KR102296796B1 - PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN layer USING THE SAME AND COLOR FILTER - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)A photosensitive resin composition comprising a compound represented by the following Chemical Formula 1, a photosensitive resin film prepared using the photosensitive resin composition, and a color filter including the photosensitive resin film are provided.
[Formula 1]

(In Formula 1, each substituent is as defined in the specification.)

Description

Photosensitive resin composition, photosensitive resin film and color filter using the same

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film using the same, and a color filter.

The liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent adhesion to integrated circuits, and thus its range of use is expanding for notebook computers, monitors, and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, an active circuit portion consisting of a liquid crystal layer, a thin film transistor, and a capacitor layer, and an upper substrate on which the ITO pixel electrode is formed. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between pixels, and a plurality of colors (typically, red (R), green (G), blue (B) to form each pixel. ) in which the three primary colors) are arranged in a predetermined order, the pixel units have a structure in which they are sequentially stacked.

The pigment dispersion method, which is one of the methods for implementing a color filter, involves coating a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposing a pattern of the shape to be formed, and then removing the unexposed area with a solvent. It is a method of forming a colored thin film by repeating a series of thermal curing processes. The colored photosensitive resin composition used for manufacturing a color filter according to the pigment dispersion method consists of a binder resin, a photopolymerization monomer, a photoinitiator, a solvent and other additives, and may further include an epoxy resin. The pigment dispersion method as described above is actively applied to the manufacture of LCDs such as mobile phones, notebook computers, monitors, and TVs.

However, in recent years, even in the photosensitive resin composition for a color filter using the pigment dispersion method, which has various advantages, it is difficult to refine the powder process, and since the dispersion state must be stable in the dispersion liquid even after dispersion, various additives are required, and the process also It is very difficult, and moreover, the pigment dispersion has to maintain the optimum quality, so storage and transportation conditions are difficult. In addition, in the color filter made of the pigment-type photosensitive resin composition, there is a limit in luminance and contrast ratio resulting from the size of the pigment particle.

Accordingly, there is a need to develop dyes having heat resistance and chemical resistance similar to pigments instead of pigments.

One embodiment is to provide a photosensitive resin composition excellent in heat resistance, chemical resistance and pattern processability.

Another embodiment is to provide a photosensitive resin film prepared using the photosensitive resin composition.

Another embodiment is to provide a color filter including the photosensitive resin film.

One embodiment of the present invention provides a photosensitive resin composition comprising a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁶ is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C2 to C20 heteroaryl group, or *-NR ^x R ^y (R ^x and R ^y are each independently a hydrogen atom, a substituted or unsubstituted C1 to 20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group or carboxyl group),

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.

R ⁶ may be any one selected from the group consisting of the following Chemical Formulas 2-1 to 2-8.

[Formula 2-1]

(In Formula 2-1, R ⁷ is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group)

[Formula 2-2]

(In Formula 2-2, R ⁸ to R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-3]

(In Formula 2-3, R ¹¹ and R ¹² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-4]

[Formula 2-5]

(In Formula 2-5, R ¹³ to R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-6]

(In Formula 2-6, R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-7]

(In Formula 2-7, R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-8]

(In Formula 2-8, R ²¹ and R ²² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

The compound represented by Formula 1 may be a dye.

The dye may be a red dye.

The red dye may have a maximum absorbance in a wavelength range of 530 nm to 570 nm.

The photosensitive resin composition may further include an acrylic binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

The acrylic binder resin may have a weight average molecular weight of 5,000 g/mol to 15,000 g/mol.

The acrylic binder resin may have an acid value of 80 mgKOH/g to 130 mgKOH/g.

The compound represented by Formula 1 may be included in an amount of 30 parts by weight to 60 parts by weight based on 100 parts by weight of the acrylic binder resin.

The photosensitive resin composition may include 3 wt% to 20 wt% of an acrylic binder resin based on the total amount of the photosensitive resin composition; 5% to 20% by weight of a photopolymerizable monomer; 1 wt% to 10 wt% of a photopolymerization initiator; It may include 0.9 wt% to 12 wt% of the compound represented by Formula 1 and the remaining amount of the solvent.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; silane-based coupling agent; leveling agent; fluorine-based surfactants; It may further include an additive of a radical polymerization initiator or a combination thereof.

Another embodiment provides a photosensitive resin film prepared using the photosensitive resin composition.

Another embodiment provides a color filter including the photosensitive resin film.

The color filter may be a red color filter.

The specific details of other aspects of the invention are included in the detailed description below.

The photosensitive resin composition according to the exemplary embodiment includes a compound that reacts with the acrylic binder resin only at a temperature above a certain temperature, thereby improving heat resistance and chemical resistance as well as color characteristics and fairness.

1 is a graph showing the transmittance of a compound represented by Formula 3;
Figure 2 is a graph showing the transmittance of the compound represented by the formula (4).
3 is a graph showing the transmittance of the compound represented by Formula 5.
Figure 4 is a graph showing the transmittance of the compound represented by the formula (X).

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified herein, "substituted" to "substituted" means that at least one hydrogen atom in the functional group of the present invention is a halogen atom (F, Cl, Br or I), a hydroxyl group, a nitro group, a cyano group, an amino group ( NH ₂ , NH(R ²⁰⁰ ) or N(R ²⁰¹ )(R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other, and each independently a C1 to C10 alkyl group), an amidino group, A hydrazine group, a hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, And it means substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, specifically means a C1 to C15 alkyl group, and "cycloalkyl group" means a C3 to C20 cycloalkyl group, specifically C3 to C18 cycloalkyl group, "alkoxy group" means a C1 to C20 alkoxy group, specifically means a C1 to C18 alkoxy group, "aryl group" means a C6 to C20 aryl group, specifically C6 to refers to a C18 aryl group, “alkenyl group” refers to a C2 to C20 alkenyl group, specifically refers to a C2 to C18 alkenyl group, and “alkylene group” refers to a C1 to C20 alkylene group, specifically C1 to C18 alkylene group, "arylene group" means C6 to C20 arylene group, specifically, C6 to C16 arylene group.

Unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" is "acrylic acid" and "methacrylic acid" It means both are possible.

Unless otherwise defined herein, "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymerization or random copolymerization.

Unless otherwise defined in the chemical formulas in the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded to the position.

In addition, unless otherwise defined in the present specification, "*" means a moiety connected to the same or different atoms or chemical formulas.

One embodiment provides a photosensitive resin composition comprising a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁶ is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C2 to C20 heteroaryl group, or *-NR ^x R ^y (R ^x and R ^y are each independently a hydrogen atom, a substituted or unsubstituted C1 to 20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group or carboxyl group),

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.

In general, rhodamine dye monomers are weak in heat resistance, chemical resistance, etc., so for the purpose of improving this, the dye is polymerized using an acylation reaction, etc. and used as a colorant in the photosensitive resin composition. However, the polymerized dye has a lower solubility in organic solvents, particularly acetate-like organic solvents, compared to monomer dyes, and aggregation tends to occur. As another method, there are efforts to improve solubility in organic solvents by copolymerizing rhodamine dye monomers with long-chain acrylates such as 2-ethylhexyl acrylate, but this is also rhodamine. Compared to the light dye monomer, the solubility in the raised solvent is lowered and the aggregation phenomenon is also observed.

However, since the photosensitive resin composition according to an embodiment contains the compound represented by Formula 1, it is possible to maintain color reproducibility when manufacturing a color filter pattern while using the conventional process as it is, and has excellent exposure sensitivity and pattern straightness, It has excellent heat resistance and chemical resistance, and can solve surface abnormalities while maintaining luminance characteristics.

For example, in Formula 1, R ⁶ may be any one selected from the group consisting of Formulas 2-1 to 2-8.

[Formula 2-1]

(In Formula 2-1, R ⁷ is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group)

[Formula 2-2]

(In Formula 2-2, R ⁸ to R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-3]

(In Formula 2-3, R ¹¹ and R ¹² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-4]

[Formula 2-5]

(In Formula 2-5, R ¹³ to R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-6]

(In Formula 2-6, R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-7]

(In Formula 2-7, R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

[Formula 2-8]

(In Formula 2-8, R ²¹ and R ²² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)

The compound represented by Formula 1 may be a dye, for example, a red dye.

The compound represented by Formula 1, for example, the red dye may have a maximum absorbance in a wavelength range of 530 nm to 570 nm.

The compound represented by Formula 1 has a structure in which an isocyanate group blocked by a blocking agent is substituted with a rhodamine-based dye. Since the isocyanate group blocked by the blocking agent is dissociated from the isocyanate group and the blocking agent only at a temperature above a certain temperature, heat resistance and chemical resistance can be improved, and thus, it may be suitable for use as a dye as a colorant in the photosensitive resin composition.

Specifically, the compound represented by Formula 1, which is included as a dye in the photosensitive resin composition according to an embodiment, does not dissociate with an isocyanate group and a blocking agent in a color filter process such as pre-baking, exposure, and development, and requires a high temperature post - Only in the baking step, the isocyanate group and the blocking agent are dissociated and react with the hydroxyl group in the binder resin, such as the acrylic binder resin, to improve heat resistance and chemical resistance. However, the isocyanate group exposed by dissociation of the blocking agent reacts with the hydroxyl group in the acrylic binder resin, not the carboxyl group.

On the other hand, the photosensitive resin composition according to an embodiment may further include the acrylic binder resin together with the compound represented by Formula 1, in this case, the compound represented by Formula 1 may be added to 100 parts by weight of the acrylic binder resin. It may be included in an amount of 30 parts by weight to 60 parts by weight. When the compound represented by Formula 1 is included in an amount of less than 30 parts by weight based on 100 parts by weight of the acrylic binder resin, it is disadvantageous to pattern formation, and the compound represented by Formula 1 is 60 parts by weight based on 100 parts by weight of the acrylic binder resin. If included in excess, it is disadvantageous to color realization.

For example, the compound represented by Formula 1 may be included in an amount of 0.9 wt% to 12 wt% based on the total amount of the photosensitive resin composition. When the compound represented by Formula 1 is included within the above range, heat resistance and chemical resistance are improved, and pattern fairness, color reproducibility, luminance and contrast ratio are also excellent.

The compound represented by Formula 1 may be represented by any one of Formulas 3 to 5, but is not limited thereto.

[Formula 3]

[Formula 4]

[Formula 5]

The photosensitive resin composition according to an embodiment may include the compound represented by Formula 1 as a colorant, such as a dye, and further include another colorant, a hydroxyl group-containing binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent. have.

Hereinafter, the components will be described in detail.

Other coloring agent

The photosensitive resin composition according to an embodiment may further include another colorant, such as an organic solvent-soluble dye and/or a pigment, in addition to the compound represented by Formula 1 as a colorant.

Examples of the organic solvent-soluble dye include triarylmethane-based compounds, anthraquinone-based compounds, benzylidene-based compounds, cyanine-based compounds, phthalocyanine-based compounds, azaporphyrin-based compounds, and indigo-based compounds.

The pigment may include a blue pigment, a violet pigment, a red pigment, a green pigment, a yellow pigment, and the like.

Examples of the blue pigment include C.I. Blue pigment 15:6, C.I. Blue pigment 15, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I. Blue pigment 16, C.I. Blue pigment 22, C.I. Blue pigment 60, C.I. Blue pigment 64, C.I. blue pigment 80 or a combination thereof.

Examples of the violet pigment include CI violet pigment 1, CI violet pigment 19, CI violet pigment 23, CI violet pigment 27, CI violet pigment 29, CI violet pigment 30, CI violet pigment 32, CI violet pigment 37, CI violet pigment 40, CI violet pigment 42, CI violet pigment 50, or a combination thereof.

Examples of the red pigment include perylene-based pigments, anthraquinone-based pigments, azo-based pigments, diazo-based pigments, quinacridone-based pigments, and anthracene-based pigments. Specific examples of the red pigment include perylene pigment, quinacridone pigment, naphthol AS, cycomine pigment, anthraquinone (sudan I, II, III, R), vis azo ), benzopyran, and the like.

Examples of the green pigment include halogenated phthalocyanine pigments.

Examples of the yellow pigment include tetra chloro isoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Specifically, hansa yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow (FGL, H10G, HR) etc. are mentioned.

The pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.

The pigment dispersion may include a solid pigment, a solvent, and a dispersing agent for uniformly dispersing the pigment in the solvent.

The solid content of the pigment is 1% to 20% by weight, such as 8% to 20% by weight, such as 8% to 15% by weight, such as 10% to 20% by weight, such as 10% to 20% by weight, based on the total amount of the pigment dispersion. It may be included in 15% by weight.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, and the like may be used. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxyalkylene, polyalcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salts, alkylamide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more.

Examples of commercially available products of the dispersant include BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemicals; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc. from Zeneka; or Ajinomoto's PB711 and PB821.

The dispersant may be included in an amount of 1 wt% to 20 wt% based on the total amount of the pigment dispersion. When the dispersant is included within the above range, it is possible to maintain an appropriate viscosity and thus the photosensitive resin composition has excellent dispersibility, thereby maintaining optical, physical and chemical quality when applying the product.

As a solvent for forming the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol (mono) methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. may be used.

Binder resin containing hydroxyl groups

The hydroxyl group-containing binder resin may be an acrylic binder resin.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin including one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, for example 10 wt% to 40 wt%, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene or vinylbenzylmethyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; Vinyl cyanide compounds, such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; and the like, and these may be used alone or in combination of two or more.

Specific examples of the acrylic binder resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl meth acrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination of two or more. have.

The weight average molecular weight of the acrylic binder resin may be 5,000 g/mol to 15,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition has excellent physical and chemical properties, has an appropriate viscosity, and has excellent adhesion to a substrate when manufacturing a color filter.

The acrylic binder resin may have an acid value of 80 mgKOH/g to 130 mgKOH/g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The acrylic binder resin may be included in an amount of 3 wt% to 20 wt%, for example 5 wt% to 15 wt%, based on the total amount of the photosensitive resin composition. When the acrylic binder resin is included within the above range, excellent developability and improved crosslinking properties can be obtained when manufacturing a color filter, thereby obtaining excellent surface smoothness.

photopolymerization monomer

The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, it is possible to form a pattern excellent in heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the photopolymerizable monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylic rate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylol propane tri (meth) ) acrylate, tris (meth) acryloyloxyethyl phosphate, and novolac epoxy (meth) acrylate.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth)acrylic acid include Aronix M-101 ^® , M-111 ^® , M-114 ^® by Toagosei Chemical Co., Ltd.; Nihon Kayaku Co., Ltd.'s KAYARAD TC-110S ^® , Copper TC-120S ^®, etc.; ^{V-158 ®} and V-2311 ^{® of} Osaka Yuki Chemical High School Co., Ltd. are mentioned. Examples of the bifunctional ester of (meth)acrylic acid, Toagosei Chemical Co., Ltd. Aronix M-210 ^® , copper M-240 ^® , copper M-6200 ^® and the like; Nihon Kayaku Co., Ltd.'s KAYARAD HDDA ^® , Copper HX-220 ^® , Copper R-604 ^®, etc.; ^{and V-260 ®} , V-312 ^® , V-335 HP ^{® of} Osaka Yuki Chemical High School Co., Ltd. and the like. Examples of the trifunctional ester of (meth)acrylic acid, Toagosei Chemical Co., Ltd. Aronix M-309 ^® , Copper M-400 ^® , Copper M-405 ^® , Copper M-450 ^® , Copper M -710 ^® , copper M-8030 ^® , copper M-8060 ^® etc; Nihon Kayaku Co., Ltd.'s KAYARAD TMPTA ^® , Copper DPCA-20 ^® , Copper-30 ^® , Copper-60 ^® , Copper-120 ^® etc.; ^{V-295 ®} , Dong-300 ^® , Dong-360 ^® , Dong-GPT ^® , Dong-3PA ^® , Dong-400 ^® etc. from Osaka Yuki Kayaku High School Co., Ltd. are mentioned. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating it with an acid anhydride in order to provide better developability.

The photopolymerizable monomer may be included in an amount of 5 wt% to 20 wt%, for example 10 wt% to 15 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, curing occurs sufficiently during exposure in the pattern forming process to provide excellent reliability and excellent developability in an alkaline developer.

light curing initiator

The photopolymerization initiator is an initiator generally used in the photosensitive resin composition, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, an oxime-based compound, or a combination thereof.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc. are mentioned.

Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis (trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc. are mentioned.

Examples of the oxime-based compound include an O-acyloxime-based compound, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, and 1-(o-acetyloxime). )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one etc. can be used. Specific examples of the O-acyloxime compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione -2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime- O-acetate etc. are mentioned.

As the photopolymerization initiator, a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, or a biimidazole-based compound may be used in addition to the above compound.

The photopolymerization initiator may be included in an amount of 1 wt% to 10 wt%, for example 1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization may occur sufficiently during exposure in the pattern forming process, and a decrease in transmittance due to the unreacted initiator may be prevented.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light to enter an excited state and then transferring the energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like. can be heard

menstruum

As the solvent, other colorants represented by Formula 1, a binder resin containing a hydroxyl group, a photopolymerizable compound, and a material that does not react with the photopolymerization initiator may be used.

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters, such as 3-oxy methyl propionate and 3-oxy ethyl propionate; 3-alkoxy propionic acid alkyl esters, such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxy propionic acid alkyl esters, such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionic acid esters such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate; 2-methoxy-2-methyl methyl propionate; 2-ethoxy-2- monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl propionate alkyls such as ethyl methyl propionate; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethyl hydroxyacetate, and 2-hydroxy-3-methyl methyl butanoate; Ketonic acid esters such as ethyl pyruvate, and the like, and N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid and high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, in consideration of compatibility and reactivity, glycol ethers, such as ethylene glycol monoethyl ether, are preferable; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included in a balance, for example, 40 wt% to 95 wt%, such as 50 wt% to 92 wt%, such as 50 wt% to 90 wt%, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition may have excellent applicability and maintain excellent flatness.

other additives

The photosensitive resin composition according to an embodiment includes malonic acid; 3-amino-1,2-propanediol; silane-based coupling agent; leveling agent; fluorine-based surfactants; A radical polymerization initiator or a combination thereof may be further included.

For example, the photosensitive resin composition may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, and an epoxy group in order to improve adhesion to the substrate.

Examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycan Cydoxy propyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. are mentioned, and these can be used individually or in mixture of 2 or more types.

The silane-based coupling agent may be included in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane-based coupling agent is included within the above range, adhesion and storage properties are excellent.

In addition, the photosensitive resin composition may further include a surfactant, such as a fluorine-based surfactant, to improve coating properties and prevent defect formation, if necessary.

Examples of the fluorine-based surfactant include BM-1000 ^® , BM-1100 ^® and the like by BM Chemie; ^{Mecha Pack F 142D ®} , F 172 ^® , F 173 ^® , F 183 ^® etc. manufactured by Dai Nippon Inky Chemical Co., Ltd.; Sumitomo 3M Co., Ltd.'s Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc.; Asahi Grass Co., Ltd.'s Saffron S-112 ^® , Copper S-113 ^® , Copper S-131 ^® , Copper S-141 ^® , Copper S-145 ^®, etc.; ^{SH-28PA ®} , Copper-190 ^® , Copper ^{-193 ®} , SZ-6032 ^® , SF-8428 ^®, etc. of Toray Silicone Co., Ltd.; F-482, F-484, F-478, F-554 commercially available fluorine-based surfactants of DIC Co., Ltd. may be used.

The fluorine-based surfactant may be used in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the fluorine-based surfactant is included within the above range, coating uniformity is ensured, stains do not occur, and wettability to a glass substrate is excellent.

In addition, a predetermined amount of other additives such as antioxidants and stabilizers may be further added to the photosensitive resin composition within a range that does not impair physical properties.

The photosensitive resin composition according to an embodiment may further include an epoxy compound to improve adhesion with the substrate.

Examples of the epoxy compound include a phenol novolac epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol A-type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be included in an amount of 0.01 parts by weight to 20 parts by weight, for example, 0.1 parts by weight to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included within the above range, adhesion and storage properties are excellent.

According to another embodiment, there is provided a photosensitive resin film prepared by using the photosensitive resin composition.

According to another embodiment, there is provided a color filter including the photosensitive resin film.

The color filter may be a red color filter.

The pattern forming process in the color filter is as follows.

applying the photosensitive resin composition onto a support substrate by spin coating, slit coating, inkjet printing, or the like; drying the applied photosensitive resin composition to form a photosensitive resin composition film; exposing the photosensitive resin composition film; developing the exposed photosensitive resin composition film with an aqueous alkali solution to prepare a photosensitive resin film; and heat-treating the photosensitive resin film. Since the process conditions and the like are well known in the art, detailed descriptions thereof will be omitted herein.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.

(synthesis of compounds)

Synthesis example 1: Synthesis of the compound represented by Formula 3

735 ml of methylene chloride was added to a flask with a stirrer, and after cooling to 0° C. under a nitrogen stream, 85 g (147 mmol) of Sulforhodamine B acid chloride was added thereto and stirred. Then, 29.2 g (177 mmol) of 2-aminoethyl methacrylate hydrochloride, 0.899 g (7.37 mmol) of N,N-dimethylamino pyridine, and 38.3 g (53 ml, 295 mmol) of triethyl amine were further added. and stirred at room temperature for 15 hours. After that, 15 g of 3,5-Dimethyl Pyrazole (DMP) was added and stirred at 80° C. for 3 hours. Thereafter, the mixture was concentrated under reduced pressure using a rotary evaporator, and the obtained red solid was washed with ethyl acetate to obtain a solid of 65.9 g (yield 67%) of the compound represented by the following Chemical Formula 3.

[Formula 3]

[NMR data]

¹ H NMR (300 MHz, CD ₃ OD) δ = 8.00 (s, 1H), 7.88 (d, 2H), 7.58-6.02 (m, 10H), 4.7 (t, 1H), 2.47-2.43 (m, 9H) , 1.90-1.85 (m, 12H)

Synthesis example 2: Synthesis of the compound represented by Formula 4

735 ml of methylene chloride was added to a flask with a stirrer, and after cooling to 0° C. under a nitrogen stream, 85 g (147 mmol) of Sulforhodamine B acid chloride was added and stirred. After that, 29.2 g (177 mmol) of 2-aminoethyl methacrylate hydrochloride, 0.899 g (7.37 mmol) of N,N-dimethylamino pyridine, and 38.3 g (53 ml, 295 mmol) of triethyl amine were further added. and stirred at room temperature for 15 hours. After that, 14 g of 1,3,5-trimethyl-1H-[1,2,4]triazole was added and stirred at 80° C. for 3 hours. Thereafter, the mixture was concentrated under reduced pressure using a rotary evaporator, and the obtained red solid was washed with ethyl acetate to obtain a solid of 65.9 g (yield 66%) of the compound represented by the following Chemical Formula 4.

[Formula 4]

[NMR data]

¹ H NMR (300 MHz, CD ₃ OD): δ = 7.78 (s, 3H), 7.58-6.01 (m, 7H), 4.70-2.47 (m, 5H), 1.90-1.85 (m, 9H), 1.25 (m) , 12H)

Synthesis example 3: Synthesis of the compound represented by Formula 5

735 ml of methylene chloride was added to a flask with a stirrer, and after cooling to 0° C. under a nitrogen stream, 85 g (147 mmol) of Sulforhodamine B acid chloride was added and stirred. After that, 29.2 g (177 mmol) of 2-aminoethyl methacrylate hydrochloride, 0.899 g (7.37 mmol) of N,N-dimethylamino pyridine, and 38.3 g (53 ml, 295 mmol) of triethyl amine were further added. and stirred at room temperature for 15 hours. After adding 17 g of diisopropyl-methyl-amine, the mixture was stirred at 80° C. for 3 hours. Thereafter, the mixture was concentrated under reduced pressure using a rotary evaporator, and the obtained red solid was washed with ethyl acetate to obtain a solid of 65.9 g (yield 66%) of the compound represented by the following Chemical Formula 5.

[Formula 5]

[NMR data]

H NMR (300 MHz, CDOD): δ = 8.00 (s, 1H), 7.88 (s, 2H), 7.58-6.01 (m, 8H), 5.71-5.20 (m, 3H), 4.70-2.35 (m, 10H) ,1.90-1.85(m, 12H),1.25(m, 12H)

comparison Synthesis example 1: Synthesis of Formula X

735 ml of methylene chloride was added to a flask with a stirrer, and after cooling to 0° C. under a nitrogen stream, 85 g (147 mmol) of Sulforhodamine B acid chloride was added and stirred. After that, 16.1 g (177 mmol) of serinol, 0.899 g (7.37 mmol) of N,N-dimethylamino pyridine, and 38.3 g (53 ml, 295 mmol) of triethylamine were further added, followed by stirring at room temperature for 15 hours. Thereafter, the mixture was concentrated under reduced pressure using a rotary evaporator, and the obtained red solid was washed with ethyl acetate to obtain a solid of 70.15 g (yield 69%) of the compound represented by the following Chemical Formula X.

[Formula X]

[NMR data]

¹ H NMR (300 MHz, CD ₃ OD): δ = 8.67 (s, 1H), 8.16 (d, 1H), 7.58 (d, 1H), 7.13-6.92 (m, 6H), 4.2 (t, 1H), 3.73-3.66(m, 8H), 3.50-2.95(m, 5H), 1.42-1.17(m, 12H)

Evaluation 1: Determination of solubility

0.5 g of the compound of Synthesis Examples 1 to 3, the compound of Comparative Synthesis Example 1, and WAKO's rhodamine-based dye (RCP-19) were added to a dilution solvent (PGMEA, Anone), respectively, and the solution was mixed After stirring for 1 hour at 25°C and 100 rpm with a rotor (MIXROTAR VMR-5 manufactured by Iuchi Corporation), the results of confirming the dissolved state (dissolved compound content) of the compound are shown in Table 1 below.

(Unit: % by weight) dissolved compound content PGMEA Anone Synthesis Example 1 10% 15% Synthesis Example 2 11% 16% Synthesis Example 3 9% 14% Comparative Synthesis Example 1 2% 4% RCP-19 5% 8%

Evaluation 2: Permeability Measurement

A solution diluted to a concentration of 0.001 wt% of each of the compounds of Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 using cyclohexanol in a quartz cell with a thickness of 10.00mm UV/VIS Spectrophotometer:UV -1800 (SHIMADZU Co., Ltd.) was used to measure the absorbance in a wavelength region between 200 nm and 800 nm, and the results are shown in FIGS. 1 to 4 .

It can be seen from Table 1 and FIGS. 1 to 4 that all of the compounds according to the embodiment have excellent solubility and spectral properties in organic solvents.

(Synthesis of photosensitive resin composition)

Example 1 to Example 3, comparative example One, comparative example 2, Reference example 1 and Reference example 2

The photosensitive resin compositions according to Examples 1 to 3, Comparative Example 1, Comparative Example 2, Reference Example 1 and Reference Example 2 were prepared by mixing the components mentioned below in the composition shown in Table 2 below.

Specifically, a photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours, then an acrylic binder resin and a photopolymerizable monomer were added thereto and stirred at room temperature for 2 hours. Then, a fluorine-based surfactant and a silane-based coupling agent were added to the obtained reaction product together with the compound prepared in Synthesis Example, and the mixture was stirred at room temperature for 1 hour. Then, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(A) Colorant

(A-1) Compound of Synthesis Example 1

(A-2) Compound of Synthesis Example 2

(A-3) Compound of Synthesis Example 3

(A-4) Compound of Comparative Synthesis Example 1

(A-5) Rhodamine dye (RCP-19, WAKO)

(B) binder resin

Acrylic binder resin (SM-CRB-400H, SMS company)

(C) photopolymerization monomer

Dipentaerythritol hexaacrylate (Nippon Kayaku Co.)

(D) light curing initiator

Oxime initiator (PBG-305, Tronyl)

(E) solvent

Propylene glycol monomethyl ether acetate (PGMEA)

(F) other additives

(F-1) Fluorine surfactant (F-554, DIC Corporation)

(F-2) γ-glycidoxy propyl trimethoxysilane (S-510, Chisso)

(Unit: % by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Reference Example 1 Reference Example 2 coloring agent (A-1) 5 - - - - 2.5 6 (A-2) - 5 - - - - - (A-3) - - 5 - - - - (A-4) - - - 5 - - - (A-5) - - - - 5 - - binder resin 9 9 9 9 9 9 9 photopolymerizable monomer 13 13 13 13 13 13 13 photopolymerization initiator 4 4 4 4 4 4 4 menstruum 68.7 68.7 68.7 68.7 68.7 71.2 67.7 other additives (F-1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (F-2) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Evaluation 3: Evaluation of color characteristics

The photosensitive resin compositions prepared in Examples 1 to 3, Comparative Examples 1, 2, Reference Example 1 and Reference Example 2 were prepared in a thickness of 1 μm to 3 μm on a degreasing-washed glass substrate having a thickness of 1 mm. It was applied and dried (pre-baked) for 2 minutes on a hot plate at 90° C. to obtain a coating film. Subsequently, the entire surface of the coating film was exposed using a high-pressure mercury lamp (exposure conditions: 50 mJ/cm ² ). Thereafter, the sample was obtained by drying (post-baking) for 30 minutes in a hot air circulation drying furnace at 230°C. The pixel layer was subjected to color measurement (color coordinates and luminance measurement) using a spectrophotometer (MCPD3000, Otsuka electronic), and the results are shown in Table 3 below. In addition, the heat resistance was evaluated by calculating the color coordinate change value before and after post-baking, and the obtained sample was immersed in N-methylpyrrolidone (NMP) for 10 minutes at room temperature, taken out, dried, and tested using a colorimeter. The chemical resistance was evaluated by converting the color difference before and after into del(E*), and the results are shown in Table 4 below. (The del(E*) value shows a color change compared to the initial after heat resistance. Usually, if it has a value of 3.0 or higher, it is evaluated as inferior in heat resistance and chemical resistance.)

Step Rx Ry Luminance (Y) del(E*) Example 1 Before post-baking 0.6682 0.3228 17.79 - After post-baking 0.6682 0.3227 17.59 0.42 Example 2 Before post-baking 0.6682 0.3228 17.79 - After post-baking 0.6682 0.3226 17.58 0.43 Example 3 Before post-baking 0.6682 0.3228 17.79 - After post-baking 0.6682 0.3228 17.61 0.42 Comparative Example 1 Before post-baking 0.6682 0.3230 17.79 - After post-baking 0.6682 0.3221 17.40 3.45 Comparative Example 2 Before post-baking 0.6682 0.3228 17.79 - After post-baking 0.6682 0.3222 17.42 3.79 Reference Example 1 Before post-baking 0.6682 0.3228 17.79 - After post-baking 0.6682 0.3226 17.58 0.36 Reference Example 2 Before post-baking 0.6682 0.3228 17.79 - After post-baking 0.6682 0.3225 17.54 1.68

chemical resistance heat resistance Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Comparative Example 1 × × Comparative Example 2 × × Reference Example 1 ○ ○ Reference Example 2 △ △

Heat resistance and chemical resistance were based on the following evaluation criteria.

○: del(E*) of color before and after oven is less than 1.5

△: before and after oven color del(E*) is 1.5 or more and less than 3.0

×: del(E*) of the color before and after the oven is 3.0 or more

Evaluation 4: Pattern Fairness Evaluation

The photosensitive resin compositions prepared in Examples 1 to 3, Comparative Examples 1, 2, Reference Example 1 and Reference Example 2 were prepared in a thickness of 1 μm to 3 μm on a degreasing-washed glass substrate having a thickness of 1 mm. It was applied and dried (pre-baked) for 2 minutes on a hot plate at 90° C. to obtain a coating film. Subsequently, the entire surface of the coating film was exposed using a high-pressure mercury lamp (exposure conditions: 50 mJ/cm ² ). After this, development was performed to show the pattern. The developer was used by diluting the KOH solution of Hoemyeong Corporation, and the time (BP) at which the pattern appeared was measured. In this case, the BP must be at least 43 seconds or less for compatibility.

The developed pattern substrate was dried (post-baked) for 30 minutes in a hot air circulation drying furnace at 230° C. to obtain a sample, which was optically zoomed 500 times through an optical microscope to evaluate the pattern fairness, and the results are shown in the table below 5 is shown. Whether or not the pattern was torn was evaluated by dividing the degree to which the pattern was torn when observed through an optical microscope according to the following criteria.

○: good pattern border and adhesion

△: occurrence of tearing of the pattern edge

x: pattern peeling occurs

50 mJ/cm ² BP (seconds) Whether the pattern is torn (adhesion) CD (Critical dimension)
(Standard: 70 μm) Hole
(Standard: 40 μm) Example 1 77.3 31.9 26 ○ Example 2 77.2 31.8 26 ○ Example 3 77.1 31.9 26 ○ Comparative Example 1 76.6 32.8 21 △ Comparative Example 2 76.1 33.1 23 △ Reference Example 1 77.4 31.8 25 ○ Reference Example 2 77.0 32.8 21 △

From Tables 3 to 5, the photosensitive resin compositions of Examples 1 to 3, Reference Example 1 and Reference Example 2 containing the compound represented by Formula 1 as a colorant include the compound represented by Formula 1 as a colorant. It can be confirmed that color characteristics, heat resistance, chemical resistance and pattern processability are superior to those of the photosensitive resin compositions of Comparative Examples 1 and 2 that are not included. In addition, when the compound represented by Formula 1 is included in an amount of 30 parts by weight to 60 parts by weight based on 100 parts by weight of the acrylic binder resin, it can be confirmed that color characteristics, heat resistance, chemical resistance and pattern fairness are better than those otherwise. can

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the appended claims, the detailed description of the invention, and the accompanying drawings. It goes without saying that it falls within the scope of the invention.

Claims (14)

A photosensitive resin composition comprising a compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ¹ to R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ⁶ is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C2 to C20 heteroaryl group, or *-NR ^x R ^y (R ^x and R ^y are each independently a hydrogen atom, a substituted or unsubstituted C1 to 20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group or carboxyl group),
L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.
(In the above, "substituted" to "substituted" means that at least one hydrogen atom in a functional group is a halogen atom (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, an amino group (NH ₂ , NH(R ²⁰⁰ ) or N(R ²⁰¹ )(R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other and are each independently a C1 to C10 alkyl group), amidino group, hydrazine group, hydrazone group, carboxyl group, means substituted with one or more substituents selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alicyclic organic group, an aryl group, and a heterocyclic group)
According to claim 1,
The R ⁶ is any one selected from the group consisting of Chemical Formulas 2-1 to 2-8, the photosensitive resin composition.
[Formula 2-1]

(In Formula 2-1, R ⁷ is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group)
[Formula 2-2]

(In Formula 2-2, R ⁸ to R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)
[Formula 2-3]

(In Formula 2-3, R ¹¹ and R ¹² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)
[Formula 2-4]

[Formula 2-5]

(In Formula 2-5, R ¹³ to R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)
[Formula 2-6]

(In Formula 2-6, R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)
[Formula 2-7]

(In Formula 2-7, R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)
[Formula 2-8]

(In Formula 2-8, R ²¹ and R ²² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group)
(In the above, "substituted" to "substituted" means that at least one hydrogen atom in a functional group is a halogen atom (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, an amino group (NH ₂ , NH(R ²⁰⁰ ) or N(R ²⁰¹ )(R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other and are each independently a C1 to C10 alkyl group), amidino group, hydrazine group, hydrazone group, carboxyl group, means substituted with one or more substituents selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alicyclic organic group, an aryl group, and a heterocyclic group)
According to claim 1,
A photosensitive resin composition wherein the compound represented by Formula 1 is a dye.
4. The method of claim 3,
The dye is a red dye photosensitive resin composition.
5. The method of claim 4,
The red dye is a photosensitive resin composition having a maximum absorbance in a wavelength range of 530 nm to 570 nm.
According to claim 1,
The photosensitive resin composition further comprises an acrylic binder resin, a photopolymerizable monomer, a photoinitiator, and a solvent.
7. The method of claim 6,
The acrylic binder resin is a photosensitive resin composition having a weight average molecular weight of 5,000 g / mol to 15,000 g / mol.
7. The method of claim 6,
The acrylic binder resin is a photosensitive resin composition having an acid value of 80 mgKOH / g to 130 mgKOH / g.
7. The method of claim 6,
The compound represented by Formula 1 is included in an amount of 30 parts by weight to 60 parts by weight based on 100 parts by weight of the acrylic binder resin.
7. The method of claim 6,
The said photosensitive resin composition with respect to the said photosensitive resin composition total amount
3 wt% to 20 wt% of an acrylic binder resin;
5% to 20% by weight of a photopolymerizable monomer;
1 wt% to 10 wt% of a photopolymerization initiator;
0.9 wt% to 12 wt% of the compound represented by Formula 1, and
50% to 90% by weight solvent
A photosensitive resin composition comprising a.
7. The method of claim 6,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; silane-based coupling agent; leveling agent; fluorine-based surfactants; The photosensitive resin composition further comprising an additive of a radical polymerization initiator or a combination thereof.
The photosensitive resin film produced using the photosensitive resin composition of any one of Claims 1-11.
A color filter comprising the photosensitive resin film of claim 12 .
14. The method of claim 13,
The color filter is a red color filter.

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