KR102072212B1 - Novel compound,photosensitive resin composition comprising the same and color filter - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)Provided is a compound represented by Formula 1, a photosensitive resin composition comprising the same, and a color filter manufactured using the photosensitive resin composition.
[Formula 1]

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

Description

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

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

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

Therefore, there is a need for research on a compound suitable as a dye used in the preparation of the 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 following formula (1).

[Formula 1]

In Chemical Formula 1,

R ¹ to R ¹⁶ each independently represent 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 group Ring C6 to C20 aryloxy group,

However, at least one of R ¹ to R ¹⁶ is represented by the following formula (2),

[Formula 2]

In Chemical Formula 2,

R ¹⁷ and R ¹⁸ are each independently a halogen atom,

n1 and n2 are each independently an integer of 0 to 5, provided that 1 ≦ n1 + n2 ≦ 5.

Formula 2 may be represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Chemical Formulas 3-1 to 3-4,

R ¹⁷ and R ¹⁸ are each independently a halogen atom.

At least one of R ¹ to R ¹⁶ may be represented by Formula 2, and at least one of R ¹ to R ¹⁶ may be represented by Formula 4.

[Formula 4]

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

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

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

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

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

The compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 5 to 14.

[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 the wavelength range of 445nm to 560nm.

Another embodiment provides a photosensitive resin composition comprising the compound.

The compound may be included in an amount of 1 wt% to 10 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.

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

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

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

Compound according to an embodiment has excellent green spectral properties and high molar absorption coefficient and excellent solubility in organic solvents, can be used as a dye when preparing a photosensitive resin composition for a green color filter, 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, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the specification, "substituted" to "substituted" means that at least one hydrogen atom of the functional group of the present invention is a halogen atom (F, Br, Cl or I), hydroxy group, nitro group, cyano group, amino group ( NH ₂ , NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), where R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other, and are each independently C 1 to C 10 alkyl groups, amidino groups, Hydrazine groups, hydrazone groups, carboxyl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted alicyclic organic groups, substituted or unsubstituted aryl groups, and Mean substituted by one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless stated otherwise in the specification, an "alkyl group" means a C1 to C20 alkyl group, specifically a C1 to C15 alkyl group, and a "cycloalkyl group" means a C3 to C20 cycloalkyl group, specifically C3 To C18 cycloalkyl group, "alkoxy group" means C1 to C20 alkoxy group, specifically C1 to C18 alkoxy group, "aryl group" means C6 to C20 aryl group, specifically C6 to Means an C18 aryl group, "alkenyl group" means a C2 to C20 alkenyl group, specifically means a C2 to C18 alkenyl group, "alkylene group" means a C1 to C20 alkylene group, specifically C1 To C18 alkylene group, an "arylene group" means a C6 to C20 arylene group, and specifically means a C6 to C16 arylene group.

Unless stated otherwise in the specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". Both mean it's possible.

Unless otherwise defined herein, “combination” means mixed or copolymerized. In addition, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymerization.

Unless otherwise defined in the chemical formulas herein, when a chemical bond is not drawn at the position where the 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 the part connected with the same or different atoms or 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 Ring C6 to C20 aryloxy group,

However, at least one of R ¹ to R ¹⁶ is represented by the following formula (2),

[Formula 2]

In Chemical Formula 2,

R ¹⁷ and R ¹⁸ are each independently a halogen atom,

n1 and n2 are each independently an integer of 0 to 5, provided that 1 ≦ n1 + n2 ≦ 5.

The compound represented by Chemical Formula 1 has excellent green spectral properties and high molar extinction coefficient. Furthermore, the compound represented by Chemical Formula 1 may include a substituent represented by Chemical Formula 2, thereby exhibiting excellent solubility in organic solvents and excellent luminance and contrast ratio when applied to a color filter.

Formula 2 may be represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Chemical Formulas 3-1 to 3-4,

R ¹⁷ and R ¹⁸ are each independently a halogen atom.

The substituents represented by Formulas 3-1 to 3-4 are all aryloxy groups in which one or more halogen atoms are substituted, especially when the halogen atoms are substituted at ortho and / or para positions, The brightness and contrast ratio can be further improved. In addition, when the halogen atom is substituted at both the ortho and para positions (two halogen atom substitutions), the halogen atom is substituted only at the ortho or para position (one It is possible to improve the brightness and contrast ratio than in the case of halogen atom substitution). However, when the halogen atom is substituted at the meta position (even though another halogen atom is also substituted at the ortho and / or para position), the effect of improving the brightness and contrast ratio is insignificant.

That is, in the substituent represented by Chemical Formula 2, for example, the substituents represented by Chemical Formulas 3-1 to 3-4, i) when at least one halogen atom is substituted at the meta position, ii) the halogen atom is ortho ( in case of substitution at only one of ortho and para position, iii) in the case of halogen atom being substituted at both ortho and para position (i → ii → iii) The brightness and contrast ratio can be further improved.

At least one of R ¹ to R ¹⁶ may be represented by Formula 2, and at least one of R ¹ to R ¹⁶ may be represented by Formula 4.

[Formula 4]

For example, the substituent represented by Formula 4 may be represented by the following Formula 4-1.

[Formula 4-1]

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

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 4, R ¹⁰ or R ¹¹ is represented by Formula 4, and R ¹⁴ or R ¹⁵ May be represented by Formula 4.

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 4, R ¹⁰ or R ¹¹ is represented by Formula 4, and R ¹⁴ or R ¹⁵ Is represented by the formula (4), and the rest not represented by the formula (2) and formula (4) may all be a halogen atom.

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

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 2, R ¹⁰ or R ¹¹ is represented by Formula 4, and R ¹⁴ or R ¹⁵ May be represented by Formula 4.

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 2, R ¹⁰ or R ¹¹ is represented by Formula 4, and R ¹⁴ or R ¹⁵ Is represented by Formula 4, and the rest not represented by Formula 2 and Formula 4 may all be halogen atoms.

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

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 4, R ¹⁰ or R ¹¹ is represented by Formula 2, and R ¹⁴ or R ¹⁵ May be represented by Formula 4.

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 4, R ¹⁰ or R ¹¹ is represented by Formula 2, and R ¹⁴ or R ¹⁵ Is represented by Formula 4, and the rest not represented by Formula 2 and Formula 4 may all be halogen atoms.

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

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 2, R ¹⁰ or R ¹¹ is represented by Formula 2, and R ¹⁴ or R ¹⁵ May be represented by Formula 4.

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 2, R ¹⁰ or R ¹¹ is represented by Formula 2, and R ¹⁴ or R ¹⁵ Is represented by Formula 4, and the rest not represented by Formula 2 and Formula 4 may all be halogen atoms.

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

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 2, R ¹⁰ or R ¹¹ is represented by Formula 2, and R ¹⁴ or R ¹⁵ May be represented by Formula 2 above.

For example, R ² or R ³ is represented by Formula 2, R ⁶ or R ⁷ is represented by Formula 2, R ¹⁰ or R ¹¹ is represented by Formula 2, and R ¹⁴ or R ¹⁵ Is represented by the formula (2), and the rest not represented by the formula (2) may all be a halogen atom.

For example, the compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 5 to 14, but is not necessarily limited thereto.

[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 a substituent represented by any one of Formula 2, for example, Formulas 3-1 to 3-4, it is possible to express more vivid colors in a small amount, and thus, luminance when used as a colorant. It is possible to manufacture a display element having excellent color characteristics such as contrast and contrast ratio. 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 the wavelength range of 445 nm to 560 nm.

In general, dyes are the most expensive of the 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. However, when using the compound according to the embodiment as a dye in the color filter, it is possible to achieve excellent color characteristics such as high brightness, high contrast ratio even in a small amount it is possible to reduce the production cost.

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

For example, the photosensitive resin composition may include a compound according to the 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 the photosensitive resin composition, thereby expressing excellent color characteristics.

The compound according to one embodiment may be included in an amount of 1 wt% to 10 wt%, such as 3 wt% to 7 wt%, based on the total amount of the photosensitive resin composition. When the compound according to the embodiment is included in the above range, color reproducibility 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 is a C.I. Pigment Yellow 139, C.I. Pigment Yellow 138, C.I. Pigment yellow 150, etc., These can be used individually or in mixture of 2 or more types.

The green pigment has a color index of C.I. Pigment Green 58, C.I. Pigment green 59, etc., and 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 pigment of solid content, 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, 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, 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, or the like may be used. Specific examples of the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, and carboxylic acids. 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 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, and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. of EFKA Chemical Co., Ltd .; Zenspera Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, and the like; Or PB711, PB821 from Ajinomoto.

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

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 an amount of 10 wt% to 20 wt%, such as 12 wt% to 18 wt%, based on the total amount of the photosensitive resin composition. When the pigment dispersion is included in the above range, it is advantageous to secure process margins, and the color reproducibility and contrast ratio are excellent.

The alkali-soluble resin may be an acrylic resin.

The acrylic resin is a copolymer of the first ethylenically unsaturated monomer and the 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%, such as 10 wt% to 40 wt%, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic 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; These etc. can be mentioned, These can be used individually or in mixture of 2 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 methacrylate 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 thereof. .

The weight average molecular weight of the alkali-soluble 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 alkali-soluble resin is within the above range, the physical and chemical physical properties of the photosensitive resin composition are excellent, the viscosity is appropriate, and the adhesion to the substrate is excellent when the color filter is manufactured.

The acid value of the alkali-soluble resin may be 15 mgKOH / g to 60 mgKOH / g, such as 20 mgKOH / g to 50 mgKOH / g. When the acid value of alkali-soluble resin is in the said range, the resolution of a pixel pattern is excellent.

The alkali-soluble resin may be included in 1% by weight to 30% by weight, such as 1% by weight to 20% by weight, based on the total amount of the photosensitive resin composition. When the alkali-soluble resin is included in the above range, it is excellent in developability in the production of color filters and crosslinkability is improved to obtain excellent surface smoothness.

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

Since the photopolymerizable compound has the ethylenically unsaturated double bond, the photopolymerizable compound can 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, 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 Latent, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monometh Tyl ether (meth) acrylate, trimethylol propane tri (meth) acrylate, a tris (meth) acryloyloxyethyl phosphate, a novolak epoxy (meth) acrylate, etc. are mentioned.

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 ^®, and the like manufactured by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ^® , TC-120S ^®, etc .; The V-158 ^® and V-2311 ^{® of} Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the difunctional ester of the (meth) acrylic acid include, but are not limited to, Aronix M-210 ^® , M-240 ^® , M-6200 ^®, etc. manufactured by Toagosei Chemical Industries, Ltd .; Nihon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; And V-260 ^® , V-312 ^® and V-335 HP ^{® from} Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-450 ^{® from} Toagosei Kagaku Kogyo Co., Ltd. -710 ^® , M-8030 ^® , M-8060 ^®, etc .; Nippon Kayaku Co., Ltd. KAYARAD TMPTA ^® , DPCA-20 ^® , East-30 ^® , East-60 ^® , East-120 ^®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. The above products can be used alone or in combination of two or more.

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

The photopolymerizable compound may be included in an amount of 1 wt% to 15 wt%, such as 5 wt% to 10 wt%, based on the total amount of the photosensitive resin composition. When a photopolymerizable compound is contained in the said range, hardening arises at the time of exposure in a pattern formation process, and it is excellent in reliability, and is excellent in developability to an alkaline developing solution.

As the photopolymerization initiator, 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 may be used. .

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

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

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chloro thioxanthone, etc. are mentioned.

Examples of the benzoin 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 (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 compounds include O-acyl oxime compounds, 2- (o-benzoyl oxime) -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-acyl oxime 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-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) -butan-1-one oxime-O- Acetate and the like.

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

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light and transferring the energy after being excited.

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

The photopolymerization initiator may be included in an amount of 0.01 wt% to 10 wt%, such as 0.1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the above range, curing occurs during exposure in the pattern forming process to obtain excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and due to unreacted initiator The fall of a transmittance | permeability can be prevented.

The solvent may be a compound having a compatibility with a compound, a pigment, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator according to one embodiment but not reacting.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propylether 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; Oxy acetic acid alkyl esters such as methyl oxy acetate, oxy ethyl acetate and oxy butyl acetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxy propionic acid alkyl esters such as methyl 3-oxy propionate and ethyl 3-oxypropionate; 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-oxy propionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate and 2-oxy propionic acid propyl; 2-alkoxy propionic acid alkyl esters such as 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 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 propionic acid alkyls such as methyl methyl propionate; Esters such as ethyl 2-hydroxy propionate, ethyl 2-hydroxy-2-methyl propionate, ethyl hydroxy acetate, and methyl 2-hydroxy-3-methyl butanoate; Ketone acid esters such as ethyl pyruvate and the like; and N-methylformamide, N, N-dimethylformamide, N-methylformanilade, N-methylacetamide, 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 High boiling point solvents, such as ethyl, diethyl oxalate, diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate, are mentioned.

Among these, glycol ethers, such as ethylene glycol monoethyl ether, in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxy ethyl propionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate, and ketones such as cyclohexanone can be used.

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

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

As an example of the said epoxy compound, a phenol novolak epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol-A epoxy compound, an alicyclic epoxy compound, or a combination thereof is mentioned.

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

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

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, and γ-glycidoxy Cipropyl trimethoxysilane, (beta)-(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 in the above range, it is excellent in adhesion, shelf life and the like.

In addition, the photosensitive resin composition may further include a surfactant in order to improve the coating properties and prevent the formation of defects as necessary.

Examples of the surfactant include BM-1000 ^® , BM-1100 ^®, etc. of BM Chemie Co .; Mecha packs F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^®, etc. from Dai Nippon Inki Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Co., Ltd .; Asahi Grass Co., Ltd. Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^®, etc .; Toray silicone (Note)社SH-28PA ^®, copper -190 ^®, may be used copper ^® -193, fluorine-based surfactants and commercially available under the name, such as ^{SZ-6032 ®, SF-8428} ®.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the above range, coating uniformity is secured, staining does not occur, and wetting on the glass substrate is excellent.

In addition, the photosensitive resin composition may be added a certain amount of other additives such as antioxidants, stabilizers, etc. within a range that does not impair the 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 on 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 produce a photosensitive resin film; And heat-processing the said photosensitive resin film. Since the process conditions and the like are well known in the art, detailed descriptions thereof will be omitted herein.

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

Synthesis of Compound

Synthesis Example 1: 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) and acetone (25ml) were added to a 100ml flask and stirred while heating to 70 ° C. After completion of the reaction, the solid obtained by filtering and distilling the liquid washed with acetone. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with nucleic acid, filtered and dried under vacuum to obtain 4- (Biphenyl-2-yloxy) -3,5,6-trichloro-phthalonitrile.

Synthesis Example 2: 3 , 4,6-Trichloro-5- (2,6- dichloro - phenoxy )- phthalonitrile  synthesis

3,4,5,6-tetrachlorophthalonitrile (5g), 2,6-dichlorophenol (3.06g), K ₂ CO ₃ (3.9g) and acetone (25ml) were added to a 100ml flask and stirred while heating to 70 ° C. After completion of the reaction, the solid obtained by filtering and distilling the liquid washed with acetone. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried in vacuo to give 3,4,6-Trichloro-5- (2,6-dichloro-phenoxy) -phthalonitrile.

Synthesis Example 3: 3 , 4,6-Trichloro-5- (2,6-dibromo- phenoxy )- phthalonitrile  synthesis

In a 100 ml flask, 3,4,5,6-tetrachlorophthalonitrile (5 g), 2,6-dibromophenol (4.75 g), K ₂ CO ₃ (3.9 g), N, N-dimethylformamide (N, N-dimethylformamide) 25 ml) and stirred while heating to 70 ℃. After the reaction was extracted with EA (ethyl acetate). Concentration after extraction gives a solid. The solid obtained at this time was dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried in vacuo to obtain 3,4,6-Trichloro-5- (2,6-dibromo-phenoxy) -phthalonitrile.

Synthesis Example 4: 3 , 4,6-Trichloro-5- (2,6- difluoro - phenoxy )- phthalonitrile  synthesis

In a 100 ml flask, 3,4,5,6-tetrachlorophthalonitrile (5 g), 2,6-difluorophenol (2.45 g), K ₂ CO ₃ (3.9 g), N, N-dimethylformamide (N, N-dimethylformamide) ( 25 ml) was added and stirred while heating to 70 ℃. After the reaction was extracted with EA (ethyl acetate). Concentration after extraction gives a solid. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried in vacuo to obtain 3,4,6-Trichloro-5- (2,6-difluoro-phenoxy) -phthalonitrile.

Synthesis Example 5: 3 , 4,6-Trichloro-5- (2- chloro - phenoxy )- phthalonitrile  synthesis

3,4,5,6-tetrachlorophthalonitrile (5g), 2-chlorophenol (2.41g), K ₂ CO ₃ (3.9g) and acetone (25ml) were added to a 100ml flask and heated to 70 ° C. After completion of the reaction, a solid obtained by filtration and distillation of the liquid obtained by washing with acetone is obtained. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried in vacuo to give 3,4,6-Trichloro-5- (2-chloro-phenoxy) -phthalonitrile.

Synthesis Example 6: 3 , 4,6-Trichloro-5- (2- bromo - phenoxy )- phthalonitrile  synthesis

3,4,5,6-tetrachlorophthalonitrile (5 g), 2-bromophenol (3.25 g), K ₂ CO ₃ (3.9 g), N, N-dimethylformamide (25 ml) in a 100 ml flask Add and stir while heating to 70 ℃. After the reaction was extracted with EA (ethyl acetate). Concentration after extraction gives a solid. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried in vacuo to give 3,4,6-Trichloro-5- (2-bromo-phenoxy) -phthalonitrile.

Synthesis Example 7: 3 , 4,6-Trichloro-5- (2-fluoro- phenoxy )- phthalonitrile  synthesis

3,4,5,6-tetrachlorophthalonitrile (5 g), 2-fluorophenol (2.10 g), K ₂ CO ₃ (3.9 g), N, N-dimethylformamide (25 ml) in a 100 ml flask Add and stir while heating to 70 ℃. After the reaction was extracted with EA (ethyl acetate). Concentration after extraction gives a solid. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed with hexane several times, filtered and dried under vacuum to obtain 3,4,6-Trichloro-5- (2-fluoro-phenoxy) -phthalonitrile.

Synthesis Example 8: 3 , 4,6-Trichloro-5- (2,5- dichloro - phenoxy )- phthalonitrile  synthesis

3,4,5,6-tetrachlorophthalonitrile (5g), 2,5-dichlorophenol (3.06g), K ₂ CO ₃ (3.9g) and acetone (25ml) were added to a 100ml flask and heated to 70 ° C. After completion of the reaction, the solid obtained by filtering and distilling the liquid washed with acetone. The solid obtained at this time is dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried in vacuo to give 3,4,6-Trichloro-5- (2,5-dichloro-phenoxy) -phthalonitrile.

Synthesis Example  9: Synthesis of Compound Represented by Formula 5

4- (Biphenyl-2-yloxy) -3,5,6-trichloro-phthalonitrile (1.5 g) of Synthesis Example 1 and 3,4,6-Trichloro-5- (2,6- of Synthesis Example 2) in a 100 mL flask Dichloro-phenoxy) -phthalonitrile (0.49g), 1,8-Diazabicycloundec-7-ene (1.52g), and 1-pentanol (14g) were added and heated to 90 ° C to dissolve the solid, followed by zinc acetate (0.23g). Put and stir while heating to 140 ℃. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried in vacuo. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is appropriately added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (5).

[Formula 5]

Maldi-tof MS: 1656.79 m / z

Synthesis Example  10: Synthesis of Compound Represented by Chemical Formula 6

4- (Biphenyl-2-yloxy) -3,5,6-trichloro-phthalonitrile (1.6 g) of Synthesis Example 1 and 3,4,6-Trichloro-5- (2,6- of Synthesis Example 2) in a 100 mL flask Dichloro-phenoxy) -phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.74g) and 1-pentanol (14g) were added and heated to 90 ° C to dissolve the solid and zinc acetate (0.34g) was added. Put and stir while heating to 140 ℃. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried in vacuo. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is appropriately added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (6).

[Formula 6]

Maldi-tof MS: 1649.57 m / z

Synthesis Example  11: Synthesis of Compound Represented by Formula 7

4- (Biphenyl-2-yloxy) -3,5,6-trichloro-phthalonitrile (1 g) of Synthesis Example 1, 3,4,6-Trichloro-5- (2,6-dichloro of Synthesis Example 2, in a 100 mL flask -phenoxy) -phthalonitrile (2.9g), 1,8-Diazabicycloundec-7-ene (3g) and 1-pentanol (27g) were added and heated to 90 ° C to melt the solid, followed by zinc acetate (0.45g) and 140 Stir while heating to ° C. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried in vacuo. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is appropriately added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following formula (7).

[Formula 7]

Maldi-tof MS: 1642.36 m / z

Synthesis Example  12: Synthesis of Compound Represented by Formula 8

3,4,6-Trichloro-5- (2,6-dichloro-phenoxy) -phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (0.87 g) and 1-pentane of Synthesis Example 2 in a 100 mL flask Add (7g) and heat to 90 ℃ to dissolve the solid, add zinc acetate (0.17g) and stir while heating to 140 ℃. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried in vacuo. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is suitably added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following formula (8).

[Formula 8]

Maldi-tof MS: 1635.14 m / z

Synthesis Example  13: Synthesis of Compound Represented by Formula 9

3,4,6-Trichloro-5- (2,6-dibromo-phenoxy) -phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (0.87 g) and 1-pentane of Synthesis Example 3 in a 100 mL flask Add (7g) and heat to 90 ℃ to dissolve the solid, add zinc acetate (0.17g) and stir while heating to 140 ℃. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is suitably added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (9).

[Formula 9]

Maldi-tof MS: 1990.78 m / z

Synthesis Example  14: Synthesis of Compound Represented by Formula 10

3,4,6-Trichloro-5- (2,6-difluoro-phenoxy) -phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (0.87 g) and 1-pentane of Synthesis Example 4 in a 100 mL flask Add (7g) and heat to 90 ℃ to dissolve the solid, add zinc acetate (0.17g) and stir while heating to 140 ℃. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried in vacuo. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is appropriately added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (10).

[Formula 10]

Maldi-tof MS: 1503.53 m / z

Synthesis Example  15: Synthesis of Compound Represented by Formula 11

In a 100 mL flask, 3,4,6-Trichloro-5- (2-chloro-phenoxy) -phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (0.87 g) and 1-pentanol of Synthesis Example 5 ( 7g) is added and heated to 90 ° C to dissolve the solid, and then zinc acetate (0.17g) is added and stirred while heating to 140 ° C. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is appropriately added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (11).

[Formula 11]

Maldi-tof MS: 1497.38 m / z

Synthesis Example  16: Synthesis of Compound Represented by Formula 12

In a 100 mL flask, 3,4,6-Trichloro-5- (2-bromo-phenoxy) -phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (0.87 g) and 1-pentanol of Synthesis Example 6 ( 7g) is added and heated to 90 ° C to dissolve the solid, and then zinc acetate (0.17g) is added and stirred while heating to 140 ° C. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried under vacuum. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is appropriately added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following formula (12).

[Formula 12]

Maldi-tof MS: 1675.19 m / z

Synthesis Example  17: Synthesis of Compound Represented by Chemical Formula 13

In a 100 mL flask, 3,4,6-Trichloro-5- (2-fluoro-phenoxy) -phthalonitrile (1.5 g), 1,8-Diazabicycloundec-7-ene (0.87 g) and 1-pentanol ( 7g) is added and heated to 90 ° C to dissolve the solid, and then zinc acetate (0.17g) is added and stirred while heating to 140 ° C. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried in vacuo. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is appropriately added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and vacuum dried to obtain a compound represented by the following formula (13).

[Formula 13]

Maldi-tof MS: 1431.57 m / z

Synthesis Example  18: Synthesis of Compound Represented by Formula 14

4- (Biphenyl-2-yloxy) -3,5,6-trichloro-phthalonitrile (1.6 g) of Synthesis Example 1 and 3,4,6-Trichloro-5- (2,5- of Synthesis Example 8) in a 100 mL flask Dichloro-phenoxy) -phthalonitrile (1.5g), 1,8-Diazabicycloundec-7-ene (1.74g) and 1-pentanol (14g) were added and heated to 90 ° C to dissolve the solid and zinc acetate (0.34g) was added. Put and stir while heating to 140 ℃. After completion of the reaction, the precipitate was confirmed by methanol, filtered and dried in vacuo. The dried solid is purified by column chromatography. Solid dichloromethane obtained after purification is appropriately added to dissolve the solid, and then crystallized by adding methanol. The crystallized solid is filtered and dried in vacuo to obtain a compound represented by the following formula (14).

[Formula 14]

Maldi-tof MS: 1649.57 m / z

compare Synthesis Example  1: Synthesis of Compound Represented by Formula (X)

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

[Formula X]

Maldi-tof MS: 1584.04 m / z

(Synthesis of Photosensitive Resin Composition)

Example  One

The photosensitive resin compositions according to Example 1 were prepared by mixing the components mentioned below in the compositions shown in Table 1 below.

Specifically, after dissolving the photopolymerization initiator in a solvent and stirred at room temperature for 2 hours, an alkali-soluble 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 5) and a pigment (in the form of a pigment dispersion) prepared in Synthesis Example 9 were added as a colorant to the obtained reactant, followed by stirring at room temperature for 1 hour. The product was then filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: weight%) Blended raw materials content coloring agent dyes Compound of Synthesis Example 9 5.0 Pigment Dispersion 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 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 Propylene Glycol Monomethyl Ether Acetate (PGMEA) 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 10 (compound represented by Formula 6) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  3

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 11 (compound represented by Formula 7) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  4

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 12 (compound represented by Formula 8) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example 5

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 13 (compound represented by Formula 9) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  6

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 14 (compound represented by Formula 10) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  7

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 15 (compound represented by Formula 11) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  8

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 16 (compound represented by Formula 12) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  9

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 17 (compound represented by Formula 13) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  10

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 18 (compound represented by Formula 14) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  11

3.7% by weight instead of 5% by weight, "2.5% by weight of Pigment G58 pigment dispersion and 13.7% by weight of Pigment Y138 pigment dispersion" instead of "15.0% by weight of Pigment Y138 pigment dispersion" and 30.1% by weight of PGMEA instead of 30.0% by weight. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the wt% was used.

Example  12

A photosensitive resin composition was prepared in the same manner as in Example 11, except that the compound of Synthesis Example 10 (compound represented by Formula 6) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  13

A photosensitive resin composition was prepared in the same manner as in Example 11 except that the compound of Synthesis Example 11 (compound represented by Formula 7) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  14

A photosensitive resin composition was prepared in the same manner as in Example 11, except that the compound of Synthesis Example 12 (compound represented by Formula 8) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  15

A photosensitive resin composition was prepared in the same manner as in Example 11 except that the compound of Synthesis Example 13 (compound represented by Formula 9) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  16

A photosensitive resin composition was prepared in the same manner as in Example 11 except that the compound of Synthesis Example 14 (compound represented by Formula 10) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  17

A photosensitive resin composition was prepared in the same manner as in Example 11, except that the compound of Synthesis Example 15 (compound represented by Formula 11) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  18

A photosensitive resin composition was prepared in the same manner as in Example 11 except that the compound of Synthesis Example 16 (compound represented by Formula 12) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  19

A photosensitive resin composition was prepared in the same manner as in Example 11, except that the compound of Synthesis Example 17 (compound represented by Formula 13) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Example  20

A photosensitive resin composition was prepared in the same manner as in Example 11 except that the compound of Synthesis Example 18 (compound represented by Formula 14) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Comparative example  One

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Comparative Synthesis Example 1 (compound represented by Formula X) was used instead of the compound of Synthesis Example 9 (compound represented by Formula 5).

Comparative example  2

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

(Unit: weight%) Blended raw materials 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 Propylene Glycol Monomethyl Ether Acetate (PGMEA) 16.0 Total 100.00

Evaluation: Luminance and Contrast Ratio Measurements

The photosensitive resin composition prepared in Example 1 to Example 20, Comparative Example 1 and Comparative Example 2 was applied to a glass substrate having a thickness of 1 mm by degreasing washing, and a 90 ° C. hot plate Drying over the bed for 2 minutes gave a coating. Subsequently, the coating film was exposed using a high pressure mercury lamp having a dominant wavelength of 365 nm. Thereafter, the sample was dried in a hot air circulation drying furnace at 200 ° C. for 5 minutes. The pixel layer measured luminance (Y) and contrast ratio using a spectrophotometer (MCPD3000, Otsuka electronic Co., Ltd.), and is shown in Table 3 below.

Brightness (Y) Contrast Ratio Example 1 63.2 15,700 Example 2 63.6 15,600 Example 3 63.3 15,200 Example 4 63.3 15,200 Example 5 63.1 15,400 Example 6 62.8 15,300 Example 7 62.9 15,200 Example 8 63.0 15,300 Example 9 62.8 15,500 Example 10 62.6 15,500 Example 11 62.8 14,900 Example 12 63.0 14,800 Example 13 62.9 14,600 Example 14 62.8 14,700 Example 15 62.7 14,800 Example 16 62.6 15,000 Example 17 62.7 14,800 Example 18 62.7 14,700 Example 19 62.5 14,900 Example 20 62.4 14,800 Comparative Example 1 62.3 14,300 Comparative Example 2 62.1 13,800

From Table 3, the photosensitive resin composition of Examples 1 to 20, and more specifically, the photosensitive resin composition of Examples 1 to 9 containing the compound according to one embodiment as a dye does not contain the compound It can be seen that color characteristics superior to the photosensitive resin compositions of Comparative Example 1 and Comparative Example 2 are exhibited.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to this, It can be variously modified and implemented in a claim, a detailed description of an invention, and the range of an accompanying drawing. Naturally, it belongs to the scope of the invention.

Claims (17)

Compound represented by the following 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 group Ring C6 to C20 aryloxy group,
Provided that at least one of R ¹ to R ¹⁶ is represented by any one selected from the group consisting of the following Chemical Formula 3-1, Chemical Formula 3-2, Chemical Formula 3-3, and Chemical Formula 3-4,
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Chemical Formula 3-1, Chemical Formula 3-2, Chemical Formula 3-3, and Chemical Formula 3-4,
R ¹⁷ and R ¹⁸ are each independently a halogen atom.
delete The method of claim 1,
At least one of the R ¹ to R ¹⁶ is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of the R ¹ to R ¹⁶ is a compound represented by the formula (4).
[Formula 4]

The method of claim 3,
At least one of R ¹ to R ⁴ is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of the R ^{5 To} R ^{8 Is} represented by the formula (4),
At least one of R ⁹ to R ¹² is represented by Formula 4,
At least one of the R ^{13 To} R ¹⁶ A compound represented by the formula (4).
The method of claim 3,
At least one of R ¹ to R ⁴ is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of R ⁵ to R ⁸ is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of R ⁹ to R ¹² is represented by Formula 4,
At least one of the R ^{13 To} R ¹⁶ A compound represented by the formula (4).
The method of claim 3,
At least one of R ¹ to R ⁴ is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of the R ^{5 To} R ^{8 Is} represented by the formula (4),
At least one of the R ⁹ to R ¹² is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of the R ^{13 To} R ¹⁶ A compound represented by the formula (4).
The method of claim 3,
At least one of R ¹ to R ⁴ is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of R ⁵ to R ⁸ is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of the R ⁹ to R ¹² is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of the R ^{13 To} R ¹⁶ A compound represented by the formula (4).
The method of claim 1,
At least one of R ¹ to R ⁴ is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of R ⁵ to R ⁸ is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of the R ⁹ to R ¹² is represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4,
At least one of R ¹³ to R ¹⁶ is a compound represented by any one selected from the group consisting of Formula 3-1 to Formula 3-4.
The method of claim 1,
The compound represented by Chemical Formula 1 is a compound represented by any one of the following Chemical Formulas 5 to 13.
[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

The method of claim 1,
The compound is a green dye.
The method of claim 10,
The green dye has a maximum transmittance in the wavelength range of 445nm to 560nm.
The photosensitive resin composition containing the compound of any one of Claims 1-11.
The method of claim 12,
The compound is 1% by weight to 10% by weight relative to the total amount of the photosensitive resin composition.
The method of claim 12,
The photosensitive resin composition further comprises an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent.
The method of claim 14,
The photosensitive resin composition further comprises a pigment.
The method of claim 15,
The pigment is a photosensitive resin composition comprising a yellow pigment, a green pigment or a combination thereof.
The color filter manufactured using the photosensitive resin composition of Claim 12.