KR20220131691A - Compound, photosensitive resin composition comprising the same, photosensitive resin layer, color filter and display device - Google Patents

Abstract

Disclosed are a compound represented by chemical formula 1, a photosensitive resin composition comprising the same, a photosensitive resin film manufactured by using the photosensitive resin composition, a color filter including the photosensitive resin film, and a display device including the color filter. In the chemical formula 1, each substituent is as defined in the specification.

Description

A compound, a photosensitive resin composition comprising the same, a photosensitive resin film, a color filter, and a display device

The present disclosure relates to a compound, a photosensitive resin composition comprising the same, a photosensitive resin film, a color filter, and a display device.

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

The pigment dispersion method, which is one of the methods for implementing a color filter, involves coating a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposing the pattern to be formed, and then removing the unexposed area with a solvent. This is a method in which a colored thin film is formed by repeating a series of thermal curing processes. The photosensitive resin composition used for manufacturing a 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 is actively applied to the manufacture of LCDs such as mobile phones, notebook computers, monitors, and TVs. However, in recent years, in the photosensitive resin composition for a color filter using a pigment dispersion method having various advantages, not only excellent pattern characteristics but also improved performance is required. In particular, the demand for a colorant that can be applied to an image sensor requiring high brightness and high contrast ratio along with high color gamut is increasing.

An image sensor refers to an image pickup device component that generates an image in a display device such as a mobile phone camera or DSC (Digital Still Camera). It can be classified into an image sensor and a complementary metal oxide semiconductor (CMOS) image sensor.

Since the photosensitive resin film for a color filter used in a solid-state image sensor requires a film thickness of 1.5 μm or less, a large amount of dye must be added to the photosensitive resin composition, thereby lowering the sensitivity, resulting in insufficient adhesion to the substrate, There is a problem in that sufficient curing cannot be obtained, or the pattern formability is remarkably reduced, such as dye eluting even in the exposed portion and losing color.

Accordingly, efforts are being made to develop a photosensitive resin composition for a color filter applicable to an image sensor that satisfies reliability such as luminance and chemical resistance while simultaneously realizing a high color.

One embodiment is to provide a compound capable of implementing a high-definition color pulser.

Another embodiment is to provide a photosensitive resin composition comprising the compound.

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

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

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

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

[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 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group, with the proviso that one of R ¹ to R ⁴ , R ⁵ At least one selected from the group consisting of one of to R ⁸ and one of R ⁹ to R ¹² is represented by the following Chemical Formula 2 or Chemical Formula 3,

[Formula 2]

In Formula 2,

R ¹⁷ is represented by the following formula 2-1,

n is an integer from 1 to 5,

[Formula 2-1]

In Formula 2-1,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or *-O(C=O)NR′-* (R′ is a hydrogen atom or a C1 to C10 alkyl group);

R ¹⁸ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[Formula 3]

In Formula 3,

L ⁴ is a substituted or unsubstituted C1 to C20 alkylene group.

In Formula 1, R ¹³ to R ¹⁶ may be all hydrogen atoms.

In Formula 1, at least one of R ¹ to R ⁴ may be represented by Formula 2 or Formula 3, and the other three may be halogen atoms.

In Formula 1, at least one of R ⁵ to R ⁸ may be represented by Formula 2 or Formula 3, and the other three may be a halogen atom.

In Formula 1, at least one of R ⁹ to R ¹² may be represented by Formula 2 or Formula 3, and the other three may be a halogen atom.

In Formula 1, at least two or more selected from the group consisting of one of R ¹ to R ⁴ , one of R ⁵ to R ⁸ , and one of R ⁹ to R ¹² may be represented by Formula 2 or Formula 3.

The compound represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-5 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

The compound may be a green dye.

The compound may have a maximum absorption wavelength in a wavelength range of 645 nm to 647 nm.

Another embodiment provides a photosensitive resin composition comprising the compound.

The compound may be included in an amount of 1 wt% to 40 wt% based on the total amount of the photosensitive resin composition.

The photosensitive resin composition may further include an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The photosensitive resin composition may further include a pigment.

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

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

Another embodiment provides a display device including the color filter.

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

The compound according to one embodiment has excellent green spectral properties and a high molar extinction coefficient, and has excellent solubility in organic solvents, so it can be used as a dye when preparing a photosensitive resin composition for a green color filter, and a photosensitive resin composition comprising the dye A photosensitive resin film prepared using the , and a color filter including the same may have excellent luminance, contrast ratio, and chemical resistance.

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

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

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

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

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

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

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

One embodiment provides a phthalocyanine-based compound represented by the following formula (1).

[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 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group, with the proviso that one of R ¹ to R ⁴ , R ⁵ At least one selected from the group consisting of one of to R ⁸ and one of R ⁹ to R ¹² is represented by the following Chemical Formula 2 or Chemical Formula 3,

[Formula 2]

In Formula 2,

R ¹⁷ is represented by the following formula 2-1,

n is an integer from 1 to 5,

[Formula 2-1]

In Formula 2-1,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or *-O(C=O)NR′-* (R′ is a hydrogen atom or a C1 to C10 alkyl group);

R ¹⁸ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[Formula 3]

In Formula 3,

L ⁴ is a substituted or unsubstituted C1 to C20 alkylene group.

In a color filter made of a photosensitive resin composition using a pigment as a colorant, there is a limit to the luminance and contrast ratio resulting from the size of the pigment particle, so the need to improve the luminance and contrast ratio is continuously raised. Efforts to implement a color filter with improved luminance and contrast ratio by preparing a photosensitive resin composition suitable for the dye by introducing a dye that does not form , has shown some effect on improving luminance or contrast ratio.

Meanwhile, in recent years, the demand for a photosensitive resin composition that can be applied to a solid-state image sensor or a complementary metal oxide semiconductor image sensor in addition to a conventional display device such as an LCD is rapidly increasing. In this case, when applied to the image sensor, it is impossible to realize a high color, so a problem that it is very difficult to manufacture a high-definition color filter is newly emerging. The reason why high color cannot be realized as described above is thought to be because the pattern size of a color filter mounted on a solid-state image sensor or the like is very small, about 1/100 to 1/200 times the size of a color filter pattern for a conventional LCD.

Therefore, the inventors of the present invention, after a long study, by modifying the structure of the phthalocyanine-based compound as shown in Chemical Formula 1, it can be easily applied to a pattern having a size 100 to 200 times smaller than the color filter pattern size for a conventional LCD, By increasing the resolution and reducing the residue, a dye compound used in a photosensitive resin composition for a color filter having excellent developability compared to a conventional photosensitive resin composition has been developed.

For example, the compound represented by Formula 1 may have a maximum absorption wavelength in a wavelength range of 645 nm to 647 nm. Even if it is a phthalocyanine-based compound of the same series, the phthalocyanine-based compound that does not have the structure as in Formula 1 has a region where the maximum absorption wavelength appears is less than 645 nm or more than 647 nm, phthalocyanine according to an embodiment represented by Formula 1 Compared with the cyanine-based compound, there is a big difference in that the solubility in an organic solvent is lowered, and the luminance and chemical resistance of the photosensitive resin composition including the same as a colorant are inferior. That is, the compound according to an embodiment controls the maximum absorption wavelength region of the phthalocyanine-based compound very finely, and thus has superior green spectral properties and a high molar extinction coefficient compared to the conventional phthalocyanine-based compound, and has color characteristics such as luminance, contrast, and resistance It is possible to provide a photosensitive resin composition with more improved chemical properties.

For example, in Formula 1, R ¹³ to R ¹⁶ may be all hydrogen atoms. In this case, it is not difficult to use the compound represented by Chemical Formula 1 as a colorant in the photosensitive resin composition for a color filter, and it can be easily implemented as a high-color reproduction image sensor.

For example, the substituent represented by Formula 2 may be represented by Formula 2A below.

[Formula 2A]

In Formula 2,

R ¹⁷ is represented by Formula 2-1.

As in Formula 2A, when the substituent represented by R ¹⁷ is substituted at the para position, brightness and chemical resistance may be further improved. For example, when the substituent represented by R ¹⁷ is substituted at an ortho and/or meta position, it may be difficult to implement a green pixel for a color filter.

For example, in Formula 1, 1 to 3 substituents represented by Formula 2 or Formula 3 may be present. In Formula 1, when the substituents represented by Formula 2 or Formula 3 do not exist, the effect of improving color characteristics such as improvement of brightness or contrast cannot be expected, and four or more substituents represented by Formula 2 or Formula 3 exist. In this case, it may be undesirable due to poor storage stability. For example, in Formula 1, i) one selected from the group consisting of one of R ¹ to R ⁴ , one of R ⁵ to R ⁸ , and one of R ⁹ to R ¹² is represented by Formula 2 or Formula 3, or ii ) one of R ¹ to R ⁴ , one of R ⁵ to R ⁸ , and one of R ⁹ to R ¹² are represented by Formula 2 or Formula 3, or iii) among R ¹ to R ⁴ One, three selected from the group consisting of one of R ⁵ to R ⁸ and one of R ⁹ to R ¹² may be represented by Formula 2 or Formula 3 above.

For example, in Formula 1, at least one of R ¹ to R ⁴ may be represented by Formula 2 or Formula 3, and the other three may be halogen atoms. In this case, R ⁵ to R ⁸ may be all hydrogen atoms or halogen atoms, and R ¹³ to R ¹⁶ may be all hydrogen atoms.

For example, in Formula 1, at least one of R ¹ to R ⁴ may be represented by Formula 2 or Formula 3, the other three may be a halogen atom, and at least one of R ⁵ to R ⁸ may be represented by Formula 2 or Formula 3 , and the remaining three may be halogen atoms. In this case, all of R ⁹ to R ¹⁶ may be hydrogen atoms.

For example, in Formula 1, at least one of R ¹ to R ⁴ may be represented by Formula 2 or Formula 3, the other three may be a halogen atom, and at least one of R ⁹ to R ¹² may be represented by Formula 2 or Formula 3 , and the remaining three may be halogen atoms. In this case, R ⁵ to R ⁸ and R ¹³ to R ¹⁶ may all be hydrogen atoms.

For example, in Formula 1, at least one of R ¹ to R ⁴ may be represented by Formula 2 or Formula 3, the other three may be a halogen atom, and at least one of R ⁵ to R ⁸ may be represented by Formula 2 or Formula 3 , the remaining three may be halogen atoms, at least one of R ⁹ to R ¹² may be represented by Formula 2 or Formula 3, and the remaining three may be halogen atoms. In this case, all of R ¹³ to R ¹⁶ may be hydrogen atoms.

For example, the phthalocyanine-based compound represented by Formula 1 includes 4 or more hydrogen atoms and 6 or more halogen atoms in the parent, and further, a substituent represented by Formula 2 or Formula 3 on the benzene ring including the halogen atom Solubility in organic solvents can be further improved due to the structural features included. More specifically, the phthalocyanine-based compound represented by Formula 1 is a) a benzene ring having a group represented by R ¹ to R ⁴ , b) a benzene ring having a group represented by R ⁵ to R ⁸ c) R ⁹ to R ¹² A benzene ring having a group represented by and d) four benzene rings of a benzene ring having a group represented by R ¹³ to R ¹⁶ are included in the parent, and a substituent represented by Formula 2 or Formula 3 among the four benzene rings is In the benzene ring including, all other three groups other than the substituents represented by Formula 2 or Formula 3 are halogen atoms, and all four groups of the benzene ring not including the substituents represented by Formula 2 or Formula 3 are hydrogen atoms or halogens. It can be an atom, and due to this structural feature, the region where the maximum absorption wavelength appears can be easily controlled from 645 nm to 647 nm, which can further improve solubility in organic solvents, and is advantageous in terms of improving luminance and securing process characteristics. can

Above all, even if it is a phthalocyanine-based compound of the same series, if it does not have the structure represented by Chemical Formula 1, the maximum absorption wavelength does not appear in the wavelength range of 645 nm to 647 nm. A photosensitive resin containing such a phthalocyanine-based compound as a colorant The composition has greatly reduced luminance and chemical resistance, or cannot achieve high color. That is, the phthalocyanine-based compound according to an embodiment is different from the conventional phthalocyanine-based compound in structural and spectroscopic aspects in that the region where the maximum absorption wavelength appears is 645 nm to 647 nm, and at the same time has the structure represented by Chemical Formula 1 there is

For example, the compound represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-5, but is not necessarily limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

For example, since the phthalocyanine-based compound represented by Formula 1 includes one to three substituents represented by Formula 2 or Formula 3, a clearer color can be expressed even with a small amount, so that when used as a colorant, luminance or It is possible to manufacture a display device having excellent color characteristics such as contrast ratio. For example, the compound may be a colorant, such as a dye, such as a green dye.

In general, the dye is the most expensive component among the components used in the color filter. Therefore, in order to achieve a desired effect, for example, high luminance or high contrast ratio, more expensive dyes must be used, which inevitably increases the production cost. However, when the compound according to one embodiment is used as a dye in a color filter, excellent color characteristics such as high brightness and high contrast ratio can be achieved even with a small amount, so that production cost can be reduced.

According to another embodiment, there is provided a photosensitive resin composition comprising the phthalocyanine-based compound according to the embodiment.

For example, the photosensitive resin composition may include a phthalocyanine-based compound, a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent according to the exemplary embodiment.

The compound according to the exemplary embodiment may serve as a colorant, such as a dye, such as a green dye, in the photosensitive resin composition, thereby exhibiting excellent color characteristics.

The compound according to one embodiment is 1% to 40% by weight, such as 10% to 40% by weight, such as 20% to 40% by weight, such as 1% to 30% by weight, such as based on the total amount of the photosensitive resin composition It may be included in an amount of 1% to 20% by weight, such as 1% to 10% by weight. When the compound according to an embodiment is included in the above range, the color gamut and contrast ratio are excellent .

The photosensitive resin composition may further include a pigment, such as a yellow pigment, a green pigment, or a combination thereof.

The yellow pigment has C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150 etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The green pigment has C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59 etc. are mentioned, These can be used individually or in mixture of 2 or more types.

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

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

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

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

Examples of commercially available products of the dispersant include BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemicals; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse24000GR, Solsperse 27000, Solsperse 28000, etc. from Zeneka; or Ajinomoto's PB711 and PB821.

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

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

The pigment dispersion may be included in an amount of 10 wt% to 20 wt%, for example 12 wt% to 18 wt%, based on the total amount of the photosensitive resin composition. When the pigment dispersion is included within the above range, it is advantageous to secure a process margin, and the color reproducibility and contrast ratio are excellent.

The binder resin may be an acrylic resin.

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

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

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

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

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

For example, the binder resin may further include an epoxy resin together with the acrylic resin.

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 acid value of the binder resin may be 15 mgKOH/g to 60 mgKOH/g, for example, 20 mgKOH/g to 50 mgKOH/g 　. When the acid value of the 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 wt% to 20 wt%, for example 1 wt% to 15 wt%, for example 1 wt% to 10 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included in the above range, excellent developability and improved crosslinking properties can be obtained during the manufacture of a color filter, thereby obtaining excellent surface smoothness.

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 forming 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, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylol propane tri ( and meth)acrylate, tris(meth)acryloyloxyethyl phosphate, and novolac epoxy (meth)acrylate.

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

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

The photopolymerizable compound may be included in an amount of 1 wt% to 15 wt%, for example 1 wt% to 10 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, curing occurs sufficiently during exposure in the pattern forming process to provide excellent reliability and excellent developability in an alkaline developer.

The photopolymerization initiator is an initiator generally used in the photosensitive resin composition, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based 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, p-t-butyltrichloroacetophenone, p-t -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino propane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoylbenzoic acid, methylbenzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc. are mentioned.

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

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

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

Examples of the oxime-based compound include an O-acyloxime-based compound, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, and 1-(o-acetyloxime). )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one etc. can be used. Specific examples of the O-acyloxime compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2 -oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O- Acetate etc. are mentioned.

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

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

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

The photopolymerization initiator may be included in an amount of 0.01 wt% to 10 wt%, for example, 0.1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure in the pattern forming process to obtain excellent reliability, and the pattern has excellent heat resistance, light resistance and chemical resistance, and also has excellent resolution and adhesion. A decrease in transmittance can be prevented.

As the solvent, materials having compatibility with but not reacting with the compound, pigment, binder resin, photopolymerizable compound, and photoinitiator according to the embodiment may be used.

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

Of these, preferably, in consideration of compatibility and reactivity, 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/or ketones such as cyclohexanone may be used.

The solvent may be included in a balance, for example, 30 wt% to 80 wt%, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, since the photosensitive resin composition has an appropriate viscosity, processability in manufacturing the color filter is excellent.

The photosensitive resin composition may further include a compound represented by the following formula (4).

[Formula 4]

In Formula 3,

R ²³ and R ²⁴ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C20 alkyl group,

L ⁵ To L ⁷ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

n1 and n2 are each independently an integer of 0 to 5, and 3 ≤ n1+n2 ≤ 5.

For example, the compound represented by Formula 4 may function as an antioxidant.

For example, in Formula 4, R ²³ may be a C1 to C20 alkyl group substituted with an alkyl group, R ²⁴ may be a hydroxyl group, n1 may be an integer of 2, and n2 may be an integer of 1.

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

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

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

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, and an epoxy group in order 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 glycidoxy propyl tri Methoxysilane, β-epoxycyclohexyl)ethyltrimethoxysilane, etc. are mentioned, and these can be used individually or in mixture of 2 or more types.

The silane coupling agent may be included in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane 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 the formation of defects, if necessary.

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

The surfactant may be used in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is secured, staining does not occur, and wettability to a 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, there is provided a color filter manufactured using the photosensitive resin composition according to the embodiment.

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

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

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

(synthesis of compounds)

Synthesis Example 1: Synthesis of the compound represented by Formula 1-1

3,4,5,6-tetrachlorophthalonitrile (10g), 4-Hydroxybenzyl Alcohol (4.8g), K ₂ CO ₃ (7.8g), N,N-dimethylformamide (N,N-dimethylformamide) (50ml) in a 100ml flask ) and stirred while heating to 70 °C. After completion of the reaction, the solid obtained by extraction with EA (ethyl acetate) and concentration was dissolved in a small amount of DCM (dichloromethane), washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro-5-(4) -Hydroxymethyl-phenoxy)-phthalonitrile is obtained.

Put the 3,4,6-Trichloro-5-(4-Hydroxymethyl-phenoxy)-phthalonitrile (5.0g), Triethylamine (2.15g) and 25ml of chloroform in a 100ml flask, cool to 0°C, and then stir while stirring Methacryloyl Chloride (1.48) g) is added slowly. After the input is complete, remove the ice bath and stir at room temperature (25°C) for 2 hours. After completion of the reaction, extraction with DCM was performed, moisture was removed with anhydrous magnesium sulfate, and the filtered filtrate was concentrated, and the resulting solid was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro Obtain -5-(4-Methyl Methacrylate-phenoxy)-phthalonitrile.

In a 100 mL flask, phthalonitrile (0.5 g), the above 3,4,6-Trichloro-5-(4-Methyl Methacrylate-phenoxy)-phthalonitrile (1.65 g), 1,8-Diazabicycloundec-7-ene (1.19 g) and 1 -Pentanol (14g) was added and heated to 90°C to confirm that the solid was dissolved. Then, zinc acetate (0.36g) was added, the temperature was raised to 140°C, and stirred while heating. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to finally obtain a compound represented by the following Chemical Formula 1-1.

[Formula 1-1]

Maldi-tof MS: 1165 m/z

Synthesis Example 2: Synthesis of a compound represented by Formula 1-2

Put 3,4,5,6-tetrachlorophthalonitrile (10g), 4-Hydroxybenzyl Alcohol (4.8g), K2CO3 (7.8g), N,N-dimethylformamide (N,N-dimethylformamide) (50ml) in a 100ml flask Stir while heating to 70°C. After completion of the reaction, the solid obtained by extraction with EA (ethyl acetate) and concentration was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro-5-(4-Hydroxymethyl-phenoxy). )-phthalonitrile is obtained.

In a 100ml flask, put 3,4,6-Trichloro-5-(4-Hydroxymethyl-phenoxy)-phthalonitrile (5.0g), Triethylamine (2.15g) and 25ml of chloroform, cooled to 0°C, and then stirred while stirring Acryloyl Chloride (1.28) g) is added slowly. After the input is complete, remove the ice bath and stir at room temperature (25°C) for 2 hours. After completion of the reaction, extraction with DCM was performed, moisture was removed with anhydrous magnesium sulfate, and the filtered filtrate was concentrated, and the resulting solid was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro Obtain -5-(4-Methyl acrylate-phenoxy)-phthalonitrile.

In a 100 mL flask, phthalonitrile (0.5 g), the above 3,4,6-Trichloro-5-(4-Methyl acrylate-phenoxy)-phthalonitrile (1.59 g), 1,8-Diazabicycloundec-7-ene (1.19 g) and 1 -Pentanol (14g) was added and heated to 90°C to confirm that the solid was dissolved. Then, zinc acetate (0.36g) was added, the temperature was raised to 140°C, and stirred while heating. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and dried under vacuum to finally obtain a compound represented by the following Chemical Formula 1-2. (Maldi-tof MS: 1136.94 m/z)

[Formula 1-2]

Maldi-tof MS: 1136.94 m/z

Synthesis Example 3: Synthesis of a compound represented by Formula 1-3

Put 3,4,5,6-tetrachlorophthalonitrile (10g), 4-Hydroxybenzyl Alcohol (4.8g), K2CO3 (7.8g), N,N-dimethylformamide (N,N-dimethylformamide) (50ml) in a 100ml flask Stir while heating to 70°C. After completion of the reaction, the solid obtained by extraction with EA (ethyl acetate) and concentration was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro-5-(4-Hydroxymethyl-phenoxy). )-phthalonitrile is obtained.

In a 100ml flask, put 3,4,6-Trichloro-5-(4-Hydroxymethyl-phenoxy)-phthalonitrile (5.0g), Triethylamine (2.15g) and 25ml of chloroform, cooled to 0°C, and then stirred while stirring Acryloyl Chloride (1.28) g) is added slowly. After the input is complete, remove the ice bath and stir at room temperature (25°C) for 2 hours. After the reaction was completed, DCM was extracted, water was removed with anhydrous magnesium sulfate, and the filtered filtrate was concentrated and the solid obtained was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro- 5-(4-Methylacrylate-phenoxy)-phthalonitrile is obtained.

In a 100 mL flask, phthalonitrile (0.5 g), 3,4,5,6-tetrachlorophthalonitrile (0.52 g), the 3,4,6-Trichloro-5- (4-Methylacrylate-phenoxy)-phthalonitrile (0.80 g), 1, 8-Diazabicycloundec-7-ene (1.19g) and 1-pentanol (14g) were added and heated to 90°C to confirm that the solid was dissolved. Then, zinc acetate (0.36g) was added, the temperature was raised to 140°C, and stirred while heating. do. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and dried under vacuum to finally obtain a compound represented by the following Chemical Formula 1-3.

[Formula 1-3]

Maldi-tof MS: 995.22 m/z

Synthesis Example 4: Synthesis of a compound represented by Formula 1-4

Put 3,4,5,6-tetrachlorophthalonitrile (10g), 4-Hydroxybenzyl Alcohol (4.8g), K2CO3 (7.8g), N,N-dimethylformamide (N,N-dimethylformamide) (50ml) in a 100ml flask Stir while heating to 70°C. After completion of the reaction, the solid obtained by extraction with EA (ethyl acetate) and concentration was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro-5-(4-Hydroxymethyl-phenoxy). )-phthalonitrile is obtained.

Put the 3,4,6-Trichloro-5-(4-Hydroxymethyl-phenoxy)-phthalonitrile (5.0g), Triethylamine (2.15g) and 25ml of chloroform in a 100ml flask, and add 2-Isocyanatoethyl Methacrylate (2.19g) while stirring. Then, it is stirred while heating to 60 °C. After completion of the reaction, DCM was extracted, water was removed with anhydrous magnesium sulfate, and the filtered filtrate was concentrated to dissolve the obtained solid in a small amount of DCM, washed several times with hexane, filtered and dried in vacuo to 2-[[4-(2) ,3,6-trichloro-4,5-dicyano-phenoxy)phenyl]methoxycarbonylamino]ethyl 2-methylprop-2-enoate is obtained.

In a 100 mL flask, phthalonitrile (0.5 g), 3,4,5,6-tetrachlorophthalonitrile (0.52 g), the above 2-[[4-(2,3,6-trichloro-4,5-dicyano-phenoxy)phenyl]methoxycarbonylamino ]ethyl 2-methylprop-2-enoate (0.99g), 1,8-Diaza bicycloundec-7-ene (1.19g) and 1-pentanol (14g) were added and heated to 90℃ to confirm that the solid was dissolved. Zinc acetate (0.36 g) was added, and the temperature was raised to 140 °C, followed by stirring while heating. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and dried under vacuum to finally obtain a compound represented by the following Chemical Formula 1-4.

[Formula 1-4]

Maldi-tof MS: 1096.32 m/z

Synthesis Example 5: Synthesis of a compound represented by Formula 1-5

3,4,5,6-tetrachlorophthalonitrile (10g), 2-(4-Hydroxyphenyl)ethanol (5.35g), K2CO3 (7.8g), N,N-dimethylformamide (N,N-dimethylformamide) ( 50ml) and stirred while heating to 70°C. After completion of the reaction, the solid obtained by extraction with EA (ethyl acetate) and concentration was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro-5-(4-Hydroxyethyl-phenoxy). )-phthalonitrile is obtained.

In a 100ml flask, put the 3,4,6-Trichloro-5-(4-Hydroxyethyl-phenoxy)-phthalonitrile (5.0g), Triethylamine (2.06g) and 25ml of chloroform, cooled to 0℃, and then stirred while Epichlorohydrin (1.26g) ) is introduced slowly. After the input is complete, remove the ice bath and stir at room temperature (25°C) for 2 hours. After completion of the reaction, extraction with DCM was performed, moisture was removed with anhydrous magnesium sulfate, and the filtered filtrate was concentrated, and the resulting solid was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro -5-(4-(2-(Oxiran-2-ylmethoxy)ethyl)phenoxy)-phthalonitrile is obtained.

In a 100 mL flask, phthalonitrile (0.5 g), the above 3,4,5,6-tetrachlorophthalonitrile (0.52 g), 3,4,6-Trichloro-5-(4-(2-(Oxiran-2-ylmethoxy)ethyl)phenoxy )-phthalonitrile (0.83g), 1,8-Diazabicycloundec-7-ene (1.19g) and 1-pentanol (14g) were added and heated to 90°C to confirm that the solid was dissolved. Then, zinc acetate (0.36g) was added. After heating to 140 ℃, and stirred while heating. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and dried under vacuum to finally obtain a compound represented by the following Chemical Formula 1-5.

[Formula 1-5]

Maldi-tof MS: 1011.26 m/z

Comparative Synthesis Example 1: Synthesis of a compound represented by Formula C-1

In a 100mL flask, 4-(2-sec-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (1g), 1,8-Diazabicycloundec-7-ene (0.30g), 1-pentanol (7g), Add zinc acetate (0.12 g) and stir while heating to 140 °C. After completion of the reaction, it is purified by column chromatography. After purification, the obtained liquid is concentrated to obtain a solid. The crystallized solid is vacuum-dried to obtain a compound represented by the following Chemical Formula C-1.

[Formula C-1]

Maldi-tof MS: 1584.04 m/z

Comparative Synthesis Example 2: Synthesis of a compound represented by Formula C-2

3,4,5,6-tetrachlorophthalonitrile (5g), 2,4-di-tert-butylphenol (2.75g), K ₂ CO ₃ (3.9 g), N,N-dimethylformamide (N,N) in a 100ml flask -dimethylformamide) (25 ml) is added and stirred while heating to 70 °C. After completion of the reaction, the solid obtained by extraction with EA (ethyl acetate) and concentration was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro-5-(2,4-dimethyl -phenoxy)-phthalonitrile is obtained.

3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (1 g), 1,8-Diazabicycloundec-7-ene (1.08 g) and 1-pentanol in a 100 mL flask (14g) was added and heated to 90℃ to dissolve the solid, then zinc acetate (0.26g) was added and stirred while heating to 140℃. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following Chemical Formula C-2.

[Formula C-2]

Maldi-tof MS: 1808.47 m/z

Comparative Synthesis Example 3: Synthesis of a compound represented by Formula C-3

3,4,5,6-tetrachlorophthalonitrile (5 g), 2,4-dimethoxyphenol (3.47 g), K ₂ CO ₃ (3.9 g), N,N-dimethylformamide (N,N-dimethylformamide) ( 25ml) and stirred while heating to 70°C. After completion of the reaction, the solid obtained by extraction with EA (ethyl acetate) and concentration was dissolved in a small amount of DCM, washed several times with hexane, filtered and dried under vacuum to 3,4,6-Trichloro-5-(2,4-dimethoxy). -phenoxy)-phthalonitrile is obtained.

3,4,6-Trichloro-5-(2,4-dimethoxy-phenoxy)-phthalonitrile (2g), 1,8-Diazabicycloundec-7-ene (0.99g) and 1-pentanol (14g) in a 100mL flask After confirming that the solid is dissolved by heating to 90°C, add zinc acetate (0.24g), increase the temperature to 140°C, and stir while heating. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following Chemical Formula C-3.

[Formula C-3]

Maldi-tof MS: 1591.80 m/z

Comparative Synthesis Example 4: Synthesis of a compound represented by Formula C-4

4-(2,4-dimethoxy-phenoxy)-3,5,6-trichloro-phthalonitrile (0.7g), 3,4,5,6-Tetrachlorophthalonitrile (1.45g), 1 of Synthesis Example 1-2 in a 100mL flask ,8-Diazabicycloundec-7-ene (1.38g) and 1-pentanol (14g) were added and heated to 90℃ to confirm that the solid was dissolved. Then, zinc acetate (0.33g) was added, the temperature was raised to 140℃, and while heating Stir. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and dried under vacuum to obtain a compound represented by the following Chemical Formula C-4.

[Formula C-4]

Maldi-tof MS: 1237.54 m/z

Comparative Synthesis Example 5: Synthesis of a compound represented by Formula C-5

4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.70g), 4,5-dichlorophthalonitrile (0.52g) in a 100mL flask ) 1,8-Diazabicycloundec-7-ene (2.01 g) and 1-pentanol (15 g) were added and heated to 90 ° C to confirm that the solid was dissolved. Then, zinc acetate (0.48 g) was added and the temperature was raised to 140 ° C. Stir while heating. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following Chemical Formula C-5.

[Formula C-5]

Maldi-tof MS: 1287.63 m/z

Comparative Synthesis Example 6: Synthesis of a compound represented by Formula C-6

4-(2-tert-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (2g), 3,4,5,6-tetrachlorophthalonitrile (0.70g), 4-dichlorophthalonitrile (0.43g) 1 in a 100mL flask ,8-Diazabicycloundec-7-ene (2.01g) and 1-pentanol (15g) were added and heated to 90℃ to confirm that the solid was dissolved. Then, zinc acetate (0.48g) was added, the temperature was raised to 140℃, and heating Stir. After completion of the reaction, precipitation is confirmed with methanol, filtered and vacuum dried. The dried solid is purified by column chromatography. The solid obtained after purification is dissolved in an appropriate amount of DCM and crystallized by adding methanol. The crystallized solid is filtered and dried under vacuum to obtain a compound represented by the following Chemical Formula C-6.

[Formula C-6]

Maldi-tof MS: 1253.19 m/z

Evaluation 1: Measurement of the maximum absorption wavelength

The compounds according to Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 6 were prepared at a concentration of 0.005wt% using a diluting solvent (PGMEA), and the Synthesis Examples 1 to 5 and comparison Absorption spectra for each of the phthalocyanine-based compounds according to Synthesis Examples 1 to 6 were obtained, and the results are shown in Table 1 below. (UV-1800, SHIMADZU)

Maximum absorption wavelength (nm) Synthesis Example 1 643 Synthesis Example 2 642 Synthesis Example 3 642 Synthesis Example 4 641 Synthesis Example 5 642 Comparative Synthesis Example 1 653 Comparative Synthesis Example 2 649 Comparative Synthesis Example 3 648 Comparative Synthesis Example 4 651 Comparative Synthesis Example 5 650 Comparative Synthesis Example 6 648

Evaluation 2: Determination of solubility

To 0.5 g of the compounds according to Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 6, respectively, a diluting solvent (PGMEA) was added, and the solution was mixed with a mixing rotor (iuchi Co., Ltd., MIXROTAR VMR-5) After stirring at 25 ℃ rpm for 1 hour, the solubility of each compound was confirmed in Table 2 below.

Solubility evaluation criteria

10% by weight or more of the compound (solute) dissolved with respect to the total amount of the diluent: ○

Less than 10% by weight of the compound (solute) dissolved with respect to the total amount of the diluent: X

(Unit: % by weight) Solubility Synthesis Example 1 ○ Synthesis Example 2 ○ Synthesis Example 3 ○ Synthesis Example 4 ○ Synthesis Example 5 ○ Comparative Synthesis Example 1 X Comparative Synthesis Example 2 X Comparative Synthesis Example 3 X Comparative Synthesis Example 4 X Comparative Synthesis Example 5 X Comparative Synthesis Example 6 X

From Table 2, the compounds of Synthesis Examples 1 to 5, which are compounds according to one embodiment, have superior solubility in organic solvents than the compounds of Comparative Synthesis Examples 1 to 6, which is excellent when used in a photosensitive resin composition, etc. It can be confirmed that color characteristics can be exhibited.

(Synthesis of photosensitive resin composition)

Examples 1 to 5 and Comparative Examples 1 to 6

The photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 6 were prepared by mixing the components mentioned below in the composition shown in Table 3 below.

Specifically, a photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours, and then a binder resin and a photopolymerizable monomer were added thereto and stirred at room temperature for 2 hours. Then, the compound (dye) and pigment (pigment dispersion form) prepared in the above Synthesis Example were added as a colorant to the obtained reactant and stirred at room temperature for 1 hour. Then, an antioxidant and a leveling agent were added, and the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: % by weight) Example comparative example One 2 3 4 5 One 2 3 4 5 6 binder resin EHPE-3150
(DAICEL, Epoxy) 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 NPR-5216
(Miwon, acrylic) 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 7.91 photopolymerizable monomer GM66G0P
(QPPC) 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 Miramer 2200
(Miwon) 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 photopolymerization initiator SPI-03
(Samyang Corporation) 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 IRG369
(BASF) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 antioxidant AO-80
(ADEKA) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 pigment G58 pigment dispersion (SANYO, AG1623) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Y138 pigment dispersion (ENF, EC-1200Y) 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 dyes 30.22 (Synthesis Example 1) 30.22 (Synthesis Example 2) 30.22 (Synthesis Example 3) 30.22 (Synthesis Example 4) 30.22 (Synthesis Example 5) 30.22 (Comparative Synthesis Example 1) 30.22 (Comparative Synthesis Example 2) 30.22 (Comparative Synthesis Example 3) 30.22 (Comparative Synthesis Example 4) 30.22 (Comparative Synthesis Example 5) 30.22
(Comparative Synthesis Example 6) menstruum PGMEA (DAICEL) 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 leveling agent F554 (DIC) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

Evaluation 3: Color coordinates, luminance, chemical resistance, developability and surface wrinkles

The photosensitive resin composition prepared in Examples 1 to 5 and Comparative Examples 1 to 6 was applied to a thickness of 1 μm to 3 μm on a degreasing-washed glass substrate having a thickness of 1 mm, and a hot plate at 90° C. A coating film was obtained by drying on the bed for 2 minutes. Subsequently, the coating film was exposed using a high-pressure mercury lamp having a dominant wavelength of 365 nm. Thereafter, the sample was obtained by drying for 5 minutes in a hot air circulation drying furnace at 200°C. The pixel layer was evaluated for color purity based on the C light source using a spectrophotometer (MCPD3000, Otsuka electronic), and the luminance and contrast ratio were calculated based on the CIE color coordinates, and are shown in Table 4 below.

In addition, after measuring the initial thickness of the sample (photoresist film) obtained by exposure and drying, it was placed in an NMP solvent at 25° C. for 10 minutes, washed with ultrapure water for 30 seconds, and then dried by blowing with compressed air. Thereafter, the del(E*) value was measured using the spectrophotometer to confirm the chemical resistance, and the results are shown in Table 4 below.

Criteria for evaluation of chemical resistance

del(E*) less than 3: ○

del(E*) is 3 or greater: X

Luminance (%) contrast ratio chemical resistance Example 1 65.5 14400 O Example 2 66.6 14900 O Example 3 66.8 15100 O Example 4 66.5 15000 O Example 5 66.6 14900 O Comparative Example 1 60.1 14300 X Comparative Example 2 60.0 14400 X Comparative Example 3 58.8 13800 X Comparative Example 4 59.8 13900 X Comparative Example 5 59.1 13700 X Comparative Example 6 58.1 13700 X

From Table 4, the photosensitive resin composition of Examples 1 to 5 including the compound according to an embodiment as a dye compared with the photosensitive resin composition of Comparative Examples 1 to 6 not including the compound, luminance , it can be confirmed that it is possible to manufacture a high-definition display device having excellent color characteristics by being easily applied to an image sensor and the like due to excellent contrast ratio and chemical resistance.

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

Claims (15)

A compound represented by the following formula (1):
[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 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group, with the proviso that one of R ¹ to R ⁴ , R ⁵ At least one selected from the group consisting of one of to R ⁸ and one of R ⁹ to R ¹² is represented by the following Chemical Formula 2 or Chemical Formula 3,
[Formula 2]

In Formula 2,
R17 is represented by the following formula 2-1,
n is an integer from 1 to 5,
[Formula 2-1]

In Formula 2-1,
L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or *-O(C=O)NR′-* (R′ is a hydrogen atom or a C1 to C10 alkyl group);
R ¹⁸ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
[Formula 3]

In Formula 3,
L ⁴ is a substituted or unsubstituted C1 to C20 alkylene group.
According to claim 1,
At least two selected from the group consisting of one of R ¹ to R ⁴ , one of R ⁵ to R ⁸ , and one of R ⁹ to R ¹² are compounds represented by Formula 2 or Formula 3.
According to claim 1,
At least one of R ¹ to R ⁴ is represented by Formula 2 or Formula 3, and the other three are halogen atoms.
According to claim 1,
At least one of R ⁵ to R ⁸ is represented by Formula 2 or Formula 3, and the other three are halogen atoms.
According to claim 1,
At least one of R ⁹ to R ¹² is represented by Formula 2 or Formula 3, and the other three are halogen atoms.
According to claim 1,
The compound represented by Formula 1 is a compound represented by any one of Formulas 1-1 to 1-5.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

According to claim 1,
The compound is a green dye.
According to claim 1,
The compound has a maximum absorption wavelength in the wavelength region of 645nm to 647nm.
The photosensitive resin composition containing the compound of any one of Claims 1-8.
10. The method of claim 9,
The compound is included in an amount of 1 wt% to 40 wt% based on the total amount of the photosensitive resin composition.
10. The method of claim 9,
The photosensitive resin composition further comprises a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent.
10. The method of claim 9,
The photosensitive resin composition further comprises a pigment.
A photosensitive resin film produced by using the photosensitive resin composition of claim 9 .
A color filter comprising the photosensitive resin film of claim 13 .
A display device comprising the color filter of claim 14 .