KR102204707B1 - 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) binder resin; (B) a colorant containing a dye and a pigment represented by the following formula (1); (C) a photopolymerizable compound; (D) a photosensitive resin composition comprising a photopolymerization initiator and (E) a solvent, and the colorant is contained in an amount of 30% to 50% by weight based on the total amount of the photosensitive resin composition, a photosensitive resin film prepared using the photosensitive resin composition, and A color filter including this is provided.
[Formula 1]

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

Description

Photosensitive resin composition, photosensitive resin film and color filter manufactured using the same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME AND COLOR FILTER}

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

A liquid crystal display device, which is one of the display devices, has advantages such as weight reduction, thinness, low cost, low power consumption, and excellent integration with 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 unit composed of a liquid crystal layer, a thin film transistor, and a capacitor layer, and an upper substrate on which an ITO pixel electrode is formed.

The color filter is a black matrix layer formed in a predetermined pattern on a transparent substrate to block the boundary between pixels, and a plurality of colors (typically, red (R), green (G), blue (B)) to form each pixel. The three primary colors of) are sequentially stacked in a fixed order. One of the methods of implementing a color filter, the pigment dispersion method, is to coat a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. , After exposing the pattern of the shape to be formed, a colored thin film is formed by repeating a series of processes of thermally curing by removing the non-exposed part with a solvent, thereby forming a colored photosensitive resin used in manufacturing a color filter according to the pigment dispersion method. The composition is generally composed of an alkali-soluble resin, a photopolymerization monomer, a photopolymerization initiator, an epoxy resin, a solvent and other additives, etc. The pigment dispersion method having the above characteristics is actively used to manufacture LCDs such as mobile phones, notebook computers, monitors, and TVs. However, in recent years, a photosensitive resin composition for a color filter using a pigment dispersion method having various advantages is required not only to have excellent pattern characteristics but also to further improved performance, especially of high brightness and high contrast ratio along with high color reproducibility. Characteristics are urgently required.

In a color filter made of a pigment-type photosensitive resin composition, there is a limit to the brightness and contrast ratio resulting from the pigment particle size. In addition, in the case of a color image sensor for an image sensor, a smaller dispersion particle size is required to form a fine pattern. In order to meet such demands, attempts to implement a color filter having improved color characteristics such as brightness and contrast ratio by preparing a photosensitive resin composition in which a dye that does not form particles is introduced instead of a pigment is continued.

Therefore, research on a compound suitable as a dye used in the production of a photosensitive resin composition and a photosensitive resin composition including the same is being continued.

One embodiment is to provide a photosensitive resin composition having excellent coloring power, transmittance, and contrast ratio.

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

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

One embodiment of the present invention is (A) a binder resin; (B) a colorant containing a dye and a pigment represented by the following formula (1); (C) a photopolymerizable compound; A photosensitive resin composition comprising (D) a photoinitiator and a solvent (E), wherein the colorant is contained in an amount of 30% to 50% by weight based on the total amount of the photosensitive resin composition is provided.

[Formula 1]

In Formula 1,

R ¹ to R ¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted A ringed C6 to C20 aryloxy group,

However, at least one of R ¹ to R ¹² is represented by the following Formula 2, and R ¹³ to R ¹⁶ are each independently a hydrogen atom or a halogen atom,

[Formula 2]

In Chemical Formula 2,

R ¹⁷ is a substituted or unsubstituted C3 to C20 cycloalkyl group.

The colorant may be included in an amount of 40% to 50% by weight based on the total amount of the photosensitive resin composition.

The dye content in the colorant may be less than the pigment content in the colorant.

Formula 2 may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ¹⁷ is a substituted or unsubstituted C3 to C20 cycloalkyl group.

Each of R ¹³ to R ¹⁶ may independently be a halogen atom.

At least two of R ¹ to R ¹² may be represented by Formula 2.

At least three of R ¹ to R ¹² may be represented by Formula 2.

At least one of R ¹ to R ⁴ is represented by Formula 2, at least one of R ⁵ to R ⁸ is represented by Formula 2, and at least one of R ⁹ to R ¹² is represented by Formula 2 I can.

All of R ¹³ to R ¹⁶ may be halogen atoms.

One of R ¹ to R ⁴ is represented by Formula 2, the other three are halogen atoms, one of R ⁵ to R ⁸ is represented by Formula 2, the other three are halogen atoms, and R ⁹ to One of R ¹² may be represented by Formula 2, and the other three may be halogen atoms.

The compound represented by Formula 1 may be represented by any one of Formulas 4 to 9 below.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

The compound represented by Formula 1 may be a green dye.

The green dye may have a maximum transmittance in a wavelength range of 445 nm to 560 nm.

The green dye may have a maximum absorbance in a wavelength range of 600 nm to 730 nm.

The pigment may include a green pigment and a yellow pigment.

The green pigment is a green pigment C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62 or combinations thereof.

The yellow pigment is C.I. Pigment Yellow 11, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 167, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 199, C.I. Pigment Yellow 215, C.I. Pigment Yellow 231 or combinations thereof.

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, the (A) binder resin 1% by weight to 10% by weight; 30% to 50% by weight of the colorant (B); 1% to 10% by weight of the (C) photopolymerizable compound; The (D) photopolymerization initiator may contain 0.1% to 5% by weight and 25% to 50% by weight of the (E) solvent.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; Leveling agents; Fluorine-based surfactant; And it may further include at least one additive selected from the radical polymerization initiator.

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

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

Other specifics of aspects of the present invention are included in the detailed description below.

The photosensitive resin composition according to an embodiment may provide a color filter having excellent luminance and reliability with respect to an organic solvent.

1 is a graph showing transmittance of dyes used in Example 3 and Comparative Example 1 according to wavelength.

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

Unless otherwise specified in the specification, "substituted" to "substituted" means that at least one hydrogen atom in the functional groups of the present invention is a halogen atom (F, Br, Cl 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 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 substituted or unsubstituted heterocyclic groups.

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

Unless otherwise specified in the specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" means "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 copolymer or random copolymer.

Unless otherwise defined in the chemical formula 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 at the position.

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

One embodiment is (A) a binder resin; (B) a colorant containing a dye and a pigment represented by the following formula (1); (C) a photopolymerizable compound; A photosensitive resin composition comprising (D) a photoinitiator and a solvent (E), wherein the colorant is contained in an amount of 30% to 50% by weight based on the total amount of the photosensitive resin composition is provided.

[Formula 1]

In Formula 1,

R ¹ to R ¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted A ringed C6 to C20 aryloxy group,

However, at least one of R ¹ to R ¹² is represented by the following Formula 2, and R ¹³ to R ¹⁶ are each independently a hydrogen atom or a halogen atom,

[Formula 2]

In Chemical Formula 2,

R ¹⁷ is a substituted or unsubstituted C3 to C20 cycloalkyl group.

The phthalocyanine-based dye represented by Chemical Formula 1 has excellent green spectral properties and a high molar absorption coefficient. Furthermore, since the dye represented by Formula 1 necessarily contains the substituent represented by Formula 2, it has excellent reliability, that is, chemical resistance, to an organic solvent.

In addition, the dye represented by Chemical Formula 1 is used together with a green pigment dispersion and a yellow pigment dispersion, so that more excellent high color coordinates can be realized, and additional luminance can be improved when implementing high color coordinates than conventional phthalocyanine dyes.

Hereinafter, each component will be described in detail.

(B) colorant

The colorant includes a dye and a pigment represented by Formula 1, and the dye represented by Formula 1 necessarily includes a substituent represented by Formula 2. However, the substituent represented by Formula 2 is not present at the positions of R ¹³ to R ¹⁶ in Formula 1. That is, in Formula 1, at least one of R ¹ to R ¹² is represented by the following Formula 2, and R ¹³ to R ¹⁶ are each independently a hydrogen atom or a halogen atom. For example, in Formula 1, at least one of R ¹ to R ⁴ , at least one of R ⁵ to R ⁸ , at least one of R ⁹ to R ¹² , and at least one of R ¹³ to R ¹⁶ are each independently represented by Formula 2 When displayed, the effect of improving luminance is inferior when implementing high color coordinates, and heat resistance and chemical resistance are also not excellent.

Formula 2 may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ¹⁷ is a substituted or unsubstituted C3 to C20 cycloalkyl group.

The substituent represented by Formula 3 is a 2-cyclohexylphenol group, and when the cyclohexyl group is substituted at the ortho position, than when the cyclohexyl group is substituted at the meta or para position, When implementing high color coordinates, the effect of improving luminance can be maximized, and heat resistance and chemical resistance can also be improved at the same time.

Each of R ¹³ to R ¹⁶ may independently be a halogen atom. When all of R ¹³ to R ¹⁶ are halogen atoms than the case where R ¹³ to R ¹⁶ are all hydrogen atoms, the effect of improving luminance, heat resistance and chemical resistance is greater.

For example, at least two of R ¹ to R ¹² may be represented by Formula 2.

For example, at least three of R ¹ to R ¹² may be represented by Formula 2.

For example, at least one of R ¹ to R ⁴ is represented by Formula 2, at least one of R ⁵ to R ⁸ is represented by Formula 2, and at least one of R ⁹ to R ¹² is represented by Formula 2 Can be displayed.

For example, at least one of R ¹ to R ⁴ is represented by Formula 2, at least one of R ⁵ to R ⁸ is represented by Formula 2, and at least one of R ⁹ to R ¹² is represented by Formula 2 And all of R ¹³ to R ¹⁶ may be halogen atoms.

For example, one of R ¹ to R ⁴ is represented by Formula 2, the remaining three are halogen atoms, one of R ⁵ to R ⁸ is represented by Formula 2, the other three are halogen atoms, and R One of ⁹ to R ¹² may be represented by Formula 2, and the other three may be halogen atoms.

For example, one of R ¹ to R ⁴ is represented by Formula 2, the remaining three are halogen atoms, one of R ⁵ to R ⁸ is represented by Formula 2, the other three are halogen atoms, and R One of ⁹ to R ¹² may be represented by Formula 2, the other three may be halogen atoms, and all of R ¹³ to R ¹⁶ may be halogen atoms.

For example, the compound represented by Formula 1 may be represented by any one of Formulas 4 to 9, but is not limited thereto.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

Since the dye represented by Formula 1 contains a substituent represented by Formula 2, for example, Formula 3, high color can be expressed even in a small amount, and thus a display device having excellent color characteristics such as luminance can be manufactured. For example, the dye represented by Formula 1 may be, for example, a green dye, for example, a dye having a maximum transmittance in a wavelength range of 445 nm to 560 nm. In addition, the green dye may be a dye having a maximum absorbance in a wavelength range of 600 nm to 730 nm.

That is, since the green dye has a maximum transmittance in a wavelength range of 445 nm to 560 nm and a maximum absorbance in a wavelength range of 600 nm to 730 nm, the green dye is used as a colorant together with a green pigment dispersion and a yellow pigment dispersion. , It is possible to implement high color coordinates with improved reliability, including coloring power, luminance characteristics and chemical resistance. For example, the colorant may be included in an amount of 30% to 50% by weight, such as 40% to 50% by weight, based on the total amount of the photosensitive resin composition. When the colorant is included in the content range, improved shelf-life can be secured when implementing high color coordinates. In particular, when the content of the dye in the colorant is less than the content of the pigment in the colorant, the shelf-life can be greatly improved when implementing high color coordinates.

The pigment may include a green pigment and a yellow pigment.

The green pigment is a green pigment C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62 or combinations thereof.

The yellow pigment is C.I. Pigment Yellow 11, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 167, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 199, C.I. Pigment Yellow 215, C.I. Pigment Yellow 231 or combinations thereof.

In general, dyes are the most expensive constituents among the constituents used in color filters. Therefore, in order to achieve a desired effect, such as high luminance or high contrast ratio, more expensive dyes must be used, resulting in an increase in production cost. However, when the compound according to an embodiment is used as a dye in a color filter, excellent color characteristics such as high luminance and high contrast ratio can be achieved even with a small amount, so that the production cost can be reduced.

A dispersant may be used together to disperse the green pigment and the yellow pigment. Specifically, the pigment may be surface-treated in advance with a dispersant, or may be used by adding a dispersant together with the pigment when preparing the composition.

Nonionic dispersants, anionic dispersants, cationic dispersants, and the like may be used as the dispersant. Specific examples of the dispersant include polyalkylene glycol and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylic acid ester, carboxylate , Alkyl amide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more.

For example, the commercially available products of the dispersant are 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 Chemical; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; Alternatively, there are PB711 and PB821 of Ajinomoto.

The 　 dispersant may be included in an amount of 0.1% to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included within the above range, stability, developability, and patternability are excellent when preparing a black column spacer according to the excellent dispersibility of the composition.

The pigment may be used after pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used after the pretreatment, the average particle diameter of the pigment can be refined.

The pretreatment may be performed through a step of kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be performed at a temperature of 40° C. to 100° C., and the filtration and washing may be performed by washing the inorganic salt with water and then filtering.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent serves as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed so that the pigment can be easily pulverized, examples of which include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc. Alkylene glycol monoalkyl ether; Alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol, and the like, and these may be used alone or in combination of two or more.

The pigment that has undergone the kneading step may have an average particle diameter of 5 nm to 200 nm, such as 5 nm to 150 nm. When the average particle diameter of the pigment is within the above range, the stability in the pigment dispersion is excellent, and there is no fear of lowering the resolution of the pixel.

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

Specifically, the pigment may be used in the form of a pigment dispersion comprising the dispersant and a solvent described later, and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. The solid pigment may be included in an amount of 5% to 20% by weight, such as 8% to 15% by weight, based on the total amount of the pigment dispersion.

(A) binder resin

The binder resin may include 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 at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxy 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% to 50% by weight, such as 10% to 40% by weight, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (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 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 binder resin may be 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol, such as 20,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the 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 binder resin may be included in an amount of 1% to 10% by weight based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, developability is excellent and crosslinking property is improved when manufacturing a color filter, thereby obtaining excellent surface smoothness.

(C) Photopolymerization compound

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

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

Specific examples of the photopolymerizable compound 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)acrylate 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, novolac epoxy (meth)acrylate, etc. are mentioned.

Commercially available products of photopolymerizable compounds are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® of Nihon Kayaku Co., Ltd., TC-120S ^®, etc.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® , R-604 ^{® of} Nihon Kayaku Co., Ltd.; Osaka Yuki Kagaku High School Co., Ltd.'s V-260 ^® , V-312 ^® , and V-335 HP ^® are listed. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -710 ^® , M-8030 ^® , M-8060 ^®, etc.; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka Yuki Kayaku High School Co., Ltd.'s V-295 ^® , East-300 ^® , East-360 ^® , East-GPT ^® , East-3PA ^® , and East-400 ^® are listed. The above products can be used alone or in combination of two or more.

The photopolymerizable compound may be used after treatment with an acid anhydride in order to impart better developability.

The photopolymerizable compound may be included in an amount of 1% to 10% by weight, such as 5% to 10% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, hardening occurs sufficiently during exposure in the pattern formation process, thereby providing excellent reliability and excellent developability in an alkaline developer.

(D) Light polymerization Initiator

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

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, 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, and the like.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-Bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- And chloro thioxanthone.

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

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 O-acyloxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 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-based 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-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2 -Oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O- Acetate, etc. are mentioned.

In addition to the above compounds, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, a fluorene compound, or the like.

The photopolymerization initiator may be used together with a photosensitizer that absorbs light and becomes excited, and then transmits the energy to cause a chemical reaction.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. Can be mentioned.

The photopolymerization initiator may be included in an amount of 0.1% to 5% by weight, such as 0.1% to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure in the pattern formation process to obtain excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and due to the unreacted initiator It can prevent a decrease in transmittance.

(E) solvent

The solvent may be a dye, a pigment, a binder resin, a photopolymerizable compound, and a photopolymerization initiator compatible with, but does not react.

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 methyl ethyl 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 methoxy 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 2-oxy methyl propionate, 2-oxy ethyl propionate, and 2-oxy propionic acid propyl; 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 alkyl 2-alkoxy-2-methyl propionate such as ethyl methyl propionate; Esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; Ketone acid esters such as ethyl pyruvate, etc., and also N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid 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, ketones such as cyclohexanone are preferred; Glycol ethers such as ethylene glycol monoethyl ether; 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, and ketones such as cyclohexanone may be used.

The solvent may be included in a balance, such as 25% to 50% by weight, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and thus processability is excellent in manufacturing a color filter.

(F) other additives

The photosensitive resin composition may include malonic acid in order to prevent spots or spots during application, to improve leveling performance, and to prevent generation of residues due to undeveloped images; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; Leveling agents; Surfactants; And it may further include at least one additive selected from a radical polymerization initiator.

The additive can be easily adjusted according to the desired physical properties.

The coupling agent may be a silane coupling agent, and examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc., and these may be used alone or in two or more It can be mixed and used.

Specifically, the silane-based coupling agent may be used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

In addition, the photosensitive resin composition for the color filter may further include a surfactant, such as a fluorine-based surfactant, if necessary.

Examples of the fluorine-based surfactant include DIC's F-482, F-484, and F-478, but are not limited thereto.

The surfactant is preferably included in an amount of 0.01% to 5% by weight, and more preferably 0.01% to 2% by weight based on the total amount of the photosensitive resin composition. If it is out of the above range, it is not preferable because there may be a problem that foreign matters are generated after development.

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

According to another embodiment, a photosensitive resin film manufactured using the photosensitive resin composition according to the embodiment is provided.

According to another embodiment, a color filter manufactured by using the above-described photosensitive resin composition is provided.

The manufacturing method of the color filter is as follows.

A photosensitive resin composition layer is formed by applying the above-described photosensitive resin composition to a thickness of, for example, 0.5 µm to 10 µm using a suitable method such as spin coating, roller coating, and spray coating on the glass substrate.

Subsequently, light is irradiated to form a pattern required for a color filter on the substrate on which the photosensitive resin composition layer is formed. As a light source used for irradiation, UV, electron beam, or X-ray may be used, and for example, UV in a region of 190 nm to 450 nm, specifically 200 nm to 400 nm may be irradiated. In the irradiation step, a photoresist mask may be further used. After performing the step of irradiating in this way, the photosensitive resin composition layer irradiated with the light source is treated with a developer. At this time, the non-exposed portion of the photosensitive resin composition layer is dissolved to form a pattern necessary for the color filter. By repeating this process according to the number of required colors, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above process is heated again or cured by irradiation with actinic rays, crack resistance, solvent resistance, and the like can be improved.

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 dyes)

Synthesis example 1: Synthesis of a compound represented by Formula 4

In a 100 mL flask, 3,4,6-Trichloro-5-(2-cyclohexylphenoxy)-phthalonitrile (0.5 g), 3,4,5,6-Tetrachlorophthalonitrile (0.98 g), 1,8-Diazabicycloundec-7-ene(0.9) g), 1-pentanol (5g) and zinc acetate (0.22g) were added and stirred while heating to 140℃. After completion of the reaction, it is concentrated and purified by column chromatography. The liquid obtained after purification is concentrated to obtain a solid. The crystallized solid was vacuum-dried to synthesize a compound represented by the following formula (4).

[Formula 4]

Maldi-tof MS: 1268.79 m/z

Synthesis example 2: Synthesis of the compound represented by Formula 5

In a 100 mL flask, 3,4,6-Trichloro-5-(2-cyclohexylphenoxy)-phthalonitrile (0.5 g), 3,4,5,6-Tetrachlorophthalonitrile (0.33 g), 1,8-Diazabicycloundec-7-ene(0.47) g), 1-pentanol (5g) and zinc acetate (0.11g) are added and stirred while heating to 140°C. After completion of the reaction, it is concentrated and purified by column chromatography. The liquid obtained after purification is concentrated to obtain a solid. The crystallized solid was vacuum-dried to synthesize a compound represented by the following formula (5).

[Formula 5]

Maldi-tof MS: 1408.59 m/z

Synthesis example 3: Synthesis of the compound represented by Formula 6

In a 100 mL flask, 3,4,6-Trichloro-5-(2-cyclohexylphenoxy)-phthalonitrile (0.5 g), 3,4,5,6-Tetrachlorophthalonitrile (0.1 g), 1,8-Diazabicycloundec-7-ene (0.3 g), 1-pentanol (5g) and zinc acetate (0.08g) were added and stirred while heating to 140℃. After completion of the reaction, it is concentrated and purified by column chromatography. The liquid obtained after purification is concentrated to obtain a solid. The crystallized solid was vacuum-dried to synthesize a compound represented by the following formula (6).

[Formula 6]

Maldi-tof MS: 1548.39 m/z

Synthesis example 4: Synthesis of a compound represented by Formula 7

In a 100 mL flask, 3,4,6-Trichloro-5-(2-cyclohexylphenoxy)-phthalonitrile (0.7 g), Phthalonitrile (0.07 g), 1,8-Diazabicycloundec-7-ene (0.44 g), 1-pentanol ( 5g) and zinc acetate (0.1g) are added and stirred while heating to 140℃. After completion of the reaction, it is concentrated and purified by column chromatography. The liquid obtained after purification is concentrated to obtain a solid. The crystallized solid was vacuum-dried to synthesize a compound represented by the following formula (7).

[Formula 7]

Maldi-tof MS: 1410.62 m/z

Synthesis example 5: Synthesis of the compound represented by Formula 8

In a 100 mL flask, 3,4,6-Trichloro-5-(3-cyclohexylphenoxy)-phthalonitrile (0.5 g), 3,4,5,6-Tetrachlorophthalonitrile (0.1 g), 1,8-Diazabicycloundec-7-ene (0.3 g), 1-pentanol (5g) and zinc acetate (0.08g) were added and stirred while heating to 140℃. After completion of the reaction, it is concentrated and purified by column chromatography. The liquid obtained after purification is concentrated to obtain a solid. The crystallized solid was vacuum-dried to synthesize a compound represented by the following formula (8).

[Formula 8]

Maldi-tof MS: 1548.39 m/z

Synthesis example 4: Synthesis of a compound represented by Formula 9

In a 100 mL flask, 3,4,6-Trichloro-5-(4-cyclohexylphenoxy)-phthalonitrile (0.5 g), 3,4,5,6-Tetrachlorophthalonitrile (0.1 g), 1,8-Diazabicycloundec-7-ene (0.3 g), 1-pentanol (5g) and zinc acetate (0.08g) were added and stirred while heating to 140℃. After completion of the reaction, it is concentrated and purified by column chromatography. The liquid obtained after purification is concentrated to obtain a solid. The crystallized solid was vacuum-dried to synthesize a compound represented by the following formula (9).

[Formula 9]

Maldi-tof MS: 1548.39 m/z

compare Synthesis example 1: formula C- 1 of synthesis

In a 100 mL flask, 4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile (1.5 g), 3,4,6-Trichloro-5-(2,6-dichloro-phenoxy)-phthalonitrile (0.49) g), 1,8-Diazabicycloundec-7-ene (1.52g), 1-pentanol (14g) and zinc acetate (0.23g) were added and stirred while heating to 140℃. After completion of the reaction, it is concentrated and purified by column chromatography. The liquid obtained after purification is concentrated to obtain a solid. The crystallized solid is vacuum-dried to obtain a compound represented by the following formula (C-1).

[Chemical Formula C-1]

Maldi-tof MS: 1656.79 m/z

(Synthesis of photosensitive resin composition)

Example 1 to Example 8 and Comparative example 1 to Comparative example 4

The constituents mentioned below were mixed in the composition shown in Table 1 to prepare a photosensitive resin composition according to Examples 1 to 8 and Comparative Examples 1 to 4.

Specifically, after dissolving a photopolymerization initiator in a solvent, the mixture was stirred at room temperature, and then an alkali-soluble resin and a photopolymerizable compound were added thereto, followed by stirring at room temperature. Subsequently, the dye (compound represented by Formula 1) and pigment prepared in Synthesis Example 1 were added to the obtained reactant as a colorant, and stirred at room temperature. Subsequently, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) binder resin 5 5 5 5 5 5 5 6 5 5 10 5 (B) colorant B-1 14 - - - - - - - - - - - B-2 - 14 - - - - - - - - - - B-3 - - 14 - - - 22 11 - - 8 9 B-4 - - - 14 - - - - - - - - B-5 - - - - 14 - - - - - - - B-6 - - - - - 14 - - - - - - B-7 - - - - - - - - 14 - - - B-8 10 10 10 10 10 10 5 9 10 10 7 19 B-9 16 16 16 16 16 16 13 15 16 16 10 28 B-10 - - - - - - - - - 14 - - (C) photopolymerizable compound 11 11 11 11 11 11 11 13 11 11 18 8 (D) photopolymerization initiator 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2.5 One (E) solvent 42 42 42 42 42 42 42 44 42 42 44 29.5 (F) additive 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

(A) binder resin

(A)/(B)=15/85 (w/w), molecular weight (Mw)=22,000 g/mol, (A): methacrylic acid, (B): benzyl methacrylate

(B) colorant

(B-1) Dye of Synthesis Example 1 (compound represented by Chemical Formula 4)

(B-2) Dye of Synthesis Example 2 (compound represented by Chemical Formula 5)

(B-3) Dye of Synthesis Example 3 (compound represented by Formula 6)

(B-4) Dye of Synthesis Example 4 (compound represented by Chemical Formula 7)

(B-5) Dye of Synthesis Example 5 (compound represented by Chemical Formula 8)

(B-6) Dye of Synthesis Example 6 (compound represented by Chemical Formula 9)

(B-7) Dye of Comparative Synthesis Example 1 (compound represented by Chemical Formula C-1)

(B-8) Pigment G59 pigment (SGTC-368, SKC company)

(B-9) Pigment Y231 Pigment (TS-036-138, TOYO Corporation)

(B-10) Pigment G58 pigment (SGTC-336M1, SKC company)

(C) Photopolymerization Monomer

Dipentaerythritol hexaacrylate (DPHA)

(D) Light polymerization Initiator

Oxime compound (IRGARCURE OXE01, BASF company)

(E) solvent

Propylene glycol monomethyl ether acetate (Sigma-Aldrich)

(F) additive

Surfactant (F-554, DIC company)

Evaluation 1: Dye spectral comparison

The photosensitive resin composition prepared in Example 3 and Comparative Example 1 was applied to a thickness of 1 µm to 3 µm on a degreasing and washed glass substrate, and dried on a hot plate at 90° C. for 2 minutes to form a coating film. Obtained. Subsequently, using a high-pressure mercury lamp having a dominant wavelength of 365 nm on the coating film, the entire surface was exposed under the condition of 60 mJ/cm ² . Thereafter, it was dried for 20 minutes in a hot air circulation drying furnace at 230° C. to obtain a sample having the same thickness. The spectral characteristics (transmittance according to wavelength) of the sample are shown in FIG. 1.

Referring to FIG. 1, a sample using the dye (compound represented by Formula 6) of Example 3, that is, Synthesis Example 3, was prepared by using the dye (compound represented by Formula C-1) of Comparative Example 1, that is, Comparative Synthesis Example 1 It can be seen that it shows blue-shifted spectroscopy in the green transmission region than in the sample used. From this, it can be seen that the composition using the dye according to the embodiment as a colorant can implement high color coordinates with only a smaller content than the composition that does not.

Evaluation 2: Measurement of brightness, heat resistance and chemical resistance

The photosensitive resin composition prepared in Examples 1 to 8 and Comparative Examples 1 to 4 was applied to a thickness of 1 µm to 3 µm on a degreasing and washed glass substrate, and a hot plate at 90°C It was dried on the bed for 2 minutes to obtain a coating film. Subsequently, using a high-pressure mercury lamp having a dominant wavelength of 365 nm on the coating film, the entire surface was exposed under the condition of 60 mJ/cm ² . Thereafter, it was dried for 20 minutes in a hot air circulation drying furnace at 230° C. to obtain a sample having the same thickness. The pixel layer was measured for luminance (GY@Gy 0.635), heat resistance and chemical resistance using a spectrophotometer (MCPD3000, Otsuka electronic), and the results are shown in Table 2 below.

(1) luminance measurement

The prepared sample was evaluated for color characteristics based on the C light source using the MCPD (Otsuka Corporation) equipment. The evaluation result was based on Gy 0.635, and the luminance (GY) was measured.

(2) Heat resistance measurement

The prepared sample was additionally treated at 230° C./60 minutes using a convection oven, and then color changes before and after treatment were evaluated using an MCPD (Otsuka Corporation) equipment to evaluate the C light source reference color characteristics. The heat resistance was measured by calculating the ΔEab* value.

(3) Chemical resistance (solubility) measurement

The prepared sample was prepared in a size of 2×2 cm, precipitated in PGMEA solution for 90° C./10 minutes, and then color changes before and after treatment were evaluated using an MCPD (Otsuka Corporation) equipment to evaluate the C light source reference color characteristics. Chemical resistance was measured by calculating the ΔEab* value.

Luminance (%) Heat resistance (△Eab*) Chemical resistance (△Eab*) Example 1 101.5 2.52 2.6 Example 2 101.8 2.47 2.55 Example 3 102.5 2.43 2.5 Example 4 100.8 2.58 2.75 Example 5 101.2 2.55 2.7 Example 6 101.1 2.55 2.7 Example 7 102.3 2.73 2.8 Example 8 102.2 2.3 2.6 Comparative Example 1 101.5 2.6 3.2 Comparative Example 2 100 1.3 2.3 Comparative Example 3 100.5 2.2 2.5 Comparative Example 4 99.5 1.5 2.6

From Table 2, the photosensitive resin compositions of Examples 1 to 8 including the compound according to an embodiment as a dye and at the same time containing a green pigment and a yellow pigment, Comparative Examples 1 to Comparative Examples not containing the compound It can be seen that superior luminance and reliability (heat resistance and chemical resistance) can be simultaneously implemented when implementing high color coordinates than the photosensitive resin composition of 4. In addition, from Comparative Examples 3 and 4, when the colorant is included in an amount of less than 30% by weight or more than 50% by weight relative to the total amount of the photosensitive resin composition, it can be seen that the luminance decreases when implementing high color coordinates. In addition, from Example 7, it can be seen that reliability (heat resistance and chemical resistance) is lowered when the dye content is greater than the pigment content.

Although the 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 claims, the detailed description of the invention, and the accompanying drawings. It is natural to fall within the scope of the invention.

Claims (21)

(A) binder resin;
(B) a colorant including a dye represented by the following formula (1), a green pigment, and a yellow pigment;
(C) a photopolymerizable compound;
(D) a photoinitiator and
(E) contains a solvent,
The colorant is included in an amount of 40% to 50% by weight based on the total amount of the photosensitive resin composition,
The green pigment is CI Pigment Green 37, CI Pigment Green 59, CI Pigment Green 62, or a combination thereof:
[Formula 1]

In Formula 1,
R ¹ to R ¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted A ringed C6 to C20 aryloxy group,
However, at least one of R ¹ to R ¹² is represented by the following Formula 2, and R ¹³ to R ¹⁶ are each independently a hydrogen atom or a halogen atom,
[Formula 2]

In Formula 2,
R ¹⁷ is a substituted or unsubstituted C3 to C20 cycloalkyl group.
delete The method of claim 1,
The photosensitive resin composition in which the dye content in the colorant is less than the pigment content in the colorant.
The method of claim 1,
Formula 2 is a photosensitive resin composition represented by the following Formula 3:
[Formula 3]

In Chemical Formula 3,
R ¹⁷ is a substituted or unsubstituted C3 to C20 cycloalkyl group.
The method of claim 1,
The R ¹³ to R ¹⁶ are each independently a halogen atom photosensitive resin composition.
The method of claim 1,
At least two of the R ¹ to R ¹² are represented by the formula (2) photosensitive resin composition.
The method of claim 1,
At least three of the R ¹ to R ¹² are represented by the formula (2).
The method of claim 1,
At least one of R ¹ to R ⁴ is represented by Formula 2,
At least one of R ⁵ to R ⁸ is represented by Formula 2,
At least one of R ⁹ to R ¹² is a photosensitive resin composition represented by Formula 2.
The method of claim 8,
The R ¹³ to R ¹⁶ are each independently a halogen atom photosensitive resin composition.
The method of claim 9,
One of R ¹ to R ⁴ is represented by Formula 2, and the other three are halogen atoms,
One of R ⁵ to R ⁸ is represented by Formula 2, and the other three are halogen atoms,
One of R ⁹ to R ¹² is represented by Formula 2, and the other three are halogen atoms.
The method of claim 1,
The compound represented by Formula 1 is a photosensitive resin composition represented by any one of the following Formulas 4 to 9.
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

The method of claim 1,
The compound represented by Formula 1 is a green dye photosensitive resin composition.
The method of claim 12,
The green dye photosensitive resin composition having a maximum transmittance in a wavelength range of 445nm to 560nm.
The method of claim 12,
The green dye photosensitive resin composition having a maximum absorbance in a wavelength range of 600nm to 730nm.
delete delete The method of claim 1,
The yellow pigment is CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 199, CI Pigment Yellow 215, CI Pigment Yellow 231, or a photosensitive resin composition comprising a combination thereof.
The method of claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
(A) 1% to 10% by weight of the binder resin;
30% to 50% by weight of the colorant (B);
1% to 10% by weight of the (C) photopolymerizable compound;
The (D) photopolymerization initiator 0.1% to 5% by weight and
The (E) solvent 25% to 50% by weight
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; Leveling agents; Fluorine-based surfactant; And a photosensitive resin composition further comprising at least one additive selected from radical polymerization initiators.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1, 3 to 14, and 17 to 19.
A color filter comprising the photosensitive resin film of claim 20.

Images