole group including a heterocyclic compound and is also directly bonded to a (C ₁ -C ₂₀ ) alkyl group or a (C ₆ -C ₂₀ ) allyl group. It provides an oxime ester compound consisting of a carbazole comprising a hetero ring having a carbazole group containing the heterocyclic compound is substituted with one or more nitro groups.

In the present invention, the carbazole group including the hetero ring includes 1) a unit having a monocyclic heterocyclic radical and 2) a unit having a polycyclic heterocyclic N-membered radical is 2) a polycyclic heterocyclic N -It may be connected to the nitrogen atom site of the unit having a member radical to form a skeleton.

1) The unit having a monocyclic heterocyclic radical may be at least one member selected from the group consisting of 2-furyl, 2-thienyl, 4-pyridine, and N- (C ₁ -C ₂ alkyl) -2-pyrroline. have.

The unit having the 2) polycyclic heterocyclic N-member radical may be at least one selected from the group consisting of chromone, flavone, quinoline, isoquinoline and carbazole.

구조를 갖고, 여기서 X는 직접 결합이고, Z는 S-, -O-, NR₃, -N(C₁-C₂ 알킬)OR₄ 또는 N(C₁-C₂ 알킬)O(CO)R₄이며; R₃는 C₃-C₁₀ 알킬이고; R₄는 C₁-C₆의 직쇄 알킬, 분지쇄 알킬 또는 고리형 알킬일 수 있다.2) the unit having a polycyclic heterocyclic radical

Structure, wherein X is a direct bond, Z is S-, -O-, NR ₃ , -N (C ₁ -C ₂ alkyl) OR ₄ or N (C ₁ -C ₂ alkyl) O (CO) R ₄ ; R ₃ is C ₃ -C ₁₀ alkyl; R ₄ may be C ₁ -C ₆ straight alkyl, branched alkyl or cyclic alkyl.

In the present invention, any one or more of the hetero ring and the carbazole group may be substituted with a nitro group.

In the present invention, the skeleton may combine with the (alpha-keto) oxime ester group to form a terminal group.

구조를 갖고, n은 0 또는 1이고, R₁은 C₁-C₁₀ 알킬, C₁-C₃ 알킬 치환 페닐, 2-메틸벤젠, C₁-C₆ 알콕시이고, R₂는 R₁-R₄ 알킬인 것일 수 있다.In the present invention, the terminal group

Having a structure, n is 0 or 1, R ₁ is C ₁ -C ₁₀ alkyl, C ₁ -C ₃ alkyl substituted phenyl, 2-methylbenzene, C ₁ -C ₆ alkoxy, R ₂ is R ₁ -R ₄ alkyl.

According to another aspect of the present invention, there is provided an oxime ester compound composed of carbazole comprising a hetero ring represented by the following general formula (1):

[Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen, nitro, cyano, alkoxy, halogen, or ester, wherein alkoxy and ester comprise an alkyl group having 1 to 8 carbon atoms, wherein R ₁ and R ₂ are hydrogen Not; R ₃ represents (C ₁ -C ₂₀ ) alkyl, (C ₆ -C ₃₀ ) aryl, (C ₁ -C ₂₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl (C ₁ -C ₂₀ ) alkyl, hydroxy ( C ₁ -C ₂₀ ) alkyl, hydroxy (C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl, (C ₁ -C ₂₀ ) alkylacyl or (C ₆ -C ₂₀ ) arylacyl; R ₄ represents (C ₁ -C ₂₀ ) alkyl, (C ₆ -C ₃₀ ) aryl, (C ₁ -C ₂₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl (C ₁ -C ₂₀ ) alkyl, hydroxy ( C ₁ -C ₂₀ ) alkyl, hydroxy (C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl, (C ₁ -C ₂₀ ) alkylacyl or (C ₆ -C ₃₀ ) arylacyl; R ₅ and R ₆ are each independently hydrogen, nitro, cyano, halogen, (C ₁ -C ₂₀ ) alkyl, (C ₁ -C ₂₀ ) alkoxy, hydroxy (C ₁ -C ₂₀ ) alkyl, hydroxy ( C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl or (C ₁ -C ₂₀ ) alkylacyl; X is S, O NH or N- (C ₁ -C ₂₀ ) alkyl, n is an integer of 0 or 1;

In the present invention, R ₁ and R ₂ are each independently hydrogen, nitro, cyano, alkoxy, halogen, or ester, alkoxy and ester include an alkyl group having 1 to 8 carbon atoms, any one of R ₁ and R ₂ It may be nitro.

In the present invention, R ₃ may be (C ₁ -C ₂₀ ) alkyl or (C ₆ -C ₃₀ ) aryl.

In the present invention, R ₄ may be straight chain (C ₁ -C ₃ ) alkyl, branched chain (C ₄ -C ₇ ) alkyl or (C ₆ -C ₈ ) aryl.

In the present invention, R ₅ , R ₆ may be each independently hydrogen, nitro or methyl.

In the present invention, X may be S or N-CH ₃ .

In addition, if R ₁ is hydrogen then R ₅ may be nitro or methyl.

In addition, R ₁ may be nitro if R ₅ is hydrogen.

In addition, R ₂ , R ₆ may be hydrogen.

R ₃ may also be methyl, propyl, pentyl, heptyl, phenyl or phenyl substituted with C 1 -C 3.

In addition, R ₄ may be methyl, ethyl, isopropyl, phenyl or phenyl substituted with C1 to C3.

In addition, X may be S or N-CH ₃ .

In addition, n may be zero.

According to another aspect of the present invention, there is provided a photopolymerization initiator comprising an oxime ester compound composed of carbazole including the hetero ring described above.

According to another aspect of the invention, the oxime ester compound consisting of a carbazole containing the above-described hetero ring; And at least one compound selected from a polymer compound soluble in a solvent or an aqueous alkali solution and a photopolymerizable compound having an ethylenically unsaturated bond; It provides a photopolymerization composition comprising a.

According to another aspect of the invention, the oxime ester compound consisting of a carbazole containing the above-described hetero ring; At least one compound selected from a polymer compound soluble in a solvent or an aqueous alkali solution and a photopolymerizable compound having an ethylenically unsaturated bond; And it provides a photopolymerization composition comprising a colorant or a pigment.

According to the present invention, it is possible to provide an oxime ester compound composed of a carbazole including a hetero ring having excellent solubility in PGMEA, etc., which is useful as a solvent for a photosensitive composition, thereby providing a cabar containing a hetero ring as a photoinitiator used in photocrosslinking reactions. The amount of the oxime ester compound composed of the sol can be minimized, and the thin film coated with the photosensitive composition including the same can be used to reduce the phase separation between the binder and the photoinitiator during solvent volatilization, thereby improving thin film properties after crosslinking. Thus, a good black matrix, color filter, column spacer, insulating film, photocrosslinkable coating substrate and the like can be provided.

In addition, the oxime ester compound composed of the carbazole including the hetero ring of the present invention has excellent sensitivity even when used in a small amount when used as a photopolymerization initiator of the photopolymerization composition, and has excellent physical properties such as residual film ratio, pattern stability, chemical resistance and ductility. Out-gassing from photopolymerization initiator can be minimized during exposure and post-baking process during display manufacturing process for TFT-LCD, OLED, TSP, etc., which can reduce contamination and minimize defects that can be caused There is this.

1 is an example of Example 1, Example 7, Example 13, Comparative Example 1, Comparative Example 2, using the oxime ester series of the oxime ester compound consisting of a carbazole containing a hetero ring according to the present invention as a photopolymerization initiator of the photopolymer composition It is a graph compared with the sensitivity measured about the comparative example 6.
Figure 2 is Example 19, Example 24, Example 29, Comparative Example 3, Comparative Example using the alpha keto oxime ester series of the oxime ester compound consisting of a carbazole containing a hetero ring according to the present invention as a photo polymerization initiator 4 and a graph comparing sensitivity measured for Comparative Example 5. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated more concretely.

Oxime ester compounds composed of carbazoles containing heterocycles of the present invention include photoinitiators useful as photoinitiators of polymerizable compounds having ethylenically unsaturated bonds capable of simultaneously achieving adequate solubility and sensitivity in solvents, and photosensitive compounds comprising the same. to provide.

The present invention provides a photopolymerization composition comprising an oxime ester compound composed of a carbazole including a hetero ring used as a photoinitiator in a photocrosslinking reaction.

As the oxime ester compound used zero photoinitiator in the photo-crosslinking reaction, the oxime ester compounds are for example carbon atom to double bond with the nitrogen atom of the oxime ester structure, coupled to carbazole containing heterocycle, (C ₁ - C ₂₀₎ alkyl or (C ₆ -C ₂₀₎ allyl group and also has a structure which is bonded directly, carbazole sol consisting of oxime ester to the carbazole group containing the hetero ring contains a hetero ring that is substituted with one or more nitro Characterized in that the compound.

The carbazole group including the hetero ring is preferably substituted, for example, one or more nitro groups may be substituted, and in particular, one type of nitro group may be substituted to provide sensitivity and solubility improvement effects. Sensitivity is expected to be good when two nitro groups are substituted but may be difficult to apply due to low solubility.

In the present invention, the carbazole group including the hetero ring includes 1) a monomer having a monocyclic heterocyclic radical and 2) a monomer having a polycyclic heterocyclic N-member radical having 2) a polycyclic heterocyclic N-member radical. It may be connected to the nitrogen atom site of the unit to form a skeleton.

1) The unit having a monocyclic heterocyclic radical may be at least one member selected from the group consisting of 2-furyl, 2-thienyl, 4-pyridine, and N- (C ₁ -C ₂ alkyl) -2-pyrroline. have.

The unit having the 2) polycyclic heterocyclic N-member radical may be at least one selected from the group consisting of chromone, flavone, quinoline, isoquinoline and carbazole.

구조를 갖고, 여기서 X는 직접 결합이고, Z는 S-, -O-, NR₇, -N(C₁-C₂ 알킬)OR₈ 또는 N(C₁-C₂ 알킬)O(CO)R₈이며; R₇는 C₃-C₁₀ 알킬이고; R₈는 C₁-C₆의 직쇄 알킬, 분지쇄 알킬 또는 고리형 알킬일 수 있다.2) the unit having a polycyclic heterocyclic radical

Structure, wherein X is a direct bond, Z is S-, -O-, NR ₇ , -N (C ₁ -C ₂ alkyl) OR ₈ or N (C ₁ -C ₂ alkyl) O (CO) R ₈ ; R ₇ is C ₃ -C ₁₀ alkyl; R ₈ may be C ₁ -C ₆ straight alkyl, branched alkyl or cyclic alkyl.

In the present invention, any one or more of the hetero ring and the carbazole group may be substituted with a nitro group.

In the present invention, the skeleton may combine with the (alpha-keto) oxime ester group to form a terminal group.

구조를 갖고, n은 0 또는 1이고, R₁은 C₁-C₁₀ 알킬, C₁-C₃ 알킬 치환 페닐, 2-메틸벤젠, C₁-C₆ 알콕시이고, R₂는 R₁-R₄ 알킬인 것일 수 있다.In the present invention, the terminal group

Having a structure, n is 0 or 1, R ₁ is C ₁ -C ₁₀ alkyl, C ₁ -C ₃ alkyl substituted phenyl, 2-methylbenzene, C ₁ -C ₆ alkoxy, R ₂ is R ₁ -R ₄ alkyl.

The oxime ester thiophencarbazole compound used as the photoinitiator in the photocrosslinking reaction may be, for example, a compound represented by Formula 1 below:

[Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen, nitro, cyano, alkoxy, halogen, or ester, wherein alkoxy and ester comprise an alkyl group having 1 to 8 carbon atoms, wherein R ₁ and R ₂ are hydrogen Not; R ₃ represents (C ₁ -C ₂₀ ) alkyl, (C ₆ -C ₃₀ ) aryl, (C ₁ -C ₂₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl (C ₁ -C ₂₀ ) alkyl, hydroxy ( C ₁ -C ₂₀ ) alkyl, hydroxy (C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl, (C ₁ -C ₂₀ ) alkylacyl or (C ₆ -C ₂₀ ) arylacyl; R ₄ represents (C ₁ -C ₂₀ ) alkyl, (C ₆ -C ₃₀ ) aryl, (C ₁ -C ₂₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl (C ₁ -C ₂₀ ) alkyl, hydroxy ( C ₁ -C ₂₀ ) alkyl, hydroxy (C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl, (C ₁ -C ₂₀ ) alkylacyl or (C ₆ -C ₃₀ ) arylacyl; R ₅ and R ₆ are each independently hydrogen, nitro, cyano, halogen, (C ₁ -C ₂₀ ) alkyl, (C ₁ -C ₂₀ ) alkoxy, hydroxy (C ₁ -C ₂₀ ) alkyl, hydroxy ( C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl or (C ₁ -C ₂₀ ) alkylacyl; X is S, O, NH or N- (C ₁ -C ₂₀ ) alkyl, n is an integer of 0 or 1;

For reference, unless otherwise stated in the present invention, the alkyl group constituting the substituent refers to having 1 to 20 carbon atoms.

In one example, R ₁ and R ₂ are each independently hydrogen, nitro, cyano, alkoxy, halogen, or ester, wherein alkoxy and ester comprise an alkyl group having 1 to 8 carbon atoms, wherein any one of R ₁ and R ₂ is Nitro is preferred when considering the sensitivity side. Wherein halogen may be F, Br, Cl.

In one example, R ₃ can be (C ₁ -C ₂₀ ) alkyl or (C ₆ -C ₃₀ ) aryl, wherein it is (C ₃ -C ₇ ) alkyl or (C ₆ -C ₇ ) aryl solubility aspect It is preferable when considering.

In one example, R ₄ may be straight chain (C ₁ -C ₃ ) alkyl, branched (C ₄ -C ₇ ) alkyl or (C ₆ -C ₈ ) aryl.

As a specific example, R ₄ may be methyl, ethyl, isopropyl, phenyl or phenyl substituted with C1 to C3.

In one example, each of R ₅ , R ₆ may be independently hydrogen, nitro or methyl.

As a specific example, if R ₁ is hydrogen, R ₅ is nitro, if R ₅ is hydrogen, R ₁ is nitro, R ₂ , R ₆ are hydrogen, and R ₃ is methyl, propyl, pentyl, heptyl, phenyl or C 1- The number of phenyl substituted by C3, R ₄ is methyl, ethyl, isopropyl, phenyl or phenyl substituted by C1-C3, and X is S or N-CH ₂ CH ₃ , respectively, to provide ease of synthesis. It is preferable.

As a specific example, preferred embodiments of the oxime ester compound consisting of a carbazole containing a hetero ring used as a photoinitiator in the photocrosslinking reaction, or the oxime ester compound consisting of a carbazole comprising a hetero ring represented by the formula (1) It may be represented by a chemical formula.

Preferred specific examples of Formula 1 may be represented by the following formula.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

[Formula 1-21]

[Formula 1-22]

[Formula 1-23]

[Formula 1-24]

[Formula 1-25]

[Formula 1-26]

[Formula 1-27]

[Formula 1-28]

[Formula 1-29]

[Formula 1-30]

[Formula 1-31]

[Formula 1-32]

[Formula 1-33]

[Formula 1-34]

The method for preparing the compounds of Formulas 1-1 to 1-12 of the present invention can be synthesized by, for example, a synthesis process described by Scheme 1 below. Of these, in the case of preparing the compounds of Formulas 1-7 to 1-12, _one of R ₁ and R ₂ of the carbazole compound is NO ₂ and R ₅ of the bromo heterocyclic compound is CH ₃ . However, the synthesis method of the compound is not limited thereto.

Scheme 1

According to Scheme 1, a halogen ketone compound prepared from a Friedel-Craft reaction of a bromo heterocyclic compound and an acyl chloride is obtained by a Ulmann reaction under 9H-carbazole and copper iodide (CuI) to obtain a carbazole ketone compound. The carbazole ketone compound in which nitro is introduced into any one of R ₁ and R ₂ of carbazole is obtained by nitration reaction with a capperate (Cu (NO ₃ ) ₂ ) 2.5 hydrate. The nitro carbazole ketone compound obtains the corresponding oxime compound by oximation reaction with hydroxylamine hydrochloride. Next, a photoinitiator having an oxime ester group represented by Chemical Formulas 1-1 to 112 may be obtained by an acetylation reaction between the nitrocarbazole oxime compound and acetyl chloride under a triethylamine catalyst.

The content ratio of the bromo hetero ring compound and the acyl chloride compound may be, for example, 3 mole weight in 1 mole of the acyl chloride compound to 1 mole weight of the bromo hetero ring compound.

The content ratio of the 9H-carbazole, the halogen ketone compound and the copper iodide is, for example, 1 mole of 9H-carbazole to 4 mole weight of 1 mole of halogen ketone compound and 4 mole weight of 1 mole of copper iodide. Can be.

The content ratio of the carbazole ketone compound and the copper nitrate may be, for example, 0.5 mole to 2 mole weights of copper nitrate to 1 mole weight of the carbazole ketone compound.

The content ratio of the nitro carbazole ketone compound and the hydroxylamine hydrochloride may be, for example, 4 mole weight in 1 mole of the hydrochloric acid hydroxylamine to 1 mole of the nitro carbazole ketone compound.

The content ratio of the nitro carbazole oxime compound, acetyl chloride, and triethylamine may be, for example, 1 mole weight to 1 mole of acetyl chloride and 1 mole weight to 1 mole of triethylamine to 1 mole of nitro carbazole oxime compound. .

In addition, the method for preparing the compounds of Formulas 1-13 to 1-18 of the present invention may be synthesized by, for example, a synthesis process described by Scheme 2 below. Where R ₅ of the resulting compound after the nitration reaction is NO ₂ . However, the synthesis method of the compound is not limited thereto.

Scheme 2

According to Scheme 2, a halogen ketone compound prepared from a Friedel-Craft reaction of a bromo heterocyclic compound and an acyl chloride is obtained by a Ulmann reaction under 9H-carbazole and copper iodide (CuI) to obtain a carbazole ketone compound. The carbazole oxime compound is obtained by subjecting the carbazole ketone compound to the corresponding oxime compound by oximation reaction with hydroxylamine hydrochloride. The carbazole oxime compound is obtained by subjecting the carbazole oxime compound to acetyl chloride under a triethylamine catalyst. The carbazole oxime ester compound has an oxime ester group represented by Chemical Formulas 1-13 to 118, wherein any one of R ₅ or R ₆ is a nitro group by nitration reaction with a capperate (Cu (NO ₃ ) ₂ ) 2.5 hydrate. Photoinitiators can be obtained.

The content ratio of the 9H-carbazole, the halogen ketone compound and the copper iodide is, for example, 1 mole of 9H-carbazole to 4 mole weight of 1 mole of halogen ketone compound and 4 mole weight of 1 mole of copper iodide. Can be.

The content ratio of the nitro carbazole ketone compound and the hydroxylamine hydrochloride may be, for example, 4 mole weight in 1 mole of the hydrochloric acid hydroxylamine to 1 mole of the nitro carbazole ketone compound.

The content ratio of the nitro carbazole oxime compound, acetyl chloride, and triethylamine may be, for example, 1 mole weight to 1 mole of acetyl chloride and 1 mole weight to 1 mole of triethylamine to 1 mole of nitro carbazole oxime compound. .

The content ratio of the carbazole ketone compound and the copper nitrate may be, for example, 0.5 mole to 2 mole weights of copper nitrate to 1 mole weight of the carbazole ketone compound.

In addition, the method for preparing the compound of Chemical Formulas 1-19 to 128 of the present invention may be synthesized by, for example, a synthesis process described by Scheme 3 below. When preparing the compounds of the formula 1-24 to 1-28, any one of R ₁ , R ₂ of the carbazole compound is NO ₂ , R ₅ of the bromo heterocyclic compound is CH ₃ . However, the synthesis method of the compound is not limited thereto.

Scheme 3

According to Scheme 3, a halogen ketone compound prepared from the Friedel-Craft reaction of a bromo heterocyclic compound and an acyl chloride is obtained by carbazole ketone compound by Ulmann reaction under 9H-carbazole and copper iodide (CuI). The carbazole ketone compound in which nitro is introduced into any one of R ₁ and R ₂ of carbazole is obtained by nitration reaction with a capperate (Cu (NO ₃ ) ₂ ) 2.5 hydrate. The nitro carbazole ketone compound is obtained with the corresponding alpha keto oxime compound by isopentyl nitrite (IPN) and oxo-oximation reaction. Next, a photoinitiator having an alphaketo oxime ester group represented by Chemical Formulas 1-19 to 128 may be obtained by acetylation of the nitro carbazole alpha keto oxime compound and acetyl chloride under a triethylamine catalyst.

The content ratio of the 9H-carbazole, the halogen ketone compound and the copper iodide is, for example, 1 mole of 9H-carbazole to 4 mole weight of 1 mole of halogen ketone compound and 4 mole weight of 1 mole of copper iodide. Can be.

The content ratio of the carbazole ketone compound and the copper nitrate may be, for example, 0.5 mole to 2 mole weights of copper nitrate to 1 mole weight of the carbazole ketone compound.

The content ratio of the nitro carbazole ketone compound and isopentyl nitrite may be, for example, 4 mole weight in 1 mole of isopentyl nitrite to 1 mole of the nitro carbazole ketone compound.

The content ratio of the nitro carbazole oxime compound, acetyl chloride, and triethylamine may be, for example, 1 mole weight to 1 mole of acetyl chloride and 1 mole weight to 1 mole of triethylamine to 1 mole of nitro carbazole oxime compound. .

In addition, the method for preparing a compound of Formulas 1-29 to 133 of the present invention may be synthesized by, for example, a synthesis process described by Scheme 4 below. When preparing the compounds of the formula 1-29 to 133, R ₅ of the bromo heterocyclic compound is NO ₂ . However, the synthesis method of the compound is not limited thereto.

Scheme 4

According to Scheme 4, a halogen ketone compound prepared from the Friedel-Craft reaction of a bromo heterocyclic compound and an acyl chloride is obtained by a Ulmann reaction under 9H-carbazole and copper iodide (CuI) to obtain a carbazole ketone compound. The carbazole ketone compound is subjected to oxo-oximation reaction with isopentnitrite (IPN) to obtain the corresponding alpha keto oxime compound. Next, the carbazole alpha keto oxime compound is subjected to an acetylation reaction of acetyl chloride under a triethylamine catalyst to obtain a carbazole alpha keto oxime ester compound. The carbazole alpha keto oxime ester compound is subjected to nitration reaction with a capperate (Cu (NO ₃ ) ₂ ) 2.5 hydrate to obtain a photoinitiator having an alpha keto oxime ester group represented by Chemical Formulas 1-29 to 133.

The content ratio of the 9H-carbazole, the halogen ketone compound and the copper iodide is, for example, 1 mole of 9H-carbazole to 4 mole weight of 1 mole of halogen ketone compound and 4 mole weight of 1 mole of copper iodide. Can be.

The content ratio of the carbazole ketone compound and the copper nitrate may be, for example, 0.5 mole to 2 mole weights of copper nitrate to 1 mole weight of the carbazole ketone compound.

The content ratio of the nitro carbazole ketone compound and isopentyl nitrite may be, for example, 4 mole weight in 1 mole of isopentyl nitrite to 1 mole of the nitro carbazole ketone compound.

The content ratio of the nitro carbazole oxime compound, acetyl chloride, and triethylamine may be, for example, 1 mole weight to 1 mole of acetyl chloride and 1 mole weight to 1 mole of triethylamine to 1 mole of nitro carbazole oxime compound. .

The photopolymerization composition according to the present invention is an oxime ester compound composed of a carbazole containing a hetero ring used as a photo initiator in the photocrosslinking reaction as a photopolymerization reaction, or an oxime ester compound composed of a carbazole containing a hetero ring represented by the formula (1). It characterized in that it comprises at least one.

The photopolymerization composition of the present invention comprises an oxime ester compound composed of a carbazole comprising a hetero ring used as a photo initiator in the photocrosslinking reaction as a photo polymerization initiator, or an oxime ester compound composed of a carbazole comprising a hetero ring represented by the formula (1). One or more kinds may be included, but may be used by mixing with other known photopolymerization initiators.

An oxime ester compound composed of a carbazole containing a hetero ring used as a photo initiator in the photocrosslinking reaction, or at least one oxime ester compound composed of a carbazole containing a hetero ring represented by the formula (1) and other known photopolymerization initiators; When used in combination, it is preferable to include at least 50% by weight of the total amount of the photopolymerization initiator oxime ester compound composed of carbazole including a hetero ring according to the present invention. That is, an oxime ester compound composed of carbazole including a hetero ring used as a photo initiator in the photocrosslinking reaction, including 50 wt% or more of the total amount of the photopolymerization initiator, or a carbazole comprising a hetero ring represented by Chemical Formula 1 When used in combination with at least one oxime ester compound and other known photopolymerization initiators, it is possible to provide an effect of increasing the solubility of the photoinitiator and maintaining the sensitivity.

Examples of known photoinitiators include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylaceto Acetophenones including phenone, benzophenone, 2-chlorobenzophenone, benzophenones including p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin Benzoin ethers including isobutyl ether, benzyldimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethyl thioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene Sulfur compounds, including 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and anthraquinone, including 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide Organic peroxides, including 2-mers Thiol compounds including captobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl Imidazolyl compounds including dimers, triazine compounds including p-methoxytriazines, 2,4,6-tris (trichloromethyl) s-triazines, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2-4 (-diethylamino-2-methylphenyl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenol) etherine] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy Halo, including styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine And amino ketone compounds including a triazine compound having a methyl group and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1one.

The photopolymerization composition of the present invention is a sensitizer, and includes cyanine, xanthene, oxazine, thiazine, diarylmethane, triarylmethane and other cationic dyes, merocyanine, coumarin, indigo, aromatic amines, phthalocyanine, azo and quinone. And neutral dyes including thioxanthene photosensitive dyes and benzophenones, acetophenones, benzoin, thioxanthones, anthraquinones, imidazoles, biimidazoles, coumarins, ketocoumarins, triazines And compounds including benzoic acid.

The photopolymerization composition of the present invention may include a polymer compound soluble in a solvent or an aqueous alkali solution alone or a mixture of these polymer compounds and a photopolymerizable compound having an ethylenically unsaturated bond.

In the photopolymerization composition of the present invention, a polymer compound soluble in a solvent or an aqueous alkali solution can be used as the binder resin. The binder resin may be an acrylic (co) polymer or an acrylic (co) polymer having an acrylic unsaturated bond in the side chain, and the amount of the binder resin may be used in a range of 3 to 50% by weight based on 100% by weight of the photopolymerization composition. It is preferable to provide thin film properties such as heat resistance and chemical resistance.

As one example, the average molecular weight of the acrylic (co) polymer may be used 2,000 to 300,000, the degree of dispersion is 1.0 to 10.0, it is more preferable to use an average molecular weight of 4,000 to 100,000.

The acrylic (co) polymer is a copolymer of monomers including the following monomers. Examples of the monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl. (Meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, la Uryl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate and hexadecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclo Fentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, acrylic acid, meta Krylic acid, itaconic acid, maleic acid, maleic acid anhydride, maleic acid monoalkyl ester, monoalkylitaconate, monoalkyl fumarate, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (Meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyloxetane-3-methyl (meth) acrylate, 3- Ethyloxetane-3-methyl (meth) acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N- Cyclohexyl maleimide, (meth) acrylamide, N-methyl (meth) acrylamide, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

An acrylic (co) polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by adding an epoxy resin to an acrylic copolymer containing carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, and the like. Acrylic monomer containing the carboxylic acid, alkyl (meth) acrylates, such as methyl (meth) acrylate and hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and Adammann Methyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl ( Meta) acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth) Ah Glycidyl acrylate, glycidyl methacrylate, 3,4-epoxy butyl to an acrylic copolymer containing carboxylic acid obtained by copolymerizing two or more kinds of monomers such as aryl amide and N-methyl (meth) acrylamide Binder resin obtained by addition reaction of epoxy resins, such as (meth) acrylate, 2, 3- epoxycyclohexyl (meth) acrylate, and 3, 4- epoxycyclohexyl methyl (meth) acrylate, at the temperature of 40-180 degreeC Can be used.

Another example of an acrylic (co) polymer having an acrylic unsaturated bond in the side chain is a copolymer in which carboxylic acid is added to an acrylic copolymer containing an epoxy group, and glycidyl acrylate, glycidyl methacrylate, 3, Acrylic monomer and methyl (meth) acryl containing epoxy groups, such as 4-epoxybutyl (meth) acrylate, 2, 3- epoxycyclohexyl (meth) acrylate, and 3, 4- epoxycyclohexyl methyl (meth) acrylate Alkyl (meth) acrylates, such as the rate and hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and dicyclopentanyl (meth) acrylate , Dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, α-methylstyrene, acetoxy styrene , N- Two or two monomers, such as methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, (meth) acrylamide, and N-methyl (meth) acrylamide To an acrylic copolymer containing an epoxy group obtained by copolymerizing at least a species, an acrylic monomer containing carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and monoalkyl ester of maleic acid is added at a temperature of 40 to 180 ° C. The binder resin obtained by reaction can be used.

The present invention also provides a colored photopolymerization composition comprising an oxime ester compound composed of carbazole including a hetero ring represented by Chemical Formula 1 and a colorant or pigment.

Examples of the colorant or pigment included for use as a color filter or a resist for forming a black matrix include cyan, magenta, yellow and black pigments of red, green, blue and navy blue mixed systems. As pigments CI Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168 , CI Pigment Orange 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, CI Pigment Green 7, 36, CI Pigment brown 23, 25, 26, CI pigment black 7, and titanium black.

According to the present invention, there is provided a substrate having a column spacer, a black matrix, a color filter, an organic insulating film, and a substrate formed by coating the same from the photopolymerization composition, wherein the film is used as a display panel of TFT-LCD, OLED, TSP, etc. Can be.

As a method of forming a pattern using such a photopolymerization composition, a layer is formed by applying a photopolymerization composition onto a substrate or a substrate, removing a volatile component such as a solvent from the applied photopolymerization composition layer, and removing the volatile component through a photomask. The method of developing after exposing this is mentioned. The cured film obtained through such a hardening process is provided.

The substrate may be, for example, a substrate having a flat surface such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, or a GaAs substrate. have. As a method of coating the photopolymerization composition on the substrate, for example, a known coating method such as spin coating, casting, roll coating, slit and spin coating, or coating using a coater such as a spinless coater may be used. It is not limited.

Subsequently, volatile components, such as a solvent, can be volatilized by heating. In this way, the layer which consists of solid content of a photopolymerization composition is formed on substrates etc. The layer of solids of the photosensitive composition is then exposed, for example an active energy ray can be selectively irradiated through a photomask. As an exposure light source, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halogen lamp, etc. are suitable, and a laser beam etc. can also be applied as an active energy ray for exposure.

Other electron beams, α rays, β rays, γ rays, X rays, neutron rays and the like can also be used. The active energy ray is irradiated through the photomask, where the photomask is provided with a light shielding layer for shielding the active energy ray, for example, on the surface of the glass film.

The portion of the glass plate where the light shielding layer is not provided is a light transmitting portion through which active energy rays are transmitted. According to the pattern of the light transmitting portion, the photopolymerizable composition is exposed to irradiate the active energy rays with the unirradiated region and the irradiation region with the active energy rays. This occurs.

The substrate exposed in this manner is developed by, for example, aqueous alkali solution. For example, after the exposure, the photopolymerization composition layer may be contacted with an aqueous alkali solution, and specifically, the substrate in a state where the photopolymerization composition layer is formed on its surface may be immersed in an aqueous alkali solution or sprayed with a diluted aqueous alkali solution. The aqueous alkali solution may, for example, be an aqueous solution of an alkaline compound such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or base amine. By the development, the area in which the active energy ray is not irradiated in the photosensitive composition layer is removed, leaving only the active energy ray irradiation area to form a pattern.

Thus, the board | substrate which performed image development can obtain a desired pattern by washing with water normally and drying.

Hereinafter, the representative compounds of the present invention will be described in detail with reference to Examples and Comparative Examples for a detailed understanding of the present invention. Embodiments according to the present invention can be modified in many different forms, not limited to the present invention.

Example 1: Synthesis of Compound of Formula 1-1

[Formula 1-1]

Step 1: Synthesis of 1- (5-Bromothiophen-2-yl) hexane-1-one

N-hexanoyl chloride (13.5 g, 100 mmol) was added to AlCl ₃ (14.6 g, 110 mmol) precipitated in DCM (40 mL) under a nitrogen atmosphere, and the reaction solution was cooled using an ice-bath. After 2-bromothiophene (16.3 g, 100 mmol) was slowly added thereto, the reaction solution was stirred at room temperature for 5 hours. After confirming completion of the reaction by TLC, the reaction solution was slowly added dropwise to a sufficiently cooled 10% HCl aqueous solution. The organic layer in the reaction solution was extracted using DCM, washed with 5% NaOH and distilled water and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 4/1) to obtain 18.3 g of a pale yellow solid powder in 70% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 7.45 (d, 1H), 7.11 (d, 1H), 2.83 (t, 2H), 1.72-1.75 (m, 2H), 1.35-1.39 (m, 4H ), 0.92 (t, 3 H).

Step 2: Synthesis of 1- (5- (9H-Carbazol-9-yl) thiophen-2-yl) hexane-1-one

The first step compound (13.1 g, 50 mmol) and N-carbazole (8.36 g, 50 mmol) were dissolved in DMF (40 mL), followed by CuI (0.95 g, 5 mmol) and 18-Crown-6 ether (0.66 g, 2.5 mmol) was added. After the reaction solution was refluxed for 24 hours in a nitrogen atmosphere, the reaction was terminated by TLC. The reaction solution was cooled to room temperature and then added dropwise to a rapidly stirring distilled water (300 mL) and DCM (20 mL) solution. After passing through Celite to filter out impurities, the organic layer was separated and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 8.9 g of a yellow solid in 80% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.13 (d, 2H), 7.82 (m, 1H), 7.66 (m, 2H), 7.26-7.49 (m, 5H), 2.97 (m, 2H), 1.71-1.77 (m, 2H), 1.32-1.38 (m, 4H), 0.97 (t, 3H).

Step 3: Synthesis of 1- (5- (3-Nitro-9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one

To a mixed solution of acetic acid (10 mL) and acetic anhydride (20 mL) Cu (NO ₃ ) ₂ ^. 2.5H ₂ O (2.79 g, 12 mmol) was added thereto, and dissolved at room temperature with stirring to prepare a nitrating mixture. In a nitrogen atmosphere, the nitrating mixture prepared for the solution of the two-step compound (6.95 g, 20 mmol) in DCM (15 mL) was slowly added dropwise at room temperature, followed by stirring for 2 hours while maintaining the temperature below 30 ° C. It was. After confirming the completion of the reaction by TLC, the reaction solution was added dropwise to distilled water and stirred for an additional 30 minutes. DCM was added, the organic layer was separated, washed with midstream, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 6.6 g of a yellow solid in 85% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.94 (d, 1H), 8.28 (d, 1H), 8.11 (d, 1H), 7.21-7.75 (m, 5H), 7.19 (dd, 1H), 2.90 (t, 2H), 1.73-1.77 (m, 2H), 1.31-1.36 (m, 4H), 0.88 (t, 3H).

Step 4: Synthesis of 5- (3-Nitro-9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one oxime

The compound of step 3 (6.05 g, 20 mmol) was dissolved in ethyl acetate (20 mL), and then ethanol (20 mL) was added dropwise. NH ₂ OH.HCl (3.48 g, 50 mmol) and triethylamine (4.04 g, 40 mmol) were sequentially added dropwise to the reaction solution under a nitrogen atmosphere, followed by stirring for 2 hours while raising the temperature to reflux. After confirming the completion of the reaction by TLC, the reaction solution was cooled and quenched by adding cooling water. The organic layer extracted with ethyl acetate was washed three times with distilled water, and then concentrated under reduced pressure. The concentrate was purified using silica gel column chromatography (n-Hex./EA = 3/1) to give 5.8 g of a yellow solid in 92% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 9.05 (d, 1H), 8.38 (d, 1H), 8.19 (d, 1H), 7.58-7.53 (m, 5H), 7.19 (d, 1H), 2.85 (t, 2H), 1.70-1.79 (m, 2H), 1.40-1.50 (m, 4H), 0.96 (t, 3H).

Step 5: Synthesis of 5- (3-Nitro-9H-carbazol-9-yl) thiophen-2-yl) hexan-1-one O-acetyl oxime

In a nitrogen atmosphere, the 4-step compound (4.07 g, 10 mmol) was dissolved in ethyl acetate (20 mL), and triethylamine (1 mL) was added thereto. After blocking the reaction vessel with aluminum foil, acetic anhydride (2.04 g, 20 mmol) was added dropwise dropwise to the ice-bath cooled reaction solution. After the addition was completed, the reaction solution was stirred at room temperature for 5 hours, and then distilled water was added dropwise. After stirring for about 10 minutes, the mixture was extracted using ethyl acetate and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 3.82 g of a yellow crystalline solid in 85% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 9.01 (d, 1H), 8.35 (d, 1H), 8.17 (d, 1H), 7.53-7.58 (m, 5H), 7.43 (d, 1H), 2.90 (t, 2H), 2.29 (s, 3H), 1.75-1.79 (m, 2H), 1.40-1.51 (m, 4H), 0.97 (t, 3H).

Example 2-6

According to the preparation method of Example 1, the following compounds were synthesized as shown in Table 1.

Example
No. Formula No. R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ ¹ H-NMR (δ, ppm) 2 1-2 -NO ₂ -H -CH ₃ -CH ₃ -H -H 9.01 (s, 1H), 8.35 (dd, 1H), 8.17 (d, 1H), 7.53-7.58 (m, 5H), 7.43 (dd, 1H), 2.89 (s, 3H), 2.29 (s, 3H) . 3 1-3 -NO ₂ -H -C ₂ H ₅ -CH ₃ -H -H 9.00 (s, 1H), 8.34 (dd, 1H), 8.16 (d, 1H), 7.54-7.58 (m, 5H), 7.42 (dd, 1H), 2.89 (q, 2H), 2.29 (s, 3H) , 0.98 (t, 3 H). 4 1-4 -NO ₂ -H -C ₃ H ₇ -CH ₃ -H -H 9.00 (s, 1H), 8.34 (dd, 1H), 8.16 (d, 1H), 7.54-7.58 (m, 5H), 7.42 (dd, 1H), 2.89 (q, 2H), 2.29 (s, 3H) , 1.62 (m, 2H), 0.98 (t, 3H). 5 1-5 -NO ₂ -H -C ₄ H ₉ -CH ₃ -H -H 9.00 (s, 1H), 8.34 (dd, 1H), 8.16 (d, 1H), 7.54-7.58 (m, 5H), 7.42 (dd, 1H), 2.89 (q, 2H), 2.29 (s, 3H) , 1.61-1.42 (m, 4H), 0.97 (t, 3H). 6 1-6 -NO ₂ -H -C ₇ H ₁₅ -CH ₃ -H -H 9.01 (s, 1H), 8.34 (dd, 1H), 8.16 (d, 1H), 7.54-7.58 (m, 5H), 7.42 (dd, 1H), 2.89 (q, 2H), 2.29 (s, 3H) , 1.32-1.62 (m, 8 H), 0.97 (t, 3 H).

Example 7: Synthesis of Compound of Formula 1-7

[Formula 1-7]

Step 1: Synthesis of 1- (5-Bromo-4-methylthiophen-2-yl) hexane-1-one

N-hexanoyl chloride (20.3 g, 150 mmol) was added to AlCl ₃ (21.9 g, 165 mmol) precipitated in DCM (60 mL) under a nitrogen atmosphere, and the reaction solution was cooled using an ice bath. . 2-bromo-3-methylthiophene (26.4 g 150 mmol) was slowly added thereto, and the reaction solution was stirred at room temperature for 8 hours. After confirming the completion of the reaction by TLC, the reaction solution was slowly added dropwise to the sufficiently cooled 10% HCl aqueous solution. The organic layer in the reaction solution was extracted using DCM, washed with 5% NaOH and distilled water, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 4/1) to obtain 32.1 g of a pale yellow solid in 78% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 7.32 (s, 1H), 2.82 (t, 2H), 2.23 (s, 3H), 1.73-1.78 (m, 2H), 1.34-1.39 (m, 4H ), 0.93 (t, 3H)

Step 2: Synthesis of 1- (5- (9H-Carbazol-9-yl) -4-methylthiophen-2-yl) hexane-1-one

N-carbazole (18.2 g, 109 mmol) and the first step compound (30.0 g, 109 mmol) were dissolved in DMF (40 mL), followed by CuI (2.1 g, 11 mmol) and 18-Crown-6 ether (1.4 g, 5.5 mmol) was added. After the reaction solution was refluxed for 48 hours in a nitrogen atmosphere, the reaction was terminated by TLC. The reaction solution was cooled to room temperature and then added dropwise to a rapidly stirring distilled water (300 mL) and DCM (20 mL) solution. After passing through Celite to filter out impurities, the organic layer was separated and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 29.7 g of a yellow solid in 75% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.12 (d, 2H), 7.81 (m, 1H), 7.64 (m, 2H), 7.25-7.48 (m, 4H), 2.95 (t, 2H), 2.19 (s, 3H), 1.70-1.76 (m, 2H), 1.31-1.36 (m, 4H), 0.92 (t, 3H).

Step 3: Synthesis of 1- (4-Methyl-5- (3-nitro-9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one

Cu (NO ₃ ) ₂ for a mixed solution of acetic acid (30 mL) and acetic anhydride (60 mL) ^. 2.5H ₂ O (8.0 g, 34.5 mmol) was added and dissolved under stirring at room temperature. To the solution of the two-step compound (20.0 g, 57.5 mmol) in DCM (15 mL) was added dropwise at room temperature under a nitrogen atmosphere, and then stirred for 2 hours while maintaining the temperature below 30 ° C. After confirming the completion of the reaction by TLC, the reaction solution was added dropwise to distilled water and stirred for additional 30 minutes. DCM was added, the organic layer was separated, washed with distilled water, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 19.1 g of a yellow solid in 85% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.93 (d, 1H), 8.27 (dd, 1H), 8.11 (d, 1H), 7.20-7.75 (m, 4H), 7.18 (dd, 1H), 2.89 (t, 2H), 2.19 (s, 3H), 1.72-1.76 (m, 2H), 1.29-1.35 (m, 4H), 0.90 (t, 3H).

Step 4: Synthesis of 4-Methyl-5- (3-nitro-9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one oxime

The third step compound (10.0 g, 33 mmol) was dissolved in ethyl acetate (35 mL) and then ethanol (35 mL) was added dropwise. NH ₂ OH.HCl (5.75 g, 83 mmol) and triethylamine (6.67 g, 66 mmol) were sequentially added dropwise to the reaction solution under nitrogen atmosphere, followed by stirring for 2 hours while heating to reflux. After confirming the completion of the reaction by TLC, the reaction solution was cooled and quenched by adding cooling water. The organic layer extracted with ethyl acetate was washed three times with distilled water, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 9.3 g of a yellow solid in 90% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 9.03 (d, 1H), 8.37 (d, 1H), 8.18 (d, 1H), 7.52-7.58 (m, 4H), 7.17 (d, 1H), 2.86 (t, 2H), 2.19 (s, 3H), 1.69-1.77 (m, 2H), 1.39-1.48 (m, 4H), 0.93 (t, 3H).

Step 5: Synthesis of 4-Methyl-5- (3-nitro-9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one O-acetyl oxime

The nitrogen compound (5.0 g, 11 mmol) was dissolved in ethyl acetate (22 mL) in a nitrogen atmosphere, and triethylamine (1.1 mL) was added thereto. After blocking the reaction vessel with aluminum foil, acetic anhydride (2.2 g, 22 mmol) was added dropwise dropwise to the ice-bath cooled reaction solution. After completion of the dropwise addition, the reaction solution was stirred at room temperature for 5 hours, and then added dropwise with distilled water. After stirring for about 10 minutes, the mixture was extracted using ethyl acetate and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 4.8 g of a yellow crystalline solid in 87% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 9.01 (s, 1H), 8.32 (d, 1H), 8.14 (d, 1H), 6.83-7.56 (m, 5H), 2.90 (t, 2H), 2.30 (s, 3H), 2.21 (s, 3H), 1.70-1.75 (m, 2H), 1.31-1.45 (m, 4H), 0.92 (t, 3H).

Example 8-12

According to the preparation method of Example 7, the following compound was synthesized as shown in Table 2.

Example
No. Formula No. R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ ¹ H-NMR (δ, ppm) 8 1-8 -NO ₂ -H -CH ₃ -CH ₃ -CH ₃ -H 9.03 (s, 1H), 8.34 (d, 1H), 8.19 (d, 1H), 6.80-7.52 (m, 5H), 2.92 (s, 3H), 2.29 (s, 3H), 2.21 (s, 3H) 9 1-9 -NO ₂ -H -C ₂ H ₅ -CH ₃ -CH ₃ -H 9.02 (s, 1H), 8.33 (d, 1H), 8.18 (d, 1H), 6.80-7.51 (m, 5H), 2.90 (t, 2H), 2.30 (s, 3H), 2.21 (s, 3H) , 0.95 (t, 3 H). 10 1-10 -NO ₂ -H -C ₃ H ₇ -CH ₃ -CH ₃ -H 9.02 (s, 1H), 8.33 (d, 1H), 8.18 (d, 1H), 6.80-7.51 (m, 5H), 2.90 (t, 2H), 2.30 (s, 3H), 2.21 (s, 3H) , 1.65 (m, 2 H), 0.95 (t, 3 H). 11 1-11 -NO ₂ -H -C ₄ H ₉ -CH ₃ -CH ₃ -H 9.01 (s, 1H), 8.32 (d, 1H), 8.14 (d, 1H), 6.82-7.56 (m, 5H), 2.90 (t, 2H), 2.30 (s, 3H), 2.21 (s, 3H) , 1.72 (m, 2H), 1.41 (m, 2H), 0.96 (t, 3H). 12 1-12 -NO ₂ -H
-C ₇ H ₁₅ -CH ₃ -CH ₃ -H 9.01 (s, 1H), 8.32 (d, 1H), 8.14 (d, 1H), 6.82-7.58 (m, 5H), 2.89 (t, 2H), 2.30 (s, 3H), 2.20 (s, 3H) , 1.74 (m, 2H), 1.27-1.54 (m, 8H), 0.96 (t, 3H).

Example 13: Synthesis of Compound of Formula 1-13

[Formula 1-13]

Step 3: Synthesis of 5- (9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one oxime

The compound (10.4 g, 30 mmol) obtained in step 2 of [Example 1] was dissolved in ethyl acetate (30 mL), and then ethanol (30 mL) was added dropwise. NH ₂ OH.HCl (4.2 g, 60 mmol) was added to the above solution under nitrogen atmosphere, and triethylamine (6.0 g, 60 mmol) was added dropwise. The reaction solution was refluxed with stirring for 3 hours, then cooled to room temperature and cooled water was added dropwise. The organic layer was separated using ethyl acetate, and washed three times with distilled water. The organic layer was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-Hex./EA = 5/1) to obtain 10.2 g of a pale yellow solid in 94% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.14 (m, 2H), 7.58 (m, 2H), 7.13-7.46 (m, 6H), 2.84 (m, 2H), 1.70-1.76 (m, 2H ), 1.31-1.36 (m, 4H), 0.92 (t, 3H).

Step 4: Synthesis of 5- (9H-Carbazol-9-yl) thiophen-2-yl) hexane-1-one O-acetyl oxime

The third step compound (9.4 g, 25 mmol) was dissolved in ethyl acetate (50 mL) and triethylamine (2.5 mL) was added. After blocking the reaction vessel with aluminum foil, acetic anhydride (5.1 g, 50 mmol) was added dropwise dropwise to the ice-bath cooled reaction solution. After the dropping was completed, the reaction solution was stirred at room temperature for 4 hours, and then distilled water was added dropwise. After stirring for about 10 minutes, the mixture was extracted using ethyl acetate and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 5/1) to obtain 9.5 g of a yellow crystalline solid in 91% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.35 (d, 2H), 8.14 (d, 2H), 7.21-7.61 (m, 6H), 2.89 (t, 2H), 2.29 (s, 3H), 1.72-1.77 (m, 2H), 1.30-1.37 (m, 4H), 0.94 (t, 3H).

Step 5: Synthesis of 5- (9H-Carbazol-9-yl) -4-nitrothiophen-2-yl) hexane-1-one O-acetyl oxime

In acetic acid (10 mL) and acetic anhydride, _{Cu (NO 3) 2 .2.5H 2} O (2.5 g, 10.8 mmol) to a mixed solution of (20 mL) and dissolved with stirring at room temperature to prepare a nitrating mixture. The nitrating mixture was slowly added dropwise at room temperature to a solution of the four step compound (7.5 g, 18 mmol) in DCM (5 mL) under a nitrogen atmosphere, and then stirred for 2 hours while maintaining the temperature at 30 ° C. or lower. . After confirming the completion of the reaction by TLC, the reaction solution was added dropwise to distilled water and stirred for a further 30 minutes. DCM was added to separate the organic layer, washed with distilled water, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 5.2 g of a yellow solid in 62% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.92 (d, 1H), 8.27 (d, 1H), 8.17 (d, 1H), 7.25-7.94 (m, 5H), 7.18 (d, 1H), 2.97 (t, 2H), 2.30 (s, 3H), 1.72-1.76 (m, 2H), 1.29-1.35 (m, 4H), 0.93 (t, 3H).

Example 14-18

According to the preparation method of Example 13, the following compound was synthesized as in Table 3.

Example
No. Formula No. R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ ¹ H-NMR (δ, ppm) 14 1-14 -H -H -CH ₃ -CH ₃ -NO ₂ -H 8.57 (d, 1H), 8.27 (d, 1H), 8.17 (s, 1H), 7.25-7.94 (m, 6H), 2.97 (s, 3H), 2.35 (s, 3H). 15 1-15 -H -H -C ₂ H ₅ -CH ₃ -NO ₂ -H 8.57 (d, 1H), 8.26 (d, 1H), 8.16 (s, 1H), 7.25-7.92 (m, 6H), 2.96 (t, 3H), 2.34 (s, 3H), 0.98 (t, 3H) . 16 1-16 -H -H -C ₃ H ₇ -CH ₃ -NO ₂ -H 8.57 (d, 1H), 8.26 (d, 1H), 8.16 (s, 1H), 7.25-7.92 (m, 6H), 2.96 (t, 3H), 2.33 (s, 3H), 1.68 (m, 2H) , 0.98 (t, 3 H). 17 1-17 -H -H -C ₄ H ₉ -CH ₃ -NO ₂ -H 8.56 (d, 1H), 8.25 (d, 1H), 8.15 (s, 1H), 7.22-7.89 (m, 6H), 2.95 (t, 3H), 2.32 (s, 3H), 1.66 (m, 2H) , 1.47 (m, 2 H), 0.98 (t, 3 H). 18 1-18 -H -H -C ₇ H ₁₅ -CH ₃ -NO ₂ -H 8.56 (d, 1H), 8.25 (d, 1H), 8.15 (s, 1H), 7.22-7.88 (m, 6H), 2.95 (t, 3H), 2.32 (s, 3H), 1.69 (m, 2H) , 1.29-1.47 (m, 8 H), 0.98 (t, 3 H).

[Comparative Example 1 to Comparative Example 2]

Comparative Example 1 was synthesized as shown in Table 4 by proceeding four steps without the three-step synthesis process of the manufacturing method of Example 1.

In Comparative Example 2, the amount of Cu (NO ₃ ) ₂ 2.5H ₂ O added in the three-step synthesis process of Example 1 was synthesized as shown in Table 4 using twice the preparation method of Example 1.

Comparative example
No. Formula No. R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ ¹ H-NMR (δ, ppm) One 1-35 -H -H -C ₅ H ₁₁ -CH ₃ -H -H 8.45 (dd, 1H), 8.09 (dd, 1H), 7.92 (dd, 1H), 7.25-7.68 (m, 7H), 2.87 (t, 2H), 2.28 (s, 3H), 1.69-1.74 (m, 2H), 1.37-1.45 (m, 4H), 0.92 (t, 3H). 2 1-36 -NO ₂ -NO ₂ -C ₅ H ₁₁ -CH ₃ -H -H 9.41 (s, 1H), 9.31 (s, 1H), 8.64 (d, 1H), 8.18 (d, 1H), 8.05 (s, 1H), 7.25-7.89 (m, 3H), 2.92 (t, 2H) , 2.31 (s, 3H), 1.71-1.76 (m, 2H), 1.34-1.41 (m, 4H), 0.95 (t, 3H).

For reference, the structure of Comparative Example 1 may be represented by the following Chemical Formula 1-35, and the structure of Comparative Example 2 may be represented by the following Chemical Formula 1-36.

[Formula 1-35]

[Formula 1-36]

Example 19 Synthesis of Compound of Formula 1-19

[Formula 1-19]

Step 4: Synthesis of (Hydroxyimino) -1- (5- (3-nitro-9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one

After dissolving the 3-step compound of Example 1 (6.5 g, 15.6 mmol) in dimethylformamide (DMF, 30 mL), isopentyl nitrate (IPN, 1.81 g, 15.5 mmol) was added at 30 ° C., and then 12 Stir at room temperature for time. HCl (0.14 g, 3.7 mmol) was added to this solution to terminate the reaction, and distilled water (100 mL) was added to the reaction mixture. Ethyl acetate (100 mL) was added to separate the organic layer, and washed repeatedly with distilled water (100 mL) three times to remove impurities. The organic layer was concentrated under reduced pressure and then subjected to the next reaction without further purification.

Step 5: Synthesis of 2- (Acetoxyimino) -1- (5- (3-nitro-9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one

The 4-step compound (6.5 g, 15 mmol) was dissolved in ethyl acetate (30 mL), and triethylamine (1.5 mL) was added thereto. After blocking the reaction vessel with aluminum foil, acetic anhydride (3.1 g, 30 mmol) was added dropwise dropwise to the ice-bath cooled reaction solution. After the dropping was completed, the reaction solution was stirred at room temperature for 4 hours, and then distilled water was added dropwise. After stirring for about 10 minutes, the mixture was extracted using ethyl acetate and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 5.1 g of a yellow crystalline solid in 70% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 9.00 (s, 1H), 8.34 (d, 1H), 8.18 (d, 1H), 7.48-7.57 (m, 5H), 7.42 (d, 1H), 2.92 (t, 2H), 2.31 (s, 3H), 1.76-1.82 (m, 2H), 1.41-1.52 (m, 2H), 0.98 (t, 3H).

Example 20-23

Compounds of Examples 20 to 23 were synthesized according to the preparation method of Example 19, as shown in Table 5.

Example
No. Formula No. R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ ¹ H-NMR (δ, ppm) 20 1-20 -NO ₂ -H -CH ₃ -CH ₃ -H -H 9.00 (s, 1H), 8.34 (dd, 1H), 8.18 (d, 1H), 7.49-7.57 (m, 5H), 7.43 (dd, 1H), 2.92 (s, 3H), 2.32 (s, 3H) . 21 1-21 -NO ₂ -H -C ₂ H ₅ -CH ₃ -H -H 9.01 (s, 1H), 8.33 (dd, 1H), 8.18 (d, 1H), 7.49-7.58 (m, 5H), 7.42 (dd, 1H), 2.91 (q, 2H), 2.30 (s, 3H) , 1.01 (t, 3 H). 22 1-22 -NO ₂ -H -C ₃ H ₇ -CH ₃ -H -H 9.01 (s, 1H), 8.33 (dd, 1H), 8.18 (d, 1H), 7.49-7.58 (m, 5H), 7.42 (dd, 1H), 2.90 (q, 2H), 2.30 (s, 3H) , 1.62 (m, 2H), 0.99 (t, 3H). 23 1-23 -NO ₂ -H -C ₆ H ₁₄ -CH ₃ -H -H 9.01 (s, 1H), 8.34 (dd, 1H), 8.16 (d, 1H), 7.48-7.58 (m, 5H), 7.42 (dd, 1H), 2.88 (q, 2H), 2.28 (s, 3H) , 1.32-1.63 (m, 8 H), 0.97 (t, 3 H).

Example 24 Synthesis of Compound 1-24

[Formula 1-24]

Step 4: Synthesis of 2- (Hydroxyimino) -1- (4-methyl-5- (3-nitro-9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one

After dissolving the 3-step compound of Example 1 (8.0 g, 19 mmol) in dimethylformamide (DMF, 35 mL), isopentyl nitrate (IPN, 2.2 g, 18.9 mmol) was added at 30 ° C. Stirred at room temperature for 12 hours. HCl (0.17 g, 4.5 mmol) was added to this solution to terminate the reaction, and distilled water (100 mL) was added to the reaction mixture. Ethyl acetate (100 mL) was added to separate the organic layer, and washed repeatedly with distilled water (100 mL) three times to remove impurities. The organic layer was concentrated under reduced pressure and then subjected to the next reaction without further purification.

Step 5: Synthesis of 2- (Acetoxyimino) -1- (4-methyl-5- (3-nitro-9H-carbazol-9-yl) thiophen-2-yl) hexane-1-one

The 4-step compound (8.0 g, 18 mmol) was dissolved in ethyl acetate (35 mL), and triethylamine (1.7 mL) was added thereto. After blocking the reaction vessel with aluminum foil, acetic anhydride (3.5 g, 33.7 mmol) was added dropwise dropwise to the ice-bath cooled reaction solution. After completion of the dropwise addition, the reaction solution was stirred at room temperature for 4 hours, and distilled water was added thereto. After stirring for about 10 minutes, the mixture was extracted using ethyl acetate and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 5.6 g of a yellow crystalline solid in 62% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.99 (s, 1H), 8.33 (d, 1H), 8.16 (d, 1H), 6.81-7.52 (m, 6H), 2.91 (t, 2H), 2.30 (s, 3H), 2.23 (s, 3H), 1.75-1.80 (m, 2H), 1.44-1.51 (m, 2H), 0.95 (t, 3H).

Example 25-28

According to the preparation method of Example 24, Examples 25 to 28 compounds were synthesized as shown in Table 6.

Example
No. Formula No. R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ ¹ H-NMR (δ, ppm) 25 1-25 -NO ₂ -H -CH ₃ -CH ₃ -CH ₃ -H 9.01 (s, 1H), 8.34 (d, 1H), 8.17 (d, 1H), 6.82-7.52 (m, 5H), 2.92 (s, 3H), 2.30 (s, 3H), 2.24 (s, 3H) . 26 1-26 -NO ₂ -H -C ₂ H ₅ -CH ₃ -CH ₃ -H 9.01 (s, 1H), 8.33 (d, 1H), 8.18 (d, 1H), 6.80-7.51 (m, 5H), 2.91 (q, 2H), 2.30 (s, 3H), 2.23 (s, 3H) , 0.96 (t, 3 H). 27 1-27 -NO ₂ -H -C ₃ H ₇ -CH ₃ -CH ₃ -H 9.00 (s, 1H), 8.33 (d, 1H), 8.17 (d, 1H), 6.81-7.50 (m, 5H), 2.91 (t, 2H), 2.30 (s, 3H), 2.22 (s, 3H) , 1.65 (m, 2 H), 0.95 (t, 3 H). 28 1-28 -NO ₂ -H -C ₆ H ₁₄ -CH ₃ -CH ₃ -H 9.00 (s, 1H), 8.32 (d, 1H), 8.14 (d, 1H), 6.82-7.58 (m, 5H), 2.89 (t, 2H), 2.30 (s, 3H), 2.20 (s, 3H) , 1.74 (m, 2H), 1.27-1.54 (m, 8H), 0.96 (t, 3H).

Example 29: Synthesis of Compound 1-29

[Formula 1-29]

Step 3: Synthesis of 5- (9H-Carbazol-9-yl) thiophen-2-yl) -2- (hydroxyimino) hexane-1-one

After dissolving the second step compound of Example 1 (12.0 g, 34 mmol) in dimethylformamide (DMF, 65 mL), isopentyl nitrate (IPN, 4.1 g, 35 mmol) was added at 30 ° C. Stirred at room temperature for 12 hours. HCl (0.3 g, 8.2 mmol) was added to the solution to terminate the reaction, and distilled water (150 mL) was added to the reaction mixture. Ethyl acetate (150 mL) was added to separate the organic layer, and washed repeatedly with distilled water (150 mL) three times to remove impurities. The organic layer was concentrated under reduced pressure and then subjected to the next reaction without further purification.

Step 4: Synthesis of 5- (9H-Carbazol-9-yl) thiophen-2-yl) -2- (acetoxyimino) hexane-1-one

The third step compound (13.2 g, 35 mmol) was dissolved in ethyl acetate (70 mL), and triethylamine (3.3 mL) was added thereto. After blocking the reaction vessel with aluminum foil, acetic anhydride (6.8 g, 65.4 mmol) was added dropwise dropwise to the cooled reaction solution in an ice-bath. After the addition was completed, the reaction solution was stirred at room temperature for 2 hours, and then distilled water was added dropwise. After stirring for about 10 minutes, the mixture was extracted using ethyl acetate and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 9.8 g of a yellow crystalline solid in 67% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.35 (d, 2H), 8.18 (d, 2H), 6.85-7.51 (m, 6H), 2.90 (t, 2H), 2.29 (s, 3H), 1.72-1.80 (m, 2H), 1.40-1.52 (m, 4H), 0.96 (t, 3H).

Step 5: Synthesis of 5- (9H-Carbazol-9-yl) -4-nitrothiophen-2-yl) -2- (acetoxyimino) hexane-1-one

Cu (NO ₃ ) ₂ .2.5H ₂ O (2.9 g, 13.2 mmol) was added to a mixed solution of acetic acid (12 mL) and acetic anhydride (23 mL), and dissolved by stirring at room temperature to prepare a nitrating mixture. The nitrating mixture was slowly added dropwise at room temperature to a solution of the fourth step compound (8.8 g, 21 mmol) in DCM (6 mL) under a nitrogen atmosphere, and then stirred for 2 hours while maintaining the temperature at 30 ° C. or lower. . After confirming completion of the reaction by TLC, the reaction solution was added dropwise to distilled water, followed by further stirring for 30 minutes. DCM was added, the organic layer was separated, washed with distilled water, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (n-Hex./EA = 3/1) to obtain 6.5 g of a yellow solid in 67% yield.

¹ H-NMR (δ, ppm), CDCl ₃ : 8.56 (d, 1H), 8.28 (d, 1H), 8.17 (s, 1H), 7.25-7.92 (m, 6H), 2.99 (t, 2H), 2.32 (s, 3H), 1.75 (m, 2H), 1.31-1.52 (m, 4H), 0.96 (t, 3H).

Example 30-33

Compounds of Examples 30 to 33 were prepared as shown in Table 7 according to the preparation method of Example 29.

Example
No. Formula No. R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ ¹ H-NMR (δ, ppm) 30 1-30 -H -H -CH ₃ -CH ₃ -NO ₂ -H 8.55 (d, 1H), 8.26 (d, 1H), 8.18 (s, 1H), 7.23-7.89 (m, 6H), 3.00 (s, 2H), 2.31 (s, 3H). 31 1-31 -H -H -C ₂ H ₅ -CH ₃ -NO ₂ -H 8.55 (d, 1H), 8.27 (d, 1H), 8.17 (s, 1H), 7.24-7.80 (m, 6H), 2.99 (q, 2H), 2.30 (s, 3H), 0.96 (t, 3H) . 32 1-32 -H -H -C ₃ H ₇ -CH ₃ -NO ₂ -H 8.55 (d, 1H), 8.26 (d, 1H), 8.17 (s, 1H), 7.24-7.81 (m, 6H), 2.98 (t, 2H), 2.29 (s, 3H), 1.71 (m, 2H) , 0.95 (t, 3 H). 33 1-33 -H -H -C ₆ H ₁₄ -CH ₃ -NO ₂ -H 8.56 (d, 1H), 8.15 (d, 1H), 8.25 (s, 1H), 7.22-7.83 (m, 6H), 2.98 (t, 3H), 2.32 (s, 3H), 1.69 (m, 2H) , 1.29-1.57 (m, 8H), 0.95 (t, 3H).

[Comparative Examples 3 to 4]

In the case of Comparative Example 3 proceeded to the preparation method of Example 19 from the compound of the compound obtained in step 2 of [Example 1] was synthesized as shown in Table 8.

In Comparative Example 4, the amount of Cu (NO ₃ ) ₂ 2.5H ₂ O was added to the compound of Example 19 from the compound obtained by using twice the amount of the preparation method of Example 1, and synthesized as shown in Table 8.

Comparative example
No. Formula No. R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ ¹ H-NMR (δ, ppm) 3 1-37 -H -H -C ₅ H ₁₁ -CH ₃ -H -H 8.57 (dd, 1H), 8.14 (d, 1H), 7.93 (d, 1H), 7.22-7.63 (m, 7H), 2.90 (t, 2H), 2.28 (s, 3H), 1.73-1.79 (m, 2H), 1.38-1.49 (m, 2H), 0.94 (t, 3H). 4 1-38 -NO ₂ -NO ₂ -C ₅ H ₁₁ -CH ₃ -H -H 9.43 (s, 1H), 9.36 (s, 1H), 8.58 (d, 1H), 8.09 (d, 1H), 7.92 (s, 1H), 7.22-7.81 (m, 3H), 2.91 (t, 2H) , 2.30 (s, 3H), 1.70-1.75 (m, 2H), 1.34-1.38 (m, 2H), 0.95 (t, 3H).

For reference, the structure of Comparative Example 3 may be represented by the following Chemical Formula 1-37, and the structure of Comparative Example 4 may be represented by the following Chemical Formula 1-38.

[Formula 1-37]

[Formula 1-38]

Using the optical compounds of Examples 1-33 and Comparative Examples 1-4 prepared above as photopolymerization initiators, and further commercially available commercial products OXE-01 and OXE-02 from BASF as Comparative Examples 5 and 6, respectively, A composition, a black resist composition, was prepared, respectively:

<Transparent resist composition>

13.6 g of dipentaerythritol hexaacrylate, 17-1 compound, Comparative Examples 1-4 compound, 1.5 g of compound of Comparative Example 5, Comparative Example 6, 67 g of propylene glycol monoethyl ether, based on 17 g of acrylic binder resin, and 500 ppm of surfactant (3M, FC-430) was added thereto, followed by stirring to prepare a transparent photosensitive resist composition. Table 9 shows the results of the evaluation of the properties of the respective photopolymerization compositions.

<Black resist composition>

30 g of carbon black, 20 g of titanium black, 13 g of polyester binder resin, 10 g of dipentaerythritol nucleoacrylate, compounds of Examples 1 to 33, compounds of Comparative Examples 1 to 4, Comparative Examples 5 and 6 A black photosensitive resist composition was prepared comprising 2.5 g of compound, 300 g of propylene glycol monoethyl ether, and 500 ppm of surfactant (manufactured by 3M, FC-430). Table 10 shows the results of the evaluation of the properties of each photopolymerization composition.

<Property evaluation>

Evaluation of the obtained transparent photosensitive resist composition was performed as follows.

The photosensitive composition is applied onto a 4 inch round glass and then coated with a spin coater at 800 to 900 rpm for 15 seconds. Dry at 90 ° C. for 100 seconds on a hot plate. After exposure using an ultrahigh pressure mercury lamp as a light source using a photomask, and then developed in a spray type at 25 ℃ 60 seconds in 0.04% potassium hydroxide solution and washed with distilled water.

After washing with water, baking was carried out at 230 ° C. for 40 minutes to obtain a pattern, and the following evaluation was performed on the obtained pattern. Evaluation results using each composition are shown in Tables 9 and 10 and FIG. 1.

(1) adhesion

The coating film obtained by the physical property evaluation was subjected to lattice crosscutting, peeling test was performed with cellophane tape, and the lattice-like peeling state was observed and evaluated. When 100 to 100 cells were not peeled off from 95 to 100, △, 80 to 95 were not peeled off and △, 80 or less were peeled off.

(2) sensitivity evaluation

Each photopolymerized composition was coated on a 4 inch circular glass, spin coated, dried at 100 ° C. for 90 seconds, and then subjected to a transmission mask having 100 cells having different transmittances, and the same exposure amount using an ultrahigh pressure mercury lamp as a light source. After exposure to a 0.04% potassium hydroxide solution was developed in a spray type for 60 seconds at 25 ℃ and washed with distilled water. After the development, the thin film cells remained above 90. ○ After developing, 70 to 90 thin cells remained △, and after developing, the thin film cells remained below 70. The sensitivity of each photopolymerizable composition was evaluated. .

(3) Evaluation of residual film rate

Each photopolymerized composition was coated on a 4 inch round glass, spin-coated, and then dried at 100 ° C. for 90 seconds, using a pattern mask including a pattern of 1 μm to 50 μm, and using an ultra-high pressure mercury lamp as a light source. After exposure to 0.04% potassium hydroxide solution was developed in a spray type for 60 seconds at 25 ℃ and washed with distilled water to form a pattern. The remaining film ratio was evaluated by measuring the film thickness ratio (%) after development compared to before development using a contact thickness meter for the thin film thickness corresponding to the 20 um pattern obtained after development. When thin film thickness ratio is over 90% after development ○, when thin film thickness ratio is 80% ~ 90% after development △, when thin film thickness ratio is less than 80% after development Membrane properties were evaluated.

(4) pattern stability evaluation

Each photopolymerized composition was coated on a 4-inch silicon wafer, spin-coated, and then dried at 100 ° C. for 90 seconds, using a pattern mask including a pattern of 1 μm to 50 μm, and using an ultrahigh pressure mercury lamp as a light source. After exposure to 0.04% potassium hydroxide solution was developed in a spray type for 60 seconds at 25 ℃ and washed with distilled water to form a pattern. The pattern stability evaluation result was shown by cutting from the perpendicular direction of the pattern formed in the silicon wafer, and observing with the electron microscope in the cross-sectional direction of the pattern. When the pattern side wall maintains a taper angle of 50 degrees or more with respect to the substrate and forms a pattern of 10 μm or less, the pattern side wall maintains a taper angle of 50 degrees or more with respect to the substrate, and is 10um to 20um. When the pattern is formed △, the pattern side wall (tape angle less than 50 degrees with respect to the substrate and 20um or more when forming a pattern represented by X to evaluate the pattern stability of the photopolymerization compositions, respectively.

(5) chemical resistance evaluation

Each composition of the photopolymerization composition is coated on a silicon wafer and then coated using a spin coater. Changes in the transmittance and thickness of the resist film after soaking the resist film formed through the process of prebake, exposure, development, postbake, etc. in a stripper solution at 40 ° C. for 10 minutes I looked at it. When the change in transmittance and thickness is less than 2%, the change in transmittance and thickness is 2% to 5%, and when the change in transmittance and thickness is 5% or more, the chemical resistance characteristics of the photopolymerizable compositions are evaluated. It was.

Example No. Sensitivity Pattern stability Chemical resistance Adhesion Residual rate Example 1 ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ○ ○ Example 6 ○ ○ ○ ○ ○ Example 7 ○ ○ ○ ○ ○ Example 8 ○ ○ ○ ○ ○ Example 9 ○ ○ ○ ○ ○ Example 10 ○ ○ ○ ○ ○ Example 11 ○ ○ ○ ○ ○ Example 12 ○ ○ ○ ○ ○ Example 13 ○ ○ ○ ○ ○ Example 14 ○ ○ ○ ○ ○ Example 15 ○ ○ ○ ○ ○ Example 16 ○ ○ ○ ○ ○ Example 17 ○ ○ ○ ○ ○ Example 18 ○ ○ ○ ○ ○ Example 19 ○ ○ ○ ○ ○ Example 20 ○ ○ ○ ○ ○ Example 21 ○ ○ ○ ○ ○ Example 22 ○ ○ ○ ○ ○ Example 23 ○ ○ ○ ○ ○ Example 24 ○ ○ △ ○ ○ Example 25 ○ ○ ○ ○ ○ Example 26 ○ ○ ○ ○ ○ Example 27 ○ ○ △ ○ ○ Example 28 △ ○ △ ○ △ Example 29 △ ○ △ ○ △ Example 30 ○ ○ △ ○ ○ Example 31 ○ ○ ○ ○ ○ Example 32 ○ ○ ○ ○ ○ Example 33 △ ○ △ △ △ Comparative Example 1 X X X X X Comparative Example 2 △ △ △ △ △ Comparative Example 3 X X X X X Comparative Example 4 △ △ X △ △ Comparative Example 5 X △ △ △ △ Comparative Example 6 △ △ ○ △ ○

Example No. Sensitivity Pattern stability Chemical resistance Adhesion Residual rate Example 1 ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ○ ○ Example 6 ○ ○ ○ ○ ○ Example 7 ○ ○ ○ ○ ○ Example 8 ○ ○ ○ ○ ○ Example 9 ○ ○ ○ ○ ○ Example 10 ○ ○ ○ ○ ○ Example 11 ○ ○ ○ ○ ○ Example 12 ○ ○ ○ ○ ○ Example 13 △ ○ ○ ○ ○ Example 14 △ ○ ○ ○ ○ Example 15 △ ○ ○ ○ ○ Example 16 △ ○ ○ ○ ○ Example 17 △ ○ ○ ○ ○ Example 18 △ ○ ○ ○ ○ Example 19 ○ ○ ○ ○ ○ Example 20 ○ ○ △ ○ ○ Example 21 ○ ○ ○ ○ ○ Example 22 ○ ○ ○ ○ ○ Example 23 ○ ○ △ ○ ○ Example 24 ○ ○ △ ○ ○ Example 25 ○ ○ △ ○ ○ Example 26 ○ ○ △ ○ ○ Example 27 △ ○ △ ○ ○ Example 28 △ △ △ △ △ Example 29 ○ △ △ △ △ Example 30 △ ○ △ ○ ○ Example 31 △ ○ △ ○ ○ Example 32 △ ○ △ ○ ○ Example 33 △ △ △ △ △ Comparative Example 1 X X X X X Comparative Example 2 △ X △ △ △ Comparative Example 3 X X X X ○ Comparative Example 4 X △ △ X X Comparative Example 5 X X X △ X Comparative Example 6 △ △ △ △ ○

As shown in Table 9, Table 10 and Figures 1 and 2, the oxime ester compound composed of a carbazole containing a hetero ring according to the present invention is excellent in sensitivity even when used in small amounts when used as a photopolymerization initiator of the photopolymerization composition, It can be seen that the physical properties such as film rate, pattern stability, chemical resistance and adhesiveness are excellent. Therefore, the outgassing generated from the photopolymerization initiator can be minimized in the exposure and post-bake processes in the display resist manufacturing process of TFT-LCD, OLED, TSP, etc., thereby reducing contamination and minimizing the defects that may occur. It can be seen that.

On the other hand, in Comparative Examples 1 and 3 containing no nitro group, not only the residual film ratio was significantly lowered, but also the pattern stability was poor, and in Comparative Examples 2 and 4 containing two nitro groups, the pattern stability compared to high residual film ratio was high. It was confirmed that the residual film ratio, pattern stability, and chemical resistance characteristics were lowered in the case of Comparative Examples 5 and 6, which were not excellent and were also products for sale.

Claims (14)

Oxime ester compound used as photoinitiator in photocrosslinking reaction,
The carbon atom which double bonds with the nitrogen atom of the oxime ester structure is bonded to the hetero carbazole group, and has a structure which is also directly bonded to the (C ₁ -C ₂₀ ) alkyl group or (C ₆ -C ₂₀ ) allyl group, the hetero carba An oxime ester compound consisting of a carbazole comprising a hetero ring in which the sol group is substituted with at least one nitro group. The method of claim 1,
The heterocarbazole group is a monomer having 1) a monocyclic heterocyclic radical and 2) a monomer having a polycyclic heterocyclic N-member radical connected at the nitrogen atom site of the monomer having a 2) polycyclic heterocyclic N-member radical. An oxime ester compound composed of a carbazole containing a hetero ring that is, to form a skeleton. The method of claim 2,
1) The monomer having a monocyclic heterocyclic radical is at least one hetero selected from the group consisting of 2-furyl, 2-thienyl, 4-pyridine, and N- (C ₁ -C ₂ alkyl) -2-pyrroline Oxime ester compound consisting of a carbazole containing a ring. The method of claim 2,
2) The monomer having a polycyclic heterocyclic N-member radical is an oxime ester composed of carbazole including at least one hetero ring selected from the group consisting of chromone, flavone, quinoline, isoquinoline and carbazole. compound. The method of claim 2,
2) the unit having a polycyclic heterocyclic radical

Structure, wherein X is a direct bond, Z is S-, -O-, NR ₇ , -N (C ₁ -C ₂ alkyl) OR ₈ or N (C ₁ -C ₂ alkyl) O (CO) R ₈ ; R ₇ is C ₃ -C ₁₀ alkyl; R ₈ is an oxime ester compound composed of a carbazole comprising a hetero ring which is C ₁ -C ₆ straight alkyl, branched alkyl or cyclic alkyl. The method of claim 1,
The carbazole group including the hetero ring is an oxime ester compound composed of a carbazole including a hetero ring that is substituted with a nitro group. The method of claim 2,
The skeleton is a terminal group by combining with the (alpha-keto) oxime ester group,
The terminal group

Having a structure, n is 0 or 1, R ₁ is C ₁ -C ₁₀ alkyl, C ₁ -C ₃ alkyl substituted phenyl, 2-methylbenzene, C ₁ -C ₆ alkoxy, R ₂ is R ₁ -R _An oxime ester compound consisting of a carbazole comprising a hetero ring which is ₄ alkyl. The method of claim 2,
An oxime ester compound composed of a carbazole comprising a hetero ring in which at least one of the heterocycle and the carbazole group is substituted with a nitro group. Oxime ester compound consisting of a carbazole containing a hetero ring represented by the formula (1):
[Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen, nitro, cyano, alkoxy, halogen, or ester, wherein alkoxy and ester comprise an alkyl group having 1 to 8 carbon atoms, wherein R ₁ and R ₂ are hydrogen Not; R ₃ represents (C ₁ -C ₂₀ ) alkyl, (C ₆ -C ₃₀ ) aryl, (C ₁ -C ₂₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl (C ₁ -C ₂₀ ) alkyl, hydroxy ( C ₁ -C ₂₀ ) alkyl, hydroxy (C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl, (C ₁ -C ₂₀ ) alkylacyl or (C ₆ -C ₂₀ ) arylacyl; R ₄ represents (C ₁ -C ₂₀ ) alkyl, (C ₆ -C ₃₀ ) aryl, (C ₁ -C ₂₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl (C ₁ -C ₂₀ ) alkyl, hydroxy ( C ₁ -C ₂₀ ) alkyl, hydroxy (C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl, (C ₁ -C ₂₀ ) alkylacyl or (C ₆ -C ₃₀ ) arylacyl; R ₅ and R ₆ are each independently hydrogen, nitro, cyano, halogen, (C ₁ -C ₂₀ ) alkyl, (C ₁ -C ₂₀ ) alkoxy, hydroxy (C ₁ -C ₂₀ ) alkyl, hydroxy ( C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₂₀ ) cycloalkyl or (C ₁ -C ₂₀ ) alkylacyl; X is S, O or N and n is an integer of 0 or 1. The method of claim 9,
R ₁ and R ₂ are each independently hydrogen, nitro, cyano, alkoxy, halogen, or ester, and alkoxy and ester include an alkyl group having 1 to 8 carbon atoms, wherein one of R ₁ and R ₂ is nitro,
R ₃ is (C ₁ -C ₂₀ ) alkyl or (C ₆ -C ₃₀ ) aryl,
R ₄ is straight chain (C ₁ -C ₃ ) alkyl, branched (C ₄ -C ₇ ) alkyl or (C ₆ -C ₈ ) aryl,
R ₅ and R ₆ are each independently hydrogen, nitro or methyl, and X is an oxime ester compound consisting of a carbazole comprising a hetero ring which is S or N-CH ₂ CH ₃ . The method of claim 9,
If R ₁ is hydrogen R ₅ is a cover configured sol oxime ester compound which is a nitro or methyl, R ₅ is hydrogen when R ₁ comprises a heterocyclic nitro. A photopolymerization initiator comprising an oxime ester compound composed of carbazoles containing the hetero ring of claim 1. An oxime ester compound composed of carbazole comprising the hetero ring of claim 1; And at least one compound selected from a polymer compound soluble in a solvent or an aqueous alkali solution and a photopolymerizable compound having an ethylenically unsaturated bond; Photopolymer composition comprising a. An oxime ester compound composed of carbazole comprising the hetero ring of claim 1; At least one compound selected from a polymer compound soluble in a solvent or an aqueous alkali solution and a photopolymerizable compound having an ethylenically unsaturated bond; And a colorant or pigment.

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