KR102129509B1 - Novel compound,photosensitive resin composition comprising the same and color filter - Google Patents

Abstract

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

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

Description

New compound, photosensitive resin composition and color filter comprising the same{NOVEL COMPOUND,PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME AND COLOR FILTER}

The present description relates to a novel compound, a photosensitive resin composition comprising the same, and a color filter.

In a color filter made of a pigment-type photosensitive resin composition, there are limitations in brightness and contrast ratio resulting from pigment particle size. In addition, in the case of a color imaging element for an image sensor, a smaller dispersion particle size is required to form a fine pattern. In order to meet these demands, attempts have been made to realize a color filter having improved color characteristics such as brightness and contrast ratio by preparing a photosensitive resin composition incorporating dyes that do not form particles instead of pigments.

Therefore, there is a need to study a compound suitable as a dye used in the production of a photosensitive resin composition.

One embodiment is to provide novel compounds.

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

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

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

[Formula 1]

In Chemical Formula 1,

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

However, at least one of R ¹ to R ¹⁶ is a halogen atom,

At least one of R ¹ to R ¹⁶ is represented by the following Chemical Formula 2-1,

At least one of R ¹ to R ¹⁶ is represented by the following Formula 2-2,

[Formula 2-1]

[Formula 2-2]

In Chemical Formulas 2-1 and 2-2,

R ¹⁷ is a C2 to C10 alkyl group substituted with a C1 to C10 alkyl group,

R ¹⁸ and R ¹⁹ are each independently a halogen atom, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n1 is an integer from 2 to 5,

n2 and n3 are each independently an integer of 0 to 5, provided that 1≦n2+n3≦5.

The Chemical Formula 2-1 may be represented by the following Chemical Formula 2-1-1.

[Formula 2-1-1]

In the above formula 2-1-1,

R ²⁰ and R ²¹ are each independently a C2 to C10 alkyl group substituted with a C1 to C5 alkyl group.

The formula 2-2 may be represented by any one of the following formulas 2-2-1 to 2-2-3.

[Formula 2-2-1]

[Formula 2-2-2]

[Formula 2-2-3]

In Formula 2-2-1 to Formula 2-2-3,

R ²² and R ²³ are each independently a substituted or unsubstituted C3 to C20 cycloalkyl group,

R ²⁴ and R ²⁵ are each independently a halogen atom.

At least one of R ¹ to R ⁴ is represented by Formula 2-1, at least one of R ⁵ to R ⁸ is represented by Formula 2-2, and at least one of R ⁹ to R ¹² is represented by Formula 2-2, and at least one of R ¹³ to R ¹⁶ may be represented by Formula 2-2.

At least one of R ¹ to R ⁴ is represented by Formula 2-1, at least one of R ⁵ to R ⁸ is represented by Formula 2-1, and at least one of R ⁹ to R ¹² is represented by Formula 2-2, and at least one of R ¹³ to R ¹⁶ may be represented by Formula 2-2.

At least one of R ¹ to R ⁴ is represented by Formula 2-1, at least one of R ⁵ to R ⁸ is represented by Formula 2-2, and at least one of R ⁹ to R ¹² is represented by Formula 2-1, and at least one of R ¹³ to R ¹⁶ may be represented by Chemical Formula 2-2.

At least one of R ¹ to R ⁴ is represented by Formula 2-1, at least one of R ⁵ to R ⁸ is represented by Formula 2-1, and at least one of R ⁹ to R ¹² is represented by Formula 2-1, and at least one of R ¹³ to R ¹⁶ may be represented by Chemical Formula 2-2.

At least one of R ¹ to R ⁴ , at least one of R ⁵ to R ⁸ , at least one of R ⁹ to R ¹² and at least one of R ¹³ to R ¹⁶ may each independently be a halogen atom.

The three of R ¹ to R ⁴ , the three of R ⁵ to R ⁸ , the three of R ⁹ to R ¹² and the three of R ¹³ to R ¹⁶ may each independently be halogen atoms.

The compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 3 to 14.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

The compound may be a green dye.

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

Another embodiment provides a photosensitive resin composition comprising the compound.

The compound may be included in 1% to 10% by weight relative to 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.

The pigment may include a yellow pigment, a green pigment, or a combination thereof.

Another embodiment provides a color filter manufactured using the photosensitive resin composition.

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

The compound according to one embodiment has excellent green spectral properties and high molar extinction coefficient and excellent solubility in an organic solvent, and thus can be used as a dye when preparing a photosensitive resin composition for a green color filter, and the color filter comprising the dye It can have excellent brightness and contrast ratio.

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 claims to be described later.

Unless otherwise specified in the present specification, "substituted" to "substituted" means that at least one hydrogen atom in the functional group of the present invention is a halogen atom (F, Br, Cl 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, each independently being a C1 to C10 alkyl group), 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 substituted or unsubstituted heterocyclic groups.

Unless otherwise specified in the present specification, "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, and "aryl group" means a C6 to C20 aryl group, specifically C6 to C18 aryl group means, "alkenyl group" means C2 to C20 alkenyl group, specifically means C2 to C18 alkenyl group, and "alkylene group" means C1 to C20 alkylene group, specifically C1 To C18 alkylene group, and "arylene group" means a C6 to C20 arylene group, specifically, a C6 to C16 arylene group.

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

In the present specification, unless otherwise specified, "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymerization or random copolymerization.

Unless otherwise defined in the chemical 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 present specification, "*" means a portion connected to the same or different atoms or chemical formulas.

One embodiment provides a compound represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

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

However, at least one of R ¹ to R ¹⁶ is a halogen atom,

At least one of R ¹ to R ¹⁶ is represented by the following Chemical Formula 2-1,

At least one of R ¹ to R ¹⁶ is represented by the following Formula 2-2,

[Formula 2-1]

[Formula 2-2]

In Chemical Formulas 2-1 and 2-2,

R ¹⁷ is a C2 to C10 alkyl group substituted with a C1 to C10 alkyl group,

R ¹⁸ and R ¹⁹ are each independently a halogen atom, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n1 is an integer from 2 to 5,

n2 and n3 are each independently an integer of 0 to 5, provided that 1≦n2+n3≦5.

The compound represented by Chemical Formula 1 has excellent green spectral properties and high molar absorption coefficient. Furthermore, the compound represented by Formula 1 may exhibit excellent solubility in an organic solvent and excellent luminance and contrast ratio when applied to a color filter, as the substituents represented by Formula 2-1 and Formula 2-2 must be included.

The substituent represented by Formula 2-1 is an aryloxy group in which two'alkyl groups substituted with an alkyl group' (eg, t-butyl group) are substituted. In particular, the'alkyl group substituted with an alkyl group' is ortho. And when the para position is substituted, the luminance and contrast ratio can be further improved. In addition, when the'alkyl group substituted with an alkyl group' is substituted at both ortho and para (para) positions, the'alkyl group substituted with an alkyl group' is an ortho or para position. The effect of improving the luminance and contrast ratio is superior to the case where only is substituted. However, when the'alkyl group substituted with an alkyl group' is substituted at the meta position (even if another'alkyl group substituted with an alkyl group' is substituted at the ortho or para position) The effect of improving luminance and contrast is negligible.

That is, in the substituent represented by Formula 2-1, the'alkyl group substituted with an alkyl group' is ortho and para ( When all are substituted at the para) position, the luminance and contrast ratio can be further improved.

In addition, since the compound represented by Formula 1 is at least one of R ¹ to R ¹⁶ is a halogen atom, it is more advantageous to implement a green pixel for color filters.

For example, the formula 2-1 may be represented by the following formula 2-1-1.

[Formula 2-1-1]

In the above formula 2-1-1,

R ²⁰ and R ²¹ are each independently a C2 to C10 alkyl group substituted with a C1 to C5 alkyl group.

For example, R ²⁰ and R ²¹ may each independently be a t-butyl group.

The substituent represented by Chemical Formula 2-2 is an aryloxy group in which one or more halogen atoms, cycloalkyl groups, or aryl groups are substituted, and in particular,'when the halogen atom is substituted at ortho and para positions' and In the case where the cycloalkyl group is substituted at the ortho or para position, the luminance and contrast ratio may be further improved. In addition, when the halogen atom is substituted in both ortho and para positions (two halogen atom substitutions), the halogen atom is substituted only in the ortho or para position (one It has the effect of improving the luminance and contrast than when the halogen atom is substituted). However, when the halogen atom is substituted at the meta position (even if another halogen atom is substituted at the ortho and/or para position together), the effect of improving the luminance and contrast is negligible. Likewise, when the cycloalkyl group is substituted at the meta position, the effect of improving brightness and contrast ratio is negligible.

That is, in the substituent represented by Chemical Formula 2-2, i) when any halogen atom or cycloalkyl group is substituted at the meta position, ii) the halogen atom is in the ortho and para position When substituted at only one position, iii-1) When the halogen atom is substituted at the ortho and para positions, iii-2) the cycloalkyl group is ortho or para (para) ) In the case of substitution at the position (i → ii → iii-1/iii-2), the luminance and contrast ratio can be further improved.

The formula 2-2 may be represented by any one of the following formulas 2-2-1 to 2-2-3.

[Formula 2-2-1]

[Formula 2-2-2]

[Formula 2-2-3]

In Formula 2-2-1 to Formula 2-2-3,

R ²² and R ²³ are each independently a substituted or unsubstituted C3 to C20 cycloalkyl group,

R ²⁴ and R ²⁵ are each independently a halogen atom.

For example, R ²⁴ and R ²⁵ may be each independently F, Cl or Br.

At least one of R ¹ to R ⁴ is represented by Formula 2-1, at least one of R ⁵ to R ⁸ is represented by Formula 2-2, and at least one of R ⁹ to R ¹² is represented by Formula 2-2, and at least one of R ¹³ to R ¹⁶ may be represented by Formula 2-2.

At least one of R ¹ to R ⁴ is represented by Formula 2-1, at least one of R ⁵ to R ⁸ is represented by Formula 2-1, and at least one of R ⁹ to R ¹² is represented by Formula 2-2, and at least one of R ¹³ to R ¹⁶ may be represented by Formula 2-2.

At least one of R ¹ to R ⁴ is represented by Formula 2-1, at least one of R ⁵ to R ⁸ is represented by Formula 2-2, and at least one of R ⁹ to R ¹² is represented by Formula 2-1, and at least one of R ¹³ to R ¹⁶ may be represented by Chemical Formula 2-2.

At least one of R ¹ to R ⁴ is represented by Formula 2-1, at least one of R ⁵ to R ⁸ is represented by Formula 2-1, and at least one of R ⁹ to R ¹² is represented by Formula 2-1, and at least one of R ¹³ to R ¹⁶ may be represented by Chemical Formula 2-2.

At least one of R ¹ to R ⁴ , at least one of R ⁵ to R ⁸ , at least one of R ⁹ to R ¹² and at least one of R ¹³ to R ¹⁶ may each independently be a halogen atom.

For example, at least one of R ¹ to R ⁴ is a halogen atom and the rest is represented by Formula 2-1 or Formula 2-2, at least one of R ⁵ to R ⁸ is a halogen atom, and the rest are Formula 2- 1 or represented by Formula 2-2, at least one of R ⁹ to R ¹² is a halogen atom, and the rest is represented by Formula 2-1 or Formula 2-2, and at least one of R ¹³ to R ¹⁶ is halogen It is an atom and the rest can be represented by Formula 2-1 or Formula 2-2.

The three of R ¹ to R ⁴ , the three of R ⁵ to R ⁸ , the three of R ⁹ to R ¹² and the three of R ¹³ to R ¹⁶ may each independently be halogen atoms.

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

The compound represented by Formula 1 may be represented by any one of the following Formulas 3 to 14, but is not limited thereto.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

Since the compound according to one embodiment includes the substituents represented by Chemical Formulas 2-1 and 2-2, it is possible to express more vivid colors in a small amount, and when used as a colorant, color characteristics such as luminance or contrast ratio It is possible to manufacture excellent display elements. For example, the compound may be a colorant, such as a dye, such as a green dye, such as a dye having a maximum transmittance in a wavelength range of 445 nm to 560 nm.

In general, dyes are the most expensive components used in color filters. Therefore, in order to achieve a desired effect, such as high brightness or high contrast ratio, more expensive dyes have to be used, which leads to an increase in production cost. However, when the compound according to one embodiment is used as a dye in a color filter, it is possible to achieve excellent color characteristics such as high brightness and high contrast ratio even in a small amount, thereby reducing production cost.

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

For example, the photosensitive resin composition may include a compound according to one embodiment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

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

The compound according to one embodiment may be included in 1 wt% to 10 wt%, for example, 3 wt% to 7 wt%, based on the total amount of the photosensitive resin composition. When the compound according to one embodiment is included in the above range, color gamut and contrast ratio become 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 is C.I. Pigment Yellow 11, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 167, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 199, C.I. And pigment yellow 215. These may be used alone or in combination of two or more.

The green pigment is C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment green 62 and the like, and these may be used alone or in combination of two or more.

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

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

The pigment of the solid content is 1% to 20% by weight relative to the total amount of the pigment dispersion, such as 8% to 20% by weight, such as 8% to 15% by weight, such as 10% to 20% by weight, such as 10% by weight 15% by weight.

As the dispersant, a nonionic dispersant, anionic dispersant, or cationic dispersant may be used. Specific examples of the dispersing agent include polyalkylene glycol and esters thereof, polyoxyalkylene, polyalcohol ester alkylene oxide adduct, alcoholalkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, and 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 dispersing agent include 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 from EFKA Chemical, etc.; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse24000GR, Solsperse 27000, Solsperse 28000, etc.; Or Ajinomoto's PB711 or PB821.

The 　 dispersant may be included in 1 to 20% by weight 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 dispersibility of the photosensitive resin composition is excellent, thereby maintaining optical, physical and chemical quality when applying the product.

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

The pigment dispersion may be included in 10% by weight to 20% by weight, such as 12% by weight to 18% by weight relative to 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 color reproduction ratio and contrast ratio are excellent.

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 comprising 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 combinations 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 vinylbenzyl methyl ether; 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 are (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzylmethacrylate/styrene copolymer, (meth)acrylic acid/benzylmethacrylate/2-hydroxyethylmeth Acrylate copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, and the like, but are not limited thereto, and these may be used alone or in combination of two or more. have.

The weight average molecular weight of the binder resin may be 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol, such as 20,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the binder resin is within the above range, physical and chemical properties of the photosensitive resin composition are excellent, viscosity is appropriate, and adhesion to a substrate is excellent when producing a color filter.

The acid value of the 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 binder resin is within the above range, the resolution of the pixel pattern is excellent.

The binder resin may be included in 1 wt% to 30 wt%, for example, 1 wt% to 20 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, when developing a color filter, developability is excellent and crosslinkability is improved to obtain 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 excellent in heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure in the 　 pattern forming process.

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

Examples of commercially available products of the photopolymerizable compound 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., and TC-120S ^® of the same; 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 ^®; Nippon Kayaku (Note)社of KAYARAD HDDA ^®, copper HX-220 ^®, copper R-604 ^®, and the like; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. 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, Dong M-8030 ^®, same M-8060 ^®, and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Examples include Osaka Yuki Kayaku High School Co., Ltd. V-295 ^® , Dong-300 ^® , Dong-360 ^® , Dong-GPT ^® , Dong-3PA ^® , and Dong-400 ^® . The above products may be used alone or in combination of two or more.

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

The photopolymerizable compound may be included in 1% to 15% by weight, for example, 5% to 10% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, curing is sufficiently performed during exposure in the 　 pattern forming process, and reliability is excellent, and developability to an alkali developer is excellent.

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

Examples of the acetophenone-based compound, 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-based compound, benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylate benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4 And'-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-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- And chlorothioxanthone.

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloro methyl)-s-triazine, 2-biphenyl 4,6-bis(trichloro methyl)-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, and the like.

Examples of the oxime-based compound, O-acyloxime-based compound, 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-acyl oxime compound, 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-one oxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butane-1-one oxime-O- And acetate.

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

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and transmitting its energy.

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 0.01 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 can occur sufficiently during exposure in the pattern forming process to obtain excellent reliability, heat resistance, light resistance and chemical resistance of the pattern are excellent, and resolution and adhesion are also excellent, due to unreacted initiator A decrease in transmittance can be prevented.

The solvent, a compound according to an embodiment, a pigment, an alkali-soluble resin, a photopolymerizable compound and a material having a compatibility with a photopolymerization initiator, but materials that do not react can 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 methylethyl 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 methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, and ethyl ethoxy acetate; 3-oxy propionic acid alkyl esters such as methyl 3-oxy propionate and ethyl 3-oxy propionate; 3-alkoxy propionic acid alkyl esters such as methyl 3-methoxy propionate, ethyl 3-methoxy propionate, ethyl 3-ethoxy propionate and methyl 3-ethoxy propionate; 2-oxy propionic acid alkyl esters, such as methyl 2-oxy propionate, ethyl 2-oxy propionate, and propyl 2-oxy propionic acid; 2-alkoxy propionic acid alkyl esters such as methyl 2-methoxy propionate, ethyl 2-methoxy propionate, ethyl 2-ethoxy propionate and methyl 2-ethoxy propionate; 2-oxy-2-methyl propionic acid esters such as methyl 2-oxy-2-methyl propionate and ethyl 2-oxy-2-methyl propionate, methyl 2-methoxy-2-methyl propionate, and 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl propionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methyl propionate, ethyl hydroxy acetate, and methyl 2-hydroxy-3-methyl butanoate; And ketone acid esters such as ethyl pyruvate, and N-methylformamide, N,N-dimethylformamide, N-methylformanirad, N-methylacetamide, and N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid And high-boiling solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, ketones such as cyclohexanone are considered 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 ketones such as cyclohexanone can be used.

The solvent may be included in a residual amount, such as 30% by weight to 80% by weight relative to the total amount of the photosensitive resin composition. When the solvent is included within the above range, as the photosensitive resin composition has an appropriate viscosity, processability in manufacturing a color filter is excellent.

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

Examples of the epoxy compound include phenol novolac epoxy compounds, tetramethyl biphenyl epoxy compounds, bisphenol A type epoxy compounds, alicyclic epoxy compounds, or combinations 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, storage, and the like are excellent.

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

Examples of the silane coupling agent, trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy Cypropyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, etc. are mentioned, 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 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 are excellent.

In addition, the photosensitive resin composition may further include a surfactant to improve coating properties and prevent defect generation, if necessary.

Examples of the surfactant include BM-1000 ^® , BM-1100 ^® of BM Chemie; Dai Nippon Inki Chemical Industry Co., Ltd. Mecca Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^®, etc.; 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 0.001 part 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 wetting of 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 color filter manufactured using the photosensitive resin composition according to the embodiment is provided.

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 photosensitive resin composition film with an aqueous alkali solution to produce a photosensitive resin film; And heat-treating the photosensitive resin film. Since the conditions in the process are well known in the art, detailed descriptions thereof will be omitted.

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

(Synthesis of compounds)

Synthetic example 1: 3 ,4,6-Trichloro-5-(2,4-di- tert -butyl- phenoxy )- phthalonitrile synthesis

3,4,5,6-tetrachlorophthalonitrile (5g), 2,4-di-tert-butylphenol (4.75g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (N,N) in a 100ml flask -dimethylformamide) (25ml) and stirred while heating to 70℃. After the reaction is completed, it is extracted with EA (ethyl acetate). After extraction and concentration, a solid can be obtained. The solid obtained at this time was dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried under vacuum to give 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile. Get

Synthetic example 2: 3 ,4,6- trichloro -5-(2- cyclohexyl - phenoxy )- phthalonitrile synthesis

3,4,5,6-tetrachlorophthalonitrile (5g), 2-cyclohexylphenol (3.06g), K ₂ CO ₃ (3.9g), acetone (25ml) was added to a 100ml flask and stirred while heating to 70℃. After completion of the reaction, a solid obtained by filtering and distilling the liquid out by washing with acetone. At this time, the obtained solid is dissolved in a small amount of dichloromethane, washed several times with nucleic acid, filtered and dried in vacuo to obtain 3,4,6-trichloro-5-(2-cyclohexyl-phenoxy)-phthalonitrile.

Synthetic example 3: 3 ,4,6- trichloro -5-(4- cyclohexyl - phenoxy )- phthalonitrile synthesis

3,4,5,6-tetrachlorophthalonitrile (5g), 4-cyclohexylphenol (3.06g), K ₂ CO ₃ (3.9g), acetone (25ml) was added to a 100ml flask and stirred while heating to 70°C. After completion of the reaction, a solid obtained by filtering and distilling the liquid out by washing with acetone. At this time, the obtained solid is dissolved in a small amount of dichloromethane, washed several times with nucleic acid, filtered and dried in vacuo to obtain 3,4,6-trichloro-5-(4-cyclohexyl-phenoxy)-phthalonitrile.

Synthetic example 4: 3 ,4,6-Trichloro-5-(2,6- dichloro - phenoxy )- phthalonitrile synthesis

3,4,5,6-tetrachlorophthalonitrile (5g), 2,6-dichlorophenol (2.45g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (N,N-dimethylformamide) 25ml) and stirred while heating to 70°C. After the reaction is completed, it is extracted with EA (ethyl acetate). After extraction and concentration, a solid can be obtained. At this time, the obtained solid is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried under vacuum to obtain 3,4,6-Trichloro-5-(2,6-dichloro-phenoxy)-phthalonitrile.

Synthetic example 5: 3 ,4,6-Trichloro-5-(2,6-dibromo- phenoxy )- phthalonitrile synthesis

3,4,5,6-tetrachlorophthalonitrile (5g), 2,6-dibromophenol (2.45g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide (N,N-dimethylformamide) 25ml) and stirred while heating to 70°C. After the reaction is completed, it is extracted with EA (ethyl acetate). After extraction and concentration, a solid can be obtained. The solid obtained at this time was dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried under vacuum to obtain 3,4,6-Trichloro-5-(2,6-dibromo-phenoxy)-phthalonitrile.

Synthetic example 6: 3 ,4,6-Trichloro-5-(2-butyl- phenoxy )- phthalonitrile synthesis

3,4,5,6-tetrachlorophthalonitrile(5g), 2-butylphenol(4.75g), K ₂ CO ₃ (3.9g), N,N-dimethylformamide(25ml) in 100ml flask And stirred while heating to 70°C. After the reaction is completed, it is extracted with EA (ethyl acetate). After extraction and concentration, a solid can be obtained. The solid obtained at this time was dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried under vacuum to obtain 3,4,6-Trichloro-5-(2-butyl-phenoxy)-phthalonitrile.

Synthetic example 7: 4 -(Biphenyl-2- yloxy )-3,5,6- trichloro - phthalonitrile synthesis

3,4,5,6-tetrachlorophthalonitrile (5g), 2-Phenylphenol (3.21g), K ₂ CO ₃ (3.9g), acetone (25ml) was added to a 100ml flask and stirred while heating to 70°C. After completion of the reaction, filter and wash with acetone to distill the liquid to obtain a solid. At this time, the obtained solid is dissolved in a small amount of dichloromethane, washed several times with nucleic acid, filtered and dried in vacuo to obtain 4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile.

Synthetic example 8: (2,4-di- tert -butyl- phenoxy )- phthalonitrile synthesis

4-nitrophthalonitrile (5 g), 2,4-di-tert-butylphenol (4.75 g), K ₂ CO ₃ (3.9 g), N,N-dimethylformamide (25 ml) in a 100 ml flask And stirred while heating to 70°C. After the reaction is completed, it is extracted with EA (ethyl acetate). After extraction and concentration, a solid can be obtained. The solid obtained at this time was dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried under vacuum to obtain (2,4-di-tert-butyl-phenoxy)-phthalonitrile.

Synthetic example 9: (2- cyclohexyl - phenoxy )- phthalonitrile synthesis

In a 100 ml flask, 4-nitrophthalonitrile (5 g), 2-cyclohexylphenol (3.06 g), K ₂ CO ₃ (3.9 g), acetone (25 ml) was added and stirred while heating to 70°C. After completion of the reaction, a solid obtained by filtering and distilling the liquid out by washing with acetone. At this time, the obtained solid is dissolved in a small amount of dichloromethane, washed several times with nucleic acid, filtered and dried in vacuo to obtain (2-cyclohexyl-phenoxy)-phthalonitrile.

Synthetic example 10: Synthesis of compound represented by formula (3)

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (0.49g) of Synthesis Example 1, 3,4,6-trichloro-5 of Synthesis Example 2 -(2-cyclohexyl-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.52g) and 1-pentanol (14g) were added and heated to 90℃ to dissolve the solid and then zinc acetate( 0.23 g) and stirred while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following Chemical Formula 3.

[Formula 3]

Maldi-tof MS: 1710.08 m/z

Synthetic example 11: Synthesis of compound represented by formula (4)

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (1.6g) of Synthesis Example 1, 3,4,6-trichloro-5 of Synthesis Example 2 -(2-cyclohexyl-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.74g) and 1-pentanol (14g) were added and heated to 90℃ to dissolve the solid and then zinc acetate ( 0.34 g) and stirred while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following Chemical Formula 4.

[Formula 4]

Maldi-tof MS: 1740.12 m/z

Synthetic example 12: Synthesis of Compound Represented by Formula 5

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (2.9 g) of Synthesis Example 1, 3,4,6-trichloro-5 of Synthesis Example 2 -(2-cyclohexyl-phenoxy)-phthalonitrile (1g), 1,8-Diazabicycloundec-7-ene (3g) and 1-pentanol (27g) were added and heated to 90℃ to dissolve the solid and then zinc acetate (0.45g ) And stirred while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following Chemical Formula 5.

[Formula 5]

Maldi-tof MS: 1770.17 m/z

Synthetic example 13: Synthesis of Compound Represented by Formula 6

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (0.49g) of Synthesis Example 1, 3,4,6-trichloro-5 of Synthesis Example 3 -(4-cyclohexyl-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.52g) and 1-pentanol (14g) were added and heated to 90℃ to dissolve the solid and then zinc acetate( 0.23 g) and stirred while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following Chemical Formula 6.

[Formula 6]

Maldi-tof MS: 1710.08 m/z

Synthetic example 14: Synthesis of compound represented by formula (7)

3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (1.6g) of Synthesis Example 1 in a 100mL flask, 3,4,6-trichloro-5 of Synthesis Example 3 -(4-cyclohexyl-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.74g) and 1-pentanol (14g) were added and heated to 90℃ to melt the solid and then zinc acetate ( 0.34 g) and stirred while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following Chemical Formula 7.

[Formula 7]

Maldi-tof MS: 1740.12 m/z

Synthetic example 15: Synthesis of Compound Represented by Formula 8

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (2.9 g) of Synthesis Example 1, 3,4,6-trichloro-5 of Synthesis Example 3 -(4-cyclohexyl-phenoxy)-phthalonitrile (1g), 1,8-Diazabicycloundec-7-ene (3g) and 1-pentanol (27g) were added and heated to 90℃ to dissolve the solid and then zinc acetate (0.45g ) And stirred while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Chemical Formula 8.

[Formula 8]

Maldi-tof MS: 1770.17 m/z

Synthetic example 16: Synthesis of compound represented by formula (9)

3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (1.6g) of Synthesis Example 1 in a 100mL flask, 3,4,6-Trichloro-5 of Synthesis Example 4 -(2,6-dichloro-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.74g) and 1-pentanol (14g) were added and heated to 90℃ to melt the solid and then zinc Add acetate (0.34 g) and stir while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following Chemical Formula 9.

[Formula 9]

Maldi-tof MS: 1711.81 m/z

Synthetic example 17: Synthesis of Compound Represented by Formula 10

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (0.49g) of Synthesis Example 1, 3,4,6-Trichloro-5 of Synthesis Example 4 -(2,6-dichloro-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.52g) and 1-pentanol (14g) were added and heated to 90℃ to dissolve the zinc Add acetate (0.23 g) and stir while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following Chemical Formula 10

[Formula 10]

Maldi-tof MS: 1667.61 m/z

Synthetic example 18: Synthesis of Compound Represented by Formula 11

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (2.9g) of Synthesis Example 1, 3,4,6-Trichloro-5 of Synthesis Example 4 -(2,6-dichloro-phenoxy)-phthalonitrile (1g), 1,8-Diazabicycloundec-7-ene (3g) and 1-pentanol (27g) were added and heated to 90℃ to dissolve the solid and then zinc acetate( 0.45 g) and stirred while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Formula 11 below.

[Formula 11]

Maldi-tof MS: 1756.01 m/z

Synthetic example 19: Synthesis of Compound Represented by Formula 12

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (0.49g) of Synthesis Example 1, 3,4,6-Trichloro-5 of Synthesis Example 5 -(2,6-dibromo-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.52g) and 1-pentanol (14g) were added and heated to 90℃ to melt the solid and then zinc Add acetate (0.23 g) and stir while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following Chemical Formula 12.

[Formula 12]

Maldi-tof MS: 1931.30 m/z

Synthetic example 20: Synthesis of compound represented by formula (13)

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (1.6g) of Synthesis Example 1, 3,4,6-Trichloro-5 of Synthesis Example 5 -(2,6-dibromo-phenoxy)-phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.74g) and 1-pentanol (14g) were added and heated to 90℃ to melt the solid and then zinc Add acetate (0.34 g) and stir while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Chemical Formula 13 below.

[Formula 13]

Maldi-tof MS: 1887.61 m/z

Synthetic example 21: Synthesis of Compound Represented by Formula 14

In a 100 mL flask, 3,4,6-Trichloro-5-(2,4-di-tert-butyl-phenoxy)-phthalonitrile (2.9g) of Synthesis Example 1, 3,4,6-Trichloro-5 of Synthesis Example 5 -(2,6-dibromo-phenoxy)-phthalonitrile (1g), 1,8-Diazabicycloundec-7-ene (3g) and 1-pentanol (27g) were added and heated to 90℃ to dissolve the solid and then zinc acetate ( 0.45 g) and stirred while heating to 140°C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Chemical Formula 14 below.

[Formula 14]

Maldi-tof MS: 1843.91 m/z

compare Synthetic example 1: Synthesis of Compound Represented by Formula 21

In a 100 mL flask, (2,4-di-tert-butyl-phenoxy)-phthalonitrile (0.49 g) of Synthesis Example 8, (2-cyclohexyl-phenoxy)-phthalonitrile (1.5 g), 1,8-Diazabicycloundec of Synthesis Example 9 After adding -7-ene (1.52 g) and 1-pentanol (14 g) and heating to 90 DEG C, zinc acetate (0.23 g) was added after the solid melted and stirred while heating to 140 DEG C. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Chemical Formula 21 below.

[Formula 21]

Maldi-tof MS: 1302.54 m/z

compare Synthetic example 2: Synthesis of Compound Represented by Formula 22

3,4,6-Trichloro-5-(2-butyl-phenoxy)-phthalonitrile (1.99 g), 1,8-Diazabicycloundec-7-ene (1.52 g) and 1-pentanol (Synthesis Example 6) in a 100 mL flask 14g), heated to 90℃, and after melting the solid, add zinc acetate (0.23g) and stir while heating to 140℃. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following Chemical Formula 22.

[Formula 22]

Maldi-tof MS: 1575.97 m/z

compare Synthetic example 3: Synthesis of compound represented by formula (23)

In a 100 mL flask, 4-(Biphenyl-2-yloxy)-3,5,6-trichloro-phthalonitrile (1.99 g), 1,8-Diazabicycloundec-7-ene (1.52 g) and 1-pentanol of Synthesis Example 7 ( 14g), heated to 90℃, and after melting the solid, add zinc acetate (0.23g) and stir while heating to 140℃. After completion of the reaction, precipitation was confirmed with methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. After purification, the obtained solid dichloromethane was appropriately added to dissolve the solid, and then methanol was added to crystallize. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by Chemical Formula 23 below.

[Formula 23]

Maldi-tof MS: 1655.84 m/z

compare Synthetic example 4: Synthesis of Compound Represented by Formula X

4-(2-sec-Butyl-phenoxy)-3,5,6-trichloro-phthalonitrile (1 g), 1,8-Diazabicycloundec-7-ene (0.30 g), 1-pentanol (7 g) in a 100 mL flask, Add zinc acetate (0.12g) and stir while heating to 140℃. After the reaction is completed, it is concentrated and purified by column chromatography. After purification, the obtained liquid is concentrated to obtain a solid. The crystallized solid was dried in vacuo to obtain a compound represented by the following formula (X).

[Formula X]

Maldi-tof MS: 1584.04 m/z

(Synthesis of photosensitive resin composition)

Example One

The photosensitive resin composition according to Example 1 was prepared by mixing the components mentioned below with the composition shown in Table 1 below.

Specifically, after the photopolymerization initiator was dissolved 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. Subsequently, a compound (a compound represented by Chemical Formula 3) and a pigment (in the form of a pigment dispersion) prepared in Synthesis Example 10 were added to the obtained reactant as a colorant and stirred at room temperature for 1 hour. Then, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit:% by weight) Ingredients content coloring agent dyes Compound of Synthesis Example 10 5.0 Pigment dispersion Pigment Y138 Pigment dispersion 15.0 Binder resin (A)/(B)=15/85(w/w),
Molecular weight (Mw) = 22,000 g/mol
(A): Methacrylic acid
(B): Benzyl methacrylate 3.5 Photopolymerizable compound Dipentaerythritol hexaacrylate (DPHA) 8.0 Photopolymerization initiator 1,2-octanedione 1.0 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one 0.5 menstruum Cyclohexanone 37.0 PGMEA (Propylene Glycol Monomethyl Ether Acetate) 30.0 Total 100.00

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 11 (the compound represented by Formula 4) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 12 (the compound represented by Formula 5) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Example 4

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 13 (the compound represented by Formula 6) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Example 5

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 14 (the compound represented by Chemical Formula 7) was used instead of the compound of Synthesis Example 10 (the compound represented by Chemical Formula 3).

Example 6

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 15 (the compound represented by Formula 8) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Example 7

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 16 (the compound represented by Formula 9) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Example 8

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 17 (the compound represented by Formula 10) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Example 9

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 18 (the compound represented by Formula 11) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Example 10

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 19 (the compound of Formula 12) was used instead of the compound of Synthesis Example 10 (the compound of Formula 3).

Example 11

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 20 (the compound represented by Formula 13) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Example 12

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Synthesis Example 21 (the compound represented by Formula 14) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Comparative example One

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Comparative Example 1 (the compound represented by Formula 21) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Comparative example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Comparative Example 2 (the compound represented by Formula 22) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Comparative example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Comparative Synthesis Example 3 (the compound represented by Formula 23) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Comparative example 4

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Comparative Synthesis Example 5 (the compound represented by Formula X) was used instead of the compound of Synthesis Example 10 (the compound represented by Formula 3).

Comparative example 5

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the composition shown in Table 2 was mixed instead of the composition shown in Table 1.

(Unit:% by weight) Ingredients content coloring agent Pigment dispersion Pigment G58 pigment dispersion 20.0 Pigment Y138 Pigment dispersion 15.0 Alkali-soluble resin (A)/(B)=15/85(w/w),
Molecular weight (Mw) = 22,000 g/mol
(A): Methacrylic acid
(B): Benzyl methacrylate 2.5 Photopolymerizable compound Dipentaerythritol hexaacrylate (DPHA) 5.0 Photopolymerization initiator 1,2-octanedione 1.0 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one 0.5 menstruum Cyclohexanone 40.0 PGMEA (Propylene Glycol Monomethyl Ether Acetate) 16.0 Total 100.00

Evaluation 1: Solubility Measurement

Compounds represented by formulas 3 to 14, compounds represented by formulas 21 to 23 and 0.5 g of compounds represented by formula X are added to dilution solvent (PGMEA), respectively, and the solution is mixed rotor (MIXROTAR VMR manufactured by iuchi Co., Ltd.) After stirring at 25°C and 100 rpm for 1 hour at -5), the results of confirming the dissolution state (content of dissolved compound) of the compound are shown in Table 3 below.

Solubility evaluation criteria

10% by weight or more of the compound (solute) is dissolved in the total amount of the diluted solvent: ○

5% by weight or more and less than 10% by weight of the compound (solute) relative to the total amount of the diluting solvent: △

Less than 5% by weight of compound (solute) relative to the total amount of diluent: X

Formula 3 ○ Formula 4 ○ Formula 5 ○ Formula 6 ○ Formula 7 ○ Formula 8 ○ Formula 9 ○ Formula 10 ○ Formula 11 ○ Formula 12 ○ Formula 13 ○ Formula 14 ○ Formula 21 ○ Formula 22 X Formula 23 ○ Formula X X

Evaluation 2: Measurement of luminance and contrast ratio

A photosensitive resin composition prepared in Examples 1 to 12 and Comparative Examples 1 to 5 was coated with a thickness of 1 μm to 3 μm on a glass substrate having a thickness of 1 mm degreased and washed, and a hot plate at 90° C. Dry on the phase for 2 minutes to obtain a coating film. Subsequently, the coating film was exposed using a high-pressure mercury lamp having a main wavelength of 365 nm. Thereafter, the sample was obtained by drying in a hot air circulation drying furnace at 200° C. for 5 minutes. The pixel layer was measured by using a spectrophotometer (MCPD3000, Otsuka electronics) to measure the luminance (Y) and contrast ratio, and the results are shown in Table 4 below.

Luminance (Y) Contrast Example 1 63.3 15400 Example 2 63.4 15600 Example 3 63.3 15300 Example 4 63.5 15200 Example 5 63.4 15400 Example 6 63.2 15700 Example 7 63.4 15900 Example 8 63.3 15400 Example 9 63.2 15200 Example 10 63.1 15500 Example 11 63.2 15300 Example 12 63.0 15200 Comparative Example 1 62.5 14,800 Comparative Example 2 61.7 14,800 Comparative Example 3 60.5 14,600 Comparative Example 4 62.3 14500 Comparative Example 5 62.2 13500

From Table 4, the photosensitive resin composition of Examples 1 to 12 containing the compound according to one embodiment as a dye has better color characteristics than the photosensitive resin composition of Comparative Examples 1 to 5 without the compound. Can be confirmed.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and it is possible to carry out various modifications within the scope of the claims and detailed description of the invention and the accompanying drawings. Naturally, it is within the scope of the invention.

Claims (18)

Compound represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
R ¹ to R ¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted A substituted C6 to C20 aryloxy group,
However, at least one of R ¹ to R ¹⁶ is a halogen atom,
At least one of R ¹ to R ¹⁶ is represented by the following Chemical Formula 2-1-1,
At least one of R ¹ to R ¹⁶ is represented by any one of the following Chemical Formulas 2-2-1 to 2-2-3:
[Formula 2-1-1]

In the above formula 2-1-1,
R ²⁰ and R ²¹ are each independently a C2 to C10 alkyl group substituted with a C1 to C5 alkyl group:
[Formula 2-2-1]

[Formula 2-2-2]

[Formula 2-2-3]

In Formula 2-2-1 to Formula 2-2-3,
R ²² and R ²³ are each independently a substituted or unsubstituted C3 to C20 cycloalkyl group,
R ²⁴ and R ²⁵ are each independently a halogen atom.
delete delete According to claim 1,
At least one of R ¹ to R ⁴ is represented by the formula 2-1-1,
At least one of R ⁵ to R ⁸ is represented by any one of Formula 2-2-1 to Formula 2-2-3,
At least one of R ⁹ to R ¹² is represented by any one of Formula 2-2-1 to Formula 2-2-3,
At least one of R ¹³ to R ¹⁶ is a compound represented by any one of Formula 2-2-1 to Formula 2-2-3.
According to claim 1,
At least one of R ¹ to R ⁴ is represented by the formula 2-1-1,
At least one of R ⁵ to R ⁸ is represented by Formula 2-1-1,
At least one of R ⁹ to R ¹² is represented by any one of Formula 2-2-1 to Formula 2-2-3,
At least one of R ¹³ to R ¹⁶ is a compound represented by any one of Formula 2-2-1 to Formula 2-2-3.
According to claim 1,
At least one of R ¹ to R ⁴ is represented by the formula 2-1-1,
At least one of R ⁵ to R ⁸ is represented by any one of Formula 2-2-1 to Formula 2-2-3,
At least one of R ⁹ to R ¹² is represented by Formula 2-1-1,
At least one of R ¹³ to R ¹⁶ is a compound represented by any one of Formula 2-2-1 to Formula 2-2-3.
According to claim 1,
At least one of R ¹ to R ⁴ is represented by the formula 2-1-1,
At least one of R ⁵ to R ⁸ is represented by Formula 2-1-1,
At least one of R ⁹ to R ¹² is represented by Formula 2-1-1,
At least one of R ¹³ to R ¹⁶ is a compound represented by any one of Formula 2-2-1 to Formula 2-2-3.
According to claim 1,
At least one of R ¹ to R ⁴ , at least one of R ⁵ to R ⁸ , at least one of R ⁹ to R ¹² and at least one of R ¹³ to R ¹⁶ are each independently a halogen atom.
According to claim 1,
The three of R ¹ to R ⁴ , the three of R ⁵ to R ⁸ , the three of R ⁹ to R ¹² and the three of R ¹³ to R ¹⁶ are each independently a halogen atom.
According to claim 1,
The compound represented by Formula 1 is a compound represented by any one of the following Formulas 3 to 14.
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

According to claim 1,
The compound is a green dye.
The method of claim 11,
The green dye is a compound having a maximum transmittance in the wavelength range of 445nm to 560nm.
The photosensitive resin composition containing the compound of any one of Claims 1 and 4-12.
The method of claim 13,
The compound is 1 to 10% by weight based on the total amount of the photosensitive resin composition Photosensitive resin composition.
The method of claim 13,
The photosensitive resin composition further comprises a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
The method of claim 15,
The photosensitive resin composition further comprises a pigment.
The method of claim 16,
The pigment is a photosensitive resin composition comprising a yellow pigment, a green pigment, or a combination thereof.
A color filter manufactured using the photosensitive resin composition of claim 13.