KR102219646B1 - Photosensitive resin composition, layer using the same, color filter and optical display device - Google Patents

Abstract

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

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

Description

Photosensitive resin composition, film, color filter, and optical display device {PHOTOSENSITIVE RESIN COMPOSITION, LAYER USING THE SAME, COLOR FILTER AND OPTICAL DISPLAY DEVICE}

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film prepared by using the photosensitive resin composition, a color filter including the photosensitive resin film, and an optical display device including the color filter.

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 bonding with integrated circuits, and thus its use range is expanding for notebook computers, monitors and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix (light shielding layer), 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 the ITO pixel electrode is formed Is composed.

The color filter includes a black matrix (light-shielding layer) formed in a predetermined pattern on a transparent substrate to shield the boundary between pixels, and a plurality of colors (typically, red (R), green (G)) to form each pixel. It has a structure in which pixel portions in which three primary colors of blue (B) are arranged in a predetermined order are sequentially stacked.

In the pigment dispersion method, one of the methods of implementing a color filter, coating a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposing the pattern to be formed, and removing the unexposed part with a solvent. This is a method in which a colored thin film is formed by repeating a series of thermal curing processes. The colored photosensitive resin composition used to manufacture the color filter according to the pigment dispersion method is generally composed of an alkali-soluble resin, a photopolymerization monomer, a photoinitiator, an epoxy resin, a solvent and other additives. The pigment dispersion method having the above characteristics has been actively applied to manufacturing LCDs such as mobile phones, notebook computers, monitors, and TVs.

However, in recent years, even in the photosensitive resin composition for color filters using the pigment dispersion method, which has various advantages, the micronization process of the powder is difficult and the dispersion state must be stable in the dispersion even if it is dispersed, so various additives are required and the process is also very difficult. Moreover, the pigment dispersion has a disadvantage that it is difficult to store and transport conditions in order to maintain an optimal quality condition.

In addition, 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. And, 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 these demands, attempts to implement a color filter with improved color characteristics such as luminance and contrast by manufacturing a photosensitive resin composition in which a dye that does not form particles is introduced instead of or together with the pigment is continued. The photosensitive resin composition has a problem of inferior durability compared to the pigment type photosensitive resin composition.

Meanwhile, a liquid crystal display device (LCD) requires a liquid crystal cell including a liquid crystal and a polarizing plate, and an appropriate adhesive layer or adhesive layer for bonding them must be used.

In addition, the polarizing plate is stretched in a certain direction, and protects both sides of a polyvinyl alcohol (PVA) polarizer (or'polarizing film') in which an iodine compound or a dichroic polarizing material is adsorbed and oriented, and both sides of the polarizer It includes a polarizer protective film laminated for this purpose. Specifically, a polarizer protective film such as triacetyl cellulose (TAC) is provided on one side of the polarizer, and an adhesive layer and a release film bonded to the liquid crystal cell on the protective film, and the other side of the polarizer Is composed of a polarizer protective film and a multi-layered surface protective film in which an adhesive layer is laminated on a base film.

In the process of attaching the polarizing plate of this structure to the liquid crystal cell, the release film is peeled from the pressure-sensitive adhesive layer, and when the role of the surface protection film is finished in the post process, it is also peeled off and removed. Since the release film and the surface protection film are made of a plastic material, they have high electrical insulation properties and generate static electricity during peeling.

The generated static electricity causes a problem of contaminating the surface due to the adsorption of foreign substances on the optical member, and a problem of staining due to distortion of liquid crystal alignment, and there is a concern of causing damage to the thin film transistor (TFT) line. In particular, as the LCD panel has become larger in recent years, the size of the polarizing plate used for manufacturing the liquid crystal display has also been enlarged, and the amount of static electricity generated further increases as the process speeds up, and thus, solving the problem becomes more urgent.

One embodiment is to provide a photosensitive resin composition comprising a compound having excellent color reproducibility as a colorant.

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

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

Another embodiment is to provide an optical display device including the color filter.

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An embodiment of the present invention is (A) a colorant comprising a compound represented by the following formula (1); (B) binder resin; (C) a photopolymerizable compound; (D) photoinitiator; And (E) It provides a photosensitive resin composition containing a solvent.

[Formula 1]

In Formula 1,

M is Zn, Co or Cu,

R ¹ to R ²⁰ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, A substituted or unsubstituted sulfonamide group or a substituted or unsubstituted C1 to C20 alkyl ester group,

However, ^{at least one of R 1} to R ⁵ , at least one of R ⁶ to R ¹⁰ , at least one of R ¹¹ to R ¹⁵ , and at least one of R ¹⁶ to R ²⁰ are each independently a hydrogen atom.

The compound may be represented by Formula 2.

[Formula 2]

In Chemical Formula 2,

M is Zn, Co or Cu,

R ²¹ to R ²⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted A cyclic sulfonamide group or a substituted or unsubstituted C1 to C20 alkyl ester group,

n1 to n8 are each independently an integer of 0 or 1, provided that 1≦n1+n2≦2, 1≦n3+n4≦2, 1≦n5+n6≦2, and 1≦n7+n8≦2.

The compound may be represented by any one of the following Formulas 1-1 to 1-20.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

In Formula 1-13,

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

m1 and m2 are each independently an integer of 0 to 20, provided that 4≦m1+m2≦20,

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

The compound represented by Formula 1 may be included in an amount of 0.01% to 7% by weight based on the total amount of the photosensitive resin composition.

The colorant may further include a blue dye, a blue pigment, a red dye, a red pigment, or a combination thereof.

The blue dye may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ²⁹ and R ³⁰ are each independently a substituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group,

R ³¹ is a hydrogen atom or a halogen group,

R ³² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ³³ is a C1 to C20 alkyl group unsubstituted or substituted with an acrylate group,

X ^- is represented by any one of the following formulas A to C.

[Formula A]

SO ₃ ^-

[Formula B]

(In Formula B, n3 is an integer from 0 to 10)

[Formula C]

The blue dye may be represented by the following Formula 3-1 or Formula 3-2.

[Formula 3-1]

[Chemical Formula 3-2]

In Formulas 3-1 and 3-2,

X ^- is represented by any one of the following formulas A to C.

[Formula A]

SO ₃ ^-

[Formula B]

(In Formula B, n3 is an integer from 0 to 10)

[Formula C]

The blue pigment is C.I. It can be Pigment Blue 15:6.

The binder resin may include an acrylic binder resin.

The photopolymerization initiator may include an oxime-based initiator and an acetophenone-based initiator.

The photosensitive resin composition includes 3% to 20% by weight of a colorant including the compound represented by (A) Formula 1, based on the total amount of the photosensitive resin composition; (B) 1% to 10% by weight of the binder resin; 1% to 10% by weight of the (C) photopolymerizable compound; The (D) photopolymerization initiator may include 0.1% to 5% by weight and the remaining amount of the (E) solvent.

The photosensitive resin composition may further include an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.

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.

Another embodiment provides an optical display device including the color filter.

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

The photosensitive resin composition according to an embodiment includes a compound that blocks a wavelength of a violet region (400 nm to 440 nm) in order to improve the color reproducibility of a color filter constituting a panel of an optical display device such as a liquid crystal display device. Also, relatively high luminance can be achieved. In particular, since the compound has a characteristic of strongly absorbing light in a very narrow area, it is possible to implement a high color (blue) by blocking spectroscopy of the corresponding area even with a very small amount.

1 is a graph showing the transmittance of the compound represented by Formula 1-1, yellow dye 1 and yellow dye 2 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, Hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, 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 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.

In addition, in this specification, when a member is positioned "on" another member, this includes not only the case where a member is in contact with the other member, but also the case where another member exists between the two members.

In addition, in the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

In one embodiment, (A) a colorant comprising a compound represented by Formula 1; (B) binder resin; (C) a photopolymerizable compound; (D) photoinitiator; And (E) It provides a photosensitive resin composition containing a solvent.

Hereinafter, each component will be described in detail.

coloring agent

The photosensitive resin composition according to an embodiment includes a compound represented by Formula 1 below as a colorant.

[Formula 1]

In Formula 1,

M is Zn, Co or Cu,

R ¹ to R ²⁰ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, A substituted or unsubstituted sulfonamide group or a substituted or unsubstituted C1 to C20 alkyl ester group,

However, ^{at least one of R 1} to R ⁵ , at least one of R ⁶ to R ¹⁰ , at least one of R ¹¹ to R ¹⁵ , and at least one of R ¹⁶ to R ²⁰ are each independently a hydrogen atom.

For example, the compound may be represented by Formula 2.

[Formula 2]

In Chemical Formula 2,

M is Zn, Co or Cu,

R ²¹ to R ²⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted A cyclic sulfonamide group or a substituted or unsubstituted C1 to C20 alkyl ester group,

n1 to n8 are each independently an integer of 0 or 1, provided that 1≦n1+n2≦2, 1≦n3+n4≦2, 1≦n5+n6≦2, and 1≦n7+n8≦2.

For example, the compound may be represented by any one of Formulas 1-1 to 1-20 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

In Formula 1-13,

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

m1 and m2 are each independently an integer of 0 to 20, provided that 4≦m1+m2≦20,

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

Among the existing color filter resists, in the case of a blue resist, it is common to add some violet colorants to the blue pigment in order to adjust the color coordinates and increase luminance. However, recently, the color coordinate of the new blue to increase the color gamut is the trend of smaller Bx. In order to realize such a blue color filter with high color reproducibility, a narrow transmission spectrum should be made near 450nm, which is the wavelength of the blue LED as a light source, and for this purpose, a pigment of beta blue is used instead of epsilon blue, which is commonly used. The direction of manufacturing a resist with a reduced transmission spectrum by increasing the PWC is also proposed. However, in this case, there is a problem that the existing luminance is very poor.

According to one embodiment, while lowering Bx, a dye that cuts the Violet region so that the luminance is advantageous compared to when using beta blue is used. Since the compound represented by Chemical Formula 1 strongly absorbs a very narrow area in the vicinity of 400 nm to 440 nm, specifically 420 nm to 440 nm, it is possible to implement a high color (blue) by blocking spectroscopy of the corresponding area even with a very small amount. In order to achieve a similar purpose, there have been attempts to absorb a region of 380nm to 420nm using a conventional azo-based yellow dye, but in this case, since a relatively large amount of the azo-based yellow dye must be added, the total composition Although there is a problem in that the process margin is not secured, according to an embodiment, sufficient high color reproduction is possible even when only a small amount of the compound represented by Formula 1 is used, and the above problem can be solved. In addition, when a conventional azo-based yellow dye is used together with an existing blue pigment (epsilon blue), since the transmission and absorption spectra overlap, the blue transmission region may be damaged, resulting in increased luminance loss. However, according to one embodiment, by controlling the transmittance according to the wavelength of the yellow dye, it mainly absorbs a wavelength region in the vicinity of 400 nm to 440 nm, specifically 420 nm to 440 nm, and the transmittance in the wavelength region less than 400 nm and 450 nm or more is 80% or more. , For example more than 95%, it is possible to minimize the luminance loss of the main spectrum from the light source. In addition, by using a compound (a compound represented by Formula 1) according to an embodiment to a colorant (dye or pigment) that has higher luminance than the existing blue pigment, but is not suitable for high color coordinates due to its large Bx, while implementing high color coordinates, the luminance is more Can increase.

The compound represented by Formula 1 may be included in an amount of 0.01% to 7% by weight based on the total amount of the photosensitive resin composition. Sufficient high color reproduction is possible in the above range and can have an excellent process margin.

For example, the colorant may further include a blue dye, a blue pigment, a red dye, a red pigment, or a combination thereof.

The blue dye may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ²⁹ and R ³⁰ are each independently a substituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group,

R ³¹ is a hydrogen atom or a halogen group,

R ³² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ³³ is a C1 to C20 alkyl group unsubstituted or substituted with an acrylate group,

X ^- is represented by any one of the following formulas A to C.

[Formula A]

SO ₃ ^-

[Formula B]

(In Formula B, n3 is an integer from 0 to 10)

[Formula C]

For example, the blue dye may be represented by the following Formula 3-1 or Formula 3-2.

[Formula 3-1]

[Chemical Formula 3-2]

In Formulas 3-1 and 3-2,

X ^- is represented by any one of the following formulas A to C.

[Formula A]

SO ₃ ^-

[Formula B]

(In Formula B, n3 is an integer from 0 to 10)

[Formula C]

Specifically, the blue dye may be represented by Formula 3-1.

Since the compound represented by Formula 3-1 contains a cyclohexyl group, heat resistance can be improved, and light resistance can be improved by the phenyl group substituted on the nitrogen atom including a methyl group, so not only high luminance at high color coordinates, but also A color filter having excellent durability such as heat resistance and light resistance can also be provided.

For example, the blue pigment may be an epsilon blue pigment. When using a blue pigment as a blue colorant according to an embodiment, it is helpful to use an epsilon blue pigment rather than a beta blue pigment to improve brightness.

For example, the blue pigment is C.I. It can be Pigment Blue 15:6.

For example, the red pigment is C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 179, C.I. It may be a red pigment 89 or the like, but is not limited thereto.

The colorant may be included in an amount of 3% to 20% by weight based on the total amount of the photosensitive resin composition according to an embodiment. When the colorant is included in the above range, high luminance at high color coordinates can be achieved.

Binder resin

The binder resin may include an acrylic binder resin. For example, the 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 containing at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxy group and/or a hydroxy 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 acrylic 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 acrylic binder resin is within the above range, the physical and chemical properties of the photosensitive resin composition are excellent, the viscosity is appropriate, and adhesion with the substrate is excellent when manufacturing a color filter.

The acid value of the acrylic binder resin may be 15 mgKOH/g to 60 mgKOH/g, such as 20 mgKOH/g to 50 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 binder resin may be included in an amount of 1% to 10% by weight, such as 3% to 7% 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.

Photopolymerizable 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 1% to 5% 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.

Photopolymerization 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, benzyldimethylketal, 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-one oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O- Acetate, etc. are mentioned.

The photopolymerization initiator may include an oxime-based initiator and an acetophenone-based initiator at the same time. In this case, it is possible to secure an excellent process margin by increasing curing efficiency compared to the case of using only one type of photopolymerization initiator. Further, in this case, the oxime-based initiator may be included in an amount higher than that of the acetophenone-based initiator. When the oxime-based initiator is included in an amount equal to or smaller than the acetophenone-based initiator, the sensitivity is low (excellent sensitivity), and the desired CD can be implemented.

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 1% 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 unreacted initiators. It is possible to prevent a decrease in transmittance.

menstruum

The solvent may be materials that have compatibility with the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator, but do 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 methyl 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; Lactate 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 propionate 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, and the like, and N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, 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 may be used.

The solvent may be included in a balance, such as 40% to 80% by weight, such as 50% to 75% 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.

Other additives

The photosensitive resin composition according to an embodiment may further include an epoxy compound to improve adhesion to 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 to 20 parts by weight, for example, 0.1 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.

In addition, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group to improve adhesion to the substrate.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidok Cypropyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldie Oxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N -2-(Aminoethyl)-3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3- Dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, Bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, and the like, and these may be used alone or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane 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 to improve coating properties and prevent defects from being generated, if necessary.

Examples of the surfactants include, BM Chemie BM-1000 ^® of社, BM-1100 ^®, and the like; ^{Mecha Pack F 142D ®} , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^{® of} Dai Nippon Inki Chemical High School Co., Ltd.; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray silicone (Note)社SH-28PA ^®, copper -190 ^®, may be used copper ^® -193, fluorine-based surfactants and commercially available under the name, such as ^{SZ-6032 ®, SF-8428} ®.

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

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 prepared by using the photosensitive resin composition according to the embodiment is provided.

The pattern formation process in the photosensitive resin film is as follows.

Applying the photosensitive resin composition onto a supporting 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 to light; Developing the exposed photosensitive resin composition film with an aqueous alkali solution to prepare a photosensitive resin film; And a step of heat treating the photosensitive resin film. Since the above process conditions are widely known in the art, detailed descriptions thereof will be omitted herein.

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

Another embodiment provides an optical display device including a color filter including the photosensitive resin film.

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The optical display device is an image display device, and may include a liquid crystal display device, an OLED, a flexible display, etc., but the present invention is not limited thereto, and all image display devices known in the art may be applicable.

For example, the optical display device may be a liquid crystal display device. In general, a liquid crystal display device includes a backlight (BLU), a polarizing plate, a thin film transistor (TFT), a liquid crystal cell, a color filter, and a polarizing plate, and the color filter may be a color filter according to an exemplary embodiment. For example, the optical display device may include a polarizing plate in which an adhesive layer is stacked on at least one surface of a color filter according to an exemplary embodiment.

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 dye represented by Chemical Formula 1-1

[Scheme 1]

(1) After adding 4-t-butylbenzaldehyde (16.2 g, 0.1 mol), propionic acid 100 g, and pyrrole (6.71 g, 0.1 mol) to a round bottom flask, the temperature was raised to 130° C. and stirred for 6 hours. When the reaction is completed, the temperature is lowered to room temperature, and 100 g of acetone is added thereto and stirred. The resulting solid compound was filtered through a filter, washed with acetone, and dried to synthesize a porphyrin intermediate (4.2g, 20%).

(2) In a round-bottom flask, intermediate (4.2g, 5 mmol) and 80 g of chloroform were added, stirred at 60°C, and Zinc acetate (2.75g, 15 mmol) was added to another round-bottom flask, and 53g of methanol was added thereto and stirred. . At this time, it should be stirred until the zinc acetate is completely dissolved. When the zinc acetate is completely dissolved, it is added to the intermediate and stirred at 60° C. for 3 hours, and the reaction is terminated. Extracted with chloroform, washed with water and filtered. After distilling the filtrate, 50 g of acetone was added thereto, stirred at room temperature for 1 hour, and filtered again to obtain a porphyrin-based dye (3.1 g, 69%) (900 m/z).

Synthesis Example 2: Synthesis of blue dye represented by Chemical Formula 3-1

1. Synthesis of compound 1

_{NaBH 4} (3.8 g, 0.1 mol) was added to a round bottom flask, and 100 g of 1,2-dichloroethane was added thereto, followed by lowering to 0 °C and stirring. After adding acetic acid (21.6g, 0.36mol), the temperature was gradually raised to room temperature and stirred for 2 hours, and then cyclohexanone (8.8g, 0.09 mol) was added dropwise. The reaction was stirred at room temperature for 1 hour, then aniline (7.9g, 0.85 mol) was added, and then overnight at room temperature. When the reaction was completed, extraction was performed using dichloromethane and washed with distilled water and 10% NaCl aqueous solution. Moisture was removed using MgSO ₄ , filtered, and dried to synthesize compound 1 (14.5 g, 97% yield).

[Compound 1]

2. Synthesis of compound 2

4,4'-dichlorobenzophenone (10g, 39.8mmol), Pd ₂ (dba) ₃ (220mg, 0.002 mol%), XPhos (230mg, 0.005mol%) and sodium t-butoxide (11.48g, 119.5mmol) under nitrogen atmosphere Was placed in a round bottom flask, 50 g of toluene was added thereto, and after stirring at room temperature for 10 minutes, Compound 1 (14 g, 79.6 mmol) was added thereto. The reaction was stirred for 2 hours while gradually raising the temperature to 80°C. When the reaction was completed, the temperature of the reactant was lowered to room temperature, and 50 g of isopropanol was added thereto, followed by stirring. The precipitate was filtered off using a filter, washed with water, and then added to acetonitrile, followed by stirring at 80° C. for 30 minutes. After lowering the temperature to room temperature, the precipitate was filtered and dried to synthesize intermediate 2 (27.3 g, 65% yield).

[Compound 2]

3. Synthesis of Compound 3 to Compound 6

[Scheme 2]

(Synthesis of compound 3)

After adding sodium ethoxide (34.2 g, 0.503 mol) and 250 g of ethanol to a round bottom flask, stirred at room temperature for 30 minutes, ethyl cyanoacetate (45.5 g, 0.402 mol) was slowly added to the reaction mixture, and then 30 at room temperature. Stir for a minute. O-tolylisothiocyanate (50g, 0.335mol) was slowly added dropwise to the reaction, and the temperature was raised to 80°C, followed by stirring for 3 hours. When the reaction is complete, the temperature is lowered, the solvent is removed, and this is extracted with dichloromethane and washed with 10% HCl and water, respectively. After removing the organic solvent, 200 g of MeOH was added to the resulting solid compound, stirred at 0° C. for 30 minutes, and filtered to synthesize compound 3 (73.8 g, 84% yield).

[Compound 3]

(Synthesis of compound 4)

After adding NaOH (45.7g, 1.14mol) and 240g of water to a round bottom flask, stirring at 0℃ for 30 minutes, and then compound 3 (30g, 0.114mol) was added, and the reaction mixture was heated to 80℃ for 3 hours. Stirred. When the reaction is complete, lower the temperature to 0℃ and conc. The reaction is acidified with HCl (pH: about 6). The resulting precipitate was filtered through a filter, washed with water, and dried to synthesize compound 4 (19.7 g, 90% yield).

[Compound 4]

(Synthesis of Intermediate 5)

After adding KOH (8.71g, 0.155mol) and 200g of MeOH to a round bottom flask and stirring at room temperature for 30 minutes, compound 4 (20.5g, 0.108mol) and 2'-chlorophenacyl bromide (26.6g, 0.114mol) were added thereto. After each addition, it was stirred at room temperature for 2 hours. Upon completion of the reaction, 200 g of water was added, and after stirring at room temperature for 1 hour, the resulting precipitate was filtered through a filter, washed with MeOH, and dried to synthesize compound 5 (29.8 g, 89% yield).

[Compound 5]

(Synthesis of compound 6)

KOH (10.4g, 0.185mol), 170g of acetone, and 80g of water were added to a round bottom flask, stirred at room temperature, and compound 5 (30g, 92.4 mmol) and 2-iodopropane (31.5g, 0.185mol) were added thereto, respectively. Then, the mixture was stirred at 60° C. for 12 hours. Upon completion of the reaction, acetone was removed through distillation, extracted with dichloromethane, and 10% HCl and sat. Wash with sodium thiosulfate. After removing the organic solvent, it was precipitated using Ethyl acetate/Hexnae to synthesize compound 6 (19g, 56% yield).

[Compound 6]

4. Synthesis of the compound represented by Formula 3-1

After adding Compound 2 (1.50g, 2.83mmol) and Compound 6 (1.0g, 2.83mmol) to a round bottom flask under nitrogen, 7.5g of toluene and _{POCl 3} (2.6g, 17.0mmol) were added, and then the temperature was gradually increased. Raised to 110 ℃ and stirred for 5 hours. When the reaction was completed, the temperature was lowered to room temperature, extracted with methyl ethyl ketone (MEK), and washed with 10% NaCl, water and 10% HCl, respectively. After the organic layer was removed and dried, Lithium bis (trifuloromethane) sulfon imide (1.2 g, 4.2 mmol) was added, and 10 g of DMSO was added thereto, followed by stirring at room temperature for 30 minutes (anion exchange process). The reactant is dropped into water to form a precipitate, which is obtained by separating it through a filter. After dissolving the solid compound obtained through the filter in 40 g of acetonitrile, 3 g of activated carbon was added thereto and stirred for 30 minutes. Activated carbon was removed through a filter, and the filtrate was removed through distillation and dried to obtain a final compound represented by Chemical Formula 3-1 (2.69g, 82% yield). The following formula X is represented by the following formula C.

[Formula 3-1]

LC-MS: 1003 m/z

[Formula C]

Synthesis Example 3: Synthesis of blue dye represented by Chemical Formula 3-2

A blue dye represented by the following Formula 3-2 was synthesized with reference to Synthesis Example 1, such as using 2-aminopropane instead of aniline. The following formula X is represented by the following formula C.

[Chemical Formula 3-2]

LC-MS: 735 m/z

[Formula C]

Synthesis Example 4: Synthesis of Yellow Dye 1

Add hydrochloric acid (2.5 mL) and sodium nitrate (2 mL of 1.25 M aqueous solution) to 4-Aminophthalonitrile (2.5 mmol) to make azonium ions, and then add barbituric acid (2.5 mmol) to a weakly basic aqueous solution dissolved in NaOH aqueous solution. Azo compounds were made. The obtained solid was filtered, purified, dried in vacuo, 1-iodobutane (5.5 mmol) and potassium carbonate (7.5 mmol) were added, reacted in a DMF solvent, purified and dried in vacuo to give a yellow dye 1.

Synthesis Example 5: Synthesis of Yellow Dye 2

(1) Synthesis of Intermediate 1

4-methoxyphenyl isocyanate (5g, 33.5mmol) was added to a round bottom flask, toluene 50g and 4-methoxyaniline (4.13g, 33.5mmol) were added thereto, followed by stirring at room temperature for 5 hours. When the reaction was completed, the filter was performed, and the solid compound on the filter was washed several times with methanol and dried to synthesize the intermediate 1 compound (8.9g, 97%).

(2) Synthesis of Intermediate 2

The intermediate 1 compound (8.87g, 32.6mmol) was added to a round bottom flask, and malonic acid (3.83g, 36.8mmol) and 80 g of acetic anhydride were added thereto, followed by stirring at 90° C. for 5 hours. When the reaction is complete, the temperature is lowered to room temperature and the solvent is removed by distillation. Extracted with dichloromethane and washed with 10% aqueous sodium hydroxide solution. After removing the organic layer, a 10% HCl aqueous solution was gradually added to the 10% NaOH aqueous solution layer to bring the pH to 6, and this was extracted using dichloromethane. After removing the solvent, 50 g of isopropyl alcohol was added, and the mixture was stirred at 50° C. for 1 hour and filtered. The solid compound on the filter was washed with isopropyl alcohol and then dried to synthesize the intermediate 2 compound (5.99g, 54%).

(3) Synthesis of yellow dye 2

Put 4-amimophthalonitrile (4.21g, 29.4 mmol) in a round bottom flask, add 30g of water thereto, and then lower the temperature to 0℃. 30 g of HCl was added thereto, followed by stirring at 0°C. After dissolving NaNO ₂ (2.03g, 29.4mmol) in 20g of water, it was added to the reaction and stirred at 0°C for 2 hours.

Put sodium carbonate (9.35g, 88.2mmol) into another round bottom flask, and add 500g of water to it and stir. When the sodium carbonate compound is dissolved in water, the intermediate 2 compound (10g, 29.4mmol) is added thereto and stirred at room temperature for 1 hour. This reaction was slowly added dropwise to the reaction mixture stirred for 2 hours, and when the addition was completed, the mixture was stirred at room temperature for 12 hours. When the reaction is complete, filter is performed, and the solid compound on the filter is washed with water and dried. After adding 100 g of MeCN to the dried compound, the mixture was stirred at 80° C. for 2 hours, followed by filtering and drying to synthesize the yellow dye 2 (12.3 g, 85%).

(Synthesis of photosensitive resin composition)

Examples 1 to 3, Comparative Example 1, Comparative Example 2, and Reference Example 1

The components mentioned below were mixed in the composition shown in Table 1 to prepare a photosensitive resin composition according to Examples 1 to 3, Comparative Examples 1, 2, and Reference Example 1.

Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture was stirred at room temperature for 2 hours, and then a binder resin and a photopolymerizable compound were added thereto, followed by stirring at room temperature for 2 hours. Then, a colorant and other additives were added to the obtained reaction product and stirred at room temperature for 1 hour. Subsequently, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: g) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Reference Example 1 (A) colorant (A-1) 1.441 1.569 1.569 - - 7.218 (A-2) - 12.582 - - - 12.582 (A-3) - - 15.293 - 15.293 - (A-4) - - - 32.218 32.218 - (A-5) 17.980 - - 17.980 - (B) binder resin 0.994 1.435 1.353 0.045 0.045 1.280 (C) photopolymerizable compound 8.949 13.937 11.308 0.012 0.012 8.443 (D) photopolymerization initiator (D-1) 0.600 0.452 0.452 0.452 0.452 0.452 (D-2) 0.016 0.005 0.005 0.005 0.005 0.005 (E) solvent (E-1) 45.220 45.220 45.220 24.488 27.175 45.220 (E-2) 24.500 24.500 24.500 24.500 24.500 24.500 (F) other additives 0.300 0.300 0.300 0.300 0.300 0.300

(A) colorant

(A-1) Compound of Synthesis Example 1 (blue dye represented by Chemical Formula 1-1)

(A-2) Compound of Synthesis Example 2 (blue dye represented by Chemical Formula 3-1)

(A-3) Compound of Synthesis Example 3 (blue dye represented by Chemical Formula 3-2)

(A-4) Compound of Synthesis Example 4 (Yellow Dye 1)

(A-5) C.I. Pigment Blue 15:6 pigment dispersion (SANYO company)

(B) binder resin

Acrylic binder resin (RY-25, Showadenko company)

(C) photopolymerizable compound

Dipentaerythritol hexaacrylate (DPHA) (Japan Explosives Co., Ltd.)

(D) photopolymerization initiator

(D-1) Oxime compound (NCI831, adeka company)

(D-2) Acetophenone-based compound (IRG369, Basf Corporation)

(E) solvent

(E-1) PGMEA (Gyohwa Corporation)

(E-2) EDM (Gyohwa Corporation)

(F) additive

γ-glycidoxy propyl trimethoxysilane (S-510, Chisso Corporation)

Evaluation 1: transmittance of dye

The dyes of Synthesis Example 1, Synthesis Example 4, and Synthesis Example 5 were included in 2% by weight based on the total amount of the composition, and the remaining conditions were the same to prepare three films having a thickness of 2 μm, and the transmittance of each of the films was Measurements are shown in Figure 1 below.

From FIG. 1, unlike the yellow dyes of Synthesis Example 4 and Synthesis Example 5, the blue dye of Synthesis Example 1 has a maximum absorption wavelength in a very narrow wavelength range of 420 nm to 440 nm, and a wavelength range of 420 nm to 440 nm sufficiently even with a small amount It can be seen that the spectroscopy of can be blocked.

Evaluation 2: brightness of photosensitive resin film

The photosensitive resin compositions prepared in Examples 1 to 3, Comparative Examples 1, 2 and Reference Example 1 were prepared in a thickness of 1 µm to 3 µm on a degreasing and washed glass substrate of 250 rpm to 350 rpm. It was applied under conditions and dried on a hot plate at 90° C. for 2 minutes to obtain a coating film. ^{Subsequently, under the condition of 50mJ/cm 2} on the coating film, perform the front exposure using a high-pressure mercury lamp with a dominant wavelength of 365 nm, and then use a KOH developer (111 times dilution) in a developer to wash/develop = 1/0.8 Development was performed for 60 seconds under the conditions of, and water washing was performed for 60 seconds to give a development history. Thereafter, it was dried for 20 minutes in a hot air circulation drying furnace at 230° C. to obtain a color chip.

The prepared color specimen was evaluated for color characteristics based on the C light source using a spectrophotometer (MCPD3000, Otsuka electronic), and the luminance (Y) was calculated based on the color coordinate value (Bx/By = 0.148/0.048), The results are shown in Table 2 below.

Luminance (%) Example 1 7.72 Example 2 8.89 Example 3 8.94 Comparative Example 1 - Comparative Example 2 - Reference Example 1 3.23

(Comparative Example 1 and Comparative Example 2, due to the excessive content of the yellow dye, all components in the allocated solvent were not dissolved, so it was impossible to prepare liquid, so luminance measurement was impossible)

From the evaluations 1 and 2, it can be seen that when the compound represented by Formula 1-1 is used, sufficiently excellent luminance and high color can be realized even with a small amount. In addition, it can be seen from Examples and Reference Examples that the luminance and high color characteristics are not further improved even if the compound represented by Formula 1-1 is contained in an excessive amount.

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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 (20)

(A) a coloring agent containing a compound represented by the following formula (1);
(B) binder resin;
(C) a photopolymerizable compound;
(D) photoinitiator; And
(E) Photosensitive resin composition containing a solvent:
[Formula 1]

In Formula 1,
M is Zn, Co or Cu,
R ¹ to R ²⁰ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, A substituted or unsubstituted sulfonamide group or a substituted or unsubstituted C1 to C20 alkyl ester group,
Provided ^{that at least one of R 1} to R ⁵ , at least one of R ⁶ to R ¹⁰ , at least one of R ¹¹ to R ¹⁵ , and at least one or more of R ¹⁶ to R ²⁰ are each independently a hydrogen atom,
If one of R ¹ to R ⁵ is a halogen atom or an unsubstituted C1 to C20 alkyl group, the remaining four are halogen atoms, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted A cyclic C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group or a substituted or unsubstituted C1 to C20 alkyl ester group,
If one of R ⁶ to R ¹⁰ is a halogen atom or an unsubstituted C1 to C20 alkyl group, the remaining four are halogen atoms, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted A cyclic C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group or a substituted or unsubstituted C1 to C20 alkyl ester group,
If one of R ¹¹ to R ¹⁵ is a halogen atom or an unsubstituted C1 to C20 alkyl group, the remaining four are halogen atoms, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted A cyclic C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group or a substituted or unsubstituted C1 to C20 alkyl ester group,
If one of R ¹⁶ to R ²⁰ is a halogen atom or an unsubstituted C1 to C20 alkyl group, the remaining four are halogen atoms, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted It is a substituted C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group, or a substituted or unsubstituted C1 to C20 alkyl ester group.
The method of claim 1,
The compound represented by Formula 1 is a photosensitive resin composition represented by the following Formula 2:
[Formula 2]

In Chemical Formula 2,
M is Zn, Co or Cu,
R ²¹ to R ²⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted A cyclic sulfonamide group or a substituted or unsubstituted C1 to C20 alkyl ester group,
n1 to n8 are each independently an integer of 0 or 1, provided that 1 ≤ n1+n2 ≤ 2, 1 ≤ n3+n4 ≤ 2, 1 ≤ n5+n6 ≤ 2, 1 ≤ n7+n8 ≤ 2,
However, if R ²¹ , R ²³ , R ²⁵ and R ²⁷ are each independently a halogen atom or an unsubstituted C1 to C20 alkyl group, R ²² , R ²⁴ , R ²⁶ and R ²⁸ are each independently a halogen atom, substituted or unsubstituted A substituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group, or a substituted or unsubstituted C1 to C20 alkyl It is an ester group, and n1 to n8 are each independently an integer of 1.
The method of claim 1,
The compound is a photosensitive resin composition represented by any one of the following Formulas 1-1 to 1-15 and Formulas 1-17 to 1-20.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

In Formula 1-13,
R is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
m1 and m2 are each independently an integer of 0 to 20, provided that 4≦m1+m2≦20,
[Formula 1-14]

[Formula 1-15]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

The method of claim 1,
The compound represented by Formula 1 is a photosensitive resin composition contained in an amount of 0.01% to 7% by weight based on the total amount of the photosensitive resin composition.
The method of claim 1,
The colorant further comprises a blue dye, a blue pigment, a red dye, a red pigment, or a combination thereof.
The method of claim 5,
The blue dye is a photosensitive resin composition represented by the following formula 3:
[Formula 3]

In Chemical Formula 3,
R ²⁹ and R ³⁰ are each independently a substituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group,
R ³¹ is a hydrogen atom or a halogen group,
R ³² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ³³ is a C1 to C20 alkyl group unsubstituted or substituted with an acrylate group,
X ^- is represented by any one of the following formulas A to C.
[Formula A]
SO ₃ ^-
[Formula B]

(In Formula B, n3 is an integer from 0 to 10)
[Formula C]

The method of claim 5,
The blue dye is a photosensitive resin composition represented by the following Formula 3-1 or Formula 3-2:
[Formula 3-1]

[Chemical Formula 3-2]

In Formulas 3-1 and 3-2,
X ^- is represented by any one of the following formulas A to C.
[Formula A]
SO ₃ ^-
[Formula B]

(In Formula B, n3 is an integer from 0 to 10)
[Formula C]

The method of claim 5,
The blue pigment is CI Pigment Blue 15:6 photosensitive resin composition.
The method of claim 1,
The photopolymerization initiator is a photosensitive resin composition comprising an oxime-based initiator and an acetophenone-based initiator.
The method of claim 1,
The photosensitive resin composition is based on the total amount of the photosensitive resin composition,
3% to 20% by weight of a colorant containing the compound represented by Formula 1;
1% to 10% by weight of the binder resin;
1% to 10% by weight of the photopolymerizable compound;
0.1% to 5% by weight of the photopolymerization initiator, and
A photosensitive resin composition comprising the remaining amount of the solvent.
The method of claim 1,
The photosensitive resin composition further comprises an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.
A photosensitive resin film produced by using the photosensitive resin composition of any one of claims 1 to 11.
A color filter comprising the photosensitive resin film of claim 12.
An optical display device comprising the color filter of claim 13.
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