WO2017018617A1

WO2017018617A1 - Novel compound, photosensitive resin composition containing same, and color filter

Info

Publication number: WO2017018617A1
Application number: PCT/KR2015/013609
Authority: WO
Inventors: 김선대; 최은정; 신명엽; 최승집
Original assignee: 삼성에스디아이 주식회사
Priority date: 2015-07-30
Filing date: 2015-12-11
Publication date: 2017-02-02

Abstract

Provided are: a compound including cations and anions, wherein the cations are represented by a specific formula; a photosensitive resin composition containing the compound; and a color filter manufactured using the photosensitive resin composition.

Description

【Specification】

[Name of invention]

Novel compounds, photosensitive resin compositions and color filters comprising the same

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

Background Art

In order to easily learn the stable dispersion and miniaturization of the pigment dispersion, a number of studies have been conducted to produce a pigment having a particle size of a certain size through a process such as salt milling the pigment obtained through the synthesis. In addition, in the case of pigments, there are limitations of brightness and contrast ratios resulting from the particle size, and in the case of color imaging devices for image sensors, a smaller dispersion particle size is required to form fine patterns, so that the pigments are not used alone. ， Research to improve physical properties of brightness, contrast ratio and the like by using a colorant of a hybrid form in which a pigment and a dye are mixed.

However, to date, no colorant having a large effect of improving physical properties such as heat resistance and luminance has been reported as compared with conventional colorants.

Therefore, there is a need for research on a compound suitable as a colorant used in the preparation of the photosensitive resin composition.

[Detailed Description of the Invention]

[Technical problem]

One embodiment is to provide novel compounds.

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

Another embodiment is prepared using the photosensitive resin composition

To provide a color filter. Technical Solution One embodiment provides a compound containing cyanide and an anion, wherein the cation is represented by the following formula (1).

In Chemical Formula 1,

R ¹ to R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,

R ⁷ is a substituted or unsubstituted C6 to C20 aryl group,

X is -Ο-, -S- or — NR ^8- (R ⁸ is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group).

X may be -0- or -S-.

R ¹ to R ⁴ may be each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.

The cation may be represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted C1 to C20 alkyl group, and R ¹¹ ¾ R ¹² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 An aryl group,

R ¹³ is a substituted or unsubstituted C6 to C20 aryl group,

R ¹⁴ to R ¹⁷ are each independently a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

nl to n4 are each independently an integer of 0 to 5, 0 ≦ nl + n2 ≦ 5, 0 ≦ n3 + n4 <5,

X is -0- or -S-.

The cation may be represented by any one selected from the group consisting of the following Chemical Formulas 3 to 7.

[Formula 3]

In Chemical Formula 3,

R ¹⁸ , R ¹⁹ and R ²¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ²² is a halogen atom,

R ²³ to R ²⁶ are each independently a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and ᅳ

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-.

[Formula 4]

In Chemical Formula 4 R ¹⁸ to R ²¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ²² is a halogen atom,

R ²³ to R ²⁶ are each independently a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-.

[Formula 5]

In Chemical Formula 5,

R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group, R ²² is a halogen atom,

R ²⁷ is a substituted or unsubstituted C6 to C20 aryl group, 'm is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-. [Formula 6]

In Chemical Formula 6,

R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group

R ²² is a halogen atom,

R ²³ to R ²⁶ are each independently a halogen atom or a substituted or unsubstituted C110 alkyl group,

R ²⁷ and R ²⁸ are each independently a substituted or unsubstituted C6 to C20 aryl group and m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-.

[Formula 7]

In Chemical Formula 7 R ^18, and R ¹⁹ and R ²¹ are C1 to C20 alkyl groups each independently substituted or unsubstituted, ^"

R ²² is a halogen atom,

2 ³ to R ²⁶ are each independently a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ²⁸ is a substituted or unsubstituted C6 to C20 aryl group,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-.

The cation may be represented by the following Chemical Formulas 5-3, 5-4, 5-5, 5-6, 7-6, 7-8, 7-10, 7-12, and 7-17. It may be represented by any one selected from the group consisting of 7-23.

[Formula 5-3]

[Formula 5_6]

[Formula 7_8]

[Formula 7-10]

7-19]

[Formula 7-21]

[Formula 7-22]

The anion may be represented by one selected from the group consisting of Formulas A to F.

[Formula A]

[Formula Β]

Ο

、-II

ο 、 ᄋ

[Formula c]

PW _{l 2} 0 '.40 [Formula D]

SiW, ₂ 0 ₄ o ^{4 "}

[Formula E]

CF3SO3 ^"

Formula F]

C10 ₄ ^"

The compound may be a dye.

The dye may be a blue dye.

The compound may have a maximum absorbance ') in the wavelength range of 600 nm to 700 nm.

The compounds may have a T _max in the wavelength range of 400 nm to 500 nm. Another embodiment provides a photosensitive resin composition comprising the compound. The photosensitive resin composition may further include a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The photosensitive resin composition may further include a pigment.

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

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

Advantageous Effects

The compound according to the embodiment has excellent coloring power and heat resistance, and by using the photosensitive resin composition including the compound, it is possible to prepare a color filter having excellent luminance.

[Best form for implementation of the invention]

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 present specification, "substituted" to "substituted" means that of the present invention At least one hydrogen atom of the functional group is a halogen atom (F, Br, Cl or I), a hydroxy group, a nitro group, a cyano group, an amino group (NH ₂ , NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ) Wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different and are each independently C1 to C10 alkyl group), amidino group, hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted A substituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. It means.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, specifically means a C1 to C15 alkyl group, and "'cycloalkyl group" means a C3 to C20 cycloalkyl group, specifically Means a C3 to C18 cycloalkyl group, "'alkoxy group" means a ci to C20 alkoxy group, specifically means a C1 to C18 alkoxy group, "aryl group" means a C6 to C20 aryl group,

Specifically, it refers to a C6 to 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 In addition, specifically, it means a C1 to C18 alkylene group, "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"

"Acrylate" and "methacrylate" mean that both are possible, and "(meth) acrylic acid" means that both "acrylic acid" and "methacrylic acid" are possible.

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

"Copolymer" means a block copolymer or a random copolymer.

Unless otherwise defined in the chemical formulas herein, 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.

Unless otherwise defined herein, "*" means a moiety connected to the same or different atoms or formulas. ^'An embodiment provides a compound comprising positive and negative silver, The cation is represented by the following formula (1).

In Chemical Formula 1,

R ⁷ is a substituted or unsubstituted C6 to C20 aryl group,

X is -Ο-, -S- or -NR ^8- (R ⁸ is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group).

For example, X may be -0- or -S-.

For example, R ¹ to R ⁴ may be each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.

Recently, in order to manufacture a color filter having a high brightness and high contrast ratio, a study to achieve a high brightness and high contrast ratio of a color filter by synthesizing a dye more durable than the pigment, and using the composition containing the dye, have. Among the dyes, studies using a triarylmethane compound known as a blue dye have been in progress. The triarylmethane dye has the advantage of having a high luminance in the wavelength range of 420 nm to 450 nm, but the solubility in organic solvents such as PGMEA and the like has a disadvantage of poor heat resistance. Attempts have been made to use anions such as naphthalenesulfonic acid and naphthylaminesulfonic acid in the triarylmethane dye to overcome the weak heat resistance, but the heat resistance has not been greatly improved.

Compound according to one embodiment includes a cation represented by the formula (1), excellent spectroscopy, compared to a compound used as a conventional colorant, such as triarylmethane compound Characteristics and high molar extinction coefficient, excellent coloring power and heat resistance, cyclonuxanone,

It also has excellent solubility in organic solvents such as PGMEA. In particular, the compound according to one embodiment has three rings linked to the central carbon, one of the three rings has an aromatic hetero ring containing a cyano group, and thus a composition comprising a compound according to one embodiment Silver can provide a color filter excellent in brightness and durability. For example, the cation may be represented by the following Chemical Formula 2.

[Formula 2]

In Chemical Formula 2,

R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ″ and R ¹² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ¹³ is a substituted or unsubstituted C6 to C20 aryl group,

nl to n4 are each independently an integer of 0 to 5, 0 ≦ nl + n2 ≦ 5, 0 <n3 + n4 <5,

X is -0- or -S-.

For example, the nl to n4 may be each independently an integer of 0 or 1. For example, the halogen atom may be F, Cl, Br or I.

For example, the cation may be represented by any one selected from the group consisting of the following Chemical Formulas 3 to 7. [Formula 3]

In Chemical Formula 3,

R ²² is a halogen atom,

And R ²³ to R ²⁶ are C1 to C10 alkyl groups each independently selected from ring a halogen atom or a substituted or unsubstituted,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or.

[Formula 4]

In Chemical Formula 4 ^1S and R to R ²¹ are C1 to C20 alkyl groups each independently substituted or unsubstituted,

R ²² is a halogen atom,

R ²³ to R ²⁶ are each independently a halogen atom or a substituted or unsubstituted C 1 to C 10 alkyl group,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-.

[Formula 5]

In Chemical Formula 5,

R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group and R ²² is a halogen atom,

R ²⁷ is a substituted or unsubstituted C6 to C20 aryl group,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-. [Formula 6]

In Chemical Formula 6,

And R ²³ to R ²⁶ each independently represent a halogen atom or a substituted or unsubstituted C110 alkyl group, ^'

R ²⁷ and R ²⁸ are each independently a substituted or unsubstituted C6 to C20 aryl group _: m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-.

[Formula 7]

In Chemical Formula 7 R ¹⁸ , R ¹⁹ and R ²¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ²² is a halogen atom,

R ²⁸ is a substituted or unsubstituted C6 to C20 aryl group,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-.

For example, the cation is represented by the following Chemical Formula 3-1, Chemical Formula 3-2, Chemical Formula 4-1 to Chemical Formula 4-3, Chemical Formula 5-1 to Chemical Formula 5-8, Chemical Formula 6-1 to Chemical Formula 6-19, and Chemical Formula 7-1. It may be represented by any one selected from the group consisting of Formula 7-23, but is not limited thereto.

[Formula 3-1]



[Formula 5-8]

[Formula 6-8]

[Formula 6-12]

[Formula 6-19]

[Formula 7-1

[Formula 7-ΙΓ]

[Formula 7-15]

[Formula 7-17]

[Formula 7-20]

[Formula 7-21]

[Formula 7-23]

The compound according to one embodiment includes an anion, and the anion may be represented by any one selected from the group consisting of Formulas A to F, but is not limited thereto.

[Formula A]

Β]

[Formula C]

PW ₁₂ O ₄₀ ^3-

[Formula D]

SiW _{! 2} O ₄₀ ^{4 "}

[Formula E]

CF ₃ S0 ₃ ^"

Formula F]

C10 ₄ ^"

Compound according to one embodiment is a cation represented by the formula (1)

By virtue of this, the vivid color can be expressed even in a small amount, and the display device can be manufactured excellent in color characteristics such as brightness and contrast ratio used as a coloring agent. for example The compound may be a colorant such as a dye such as a blue dye such as a dye having a maximum absorbance (^ in a wavelength range of 600 nm to 700 nm, such as a wavelength range of 610 nm to 680 nm, such as 610 nm to 650 rnn. may. for example, the compound may be a dye having a T應in the wavelength range of 400 nm to a wavelength range of 500 nm, for example 420 nm to the 450 nm wavelength range, such as 430 nm to 440 nm. T _max is the maximum Permeability may mean.

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 including the compound according to the embodiment is provided.

For example, the photosensitive resin composition may include a compound, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent according to the embodiment.

For example, the photosensitive resin composition may further include a pigment.

The compound according to the embodiment may serve as a colorant such as a dye such as a blue dye in the photosensitive resin composition, and may express excellent color characteristics. The compounds according to the embodiment can be included as ^1% to 10% by weight, for example, 3 parts by weight ^_0/0 to 7 parts by weight ⁰ /. With respect to the photosensitive resin composition the total amount of the compounds according to the embodiment as eu the range When included, color reproducibility and contrast ratio are excellent.

The pigment may include, but is not limited to, a blue pigment, a yellow pigment, a green pigment, a red pigment, a violet pigment, or a combination thereof. For example, the pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.

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

Pigments of the solid is 1 wt. ^_0/0 to 20 parts by weight ^_0/0, for example, 8% by weight to 20 parts by weight ⁰ / with respect to the pigment dispersion the total amount., Such as 15 wt. ⁰ /. To about 20 wt%, such as 8% to about 15 weight ^_0/0, for example, 10 parts by weight ⁰ /. to 20 parts by weight ⁰ /., such as 10 wt. ^_0/0 to 15 It may be included in weight percent.

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 BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165,

DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182,

DISPERBYK-2000, DISPERBYK-2001, 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, Solsperse24000GR, Solsperse 27000, Solsperse 28000, and the like; Or Ajinomoto, ΡΒ7Π, ΡΒ821.

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

Examples of the solvent for forming the pigment dispersion include ethylene glycol acetate,

Ethyl salosolve, propylene glycol monomethyl ether acetate, ethyl lactate,

Polyethylene glycol, cyclonucleanone, propylene glycol methyl ether and the like can be used.

The pigment dispersion liquid was 5 parts by weight _{^0/0 and} with respect to the photosensitive resin composition, a total amount

30 weight percent, such as 10 weight percent to 25 weight ⁰ /. remind

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 binder resin may be an acrylic binder resin, a cardo binder resin, or a combination thereof. The acrylic resin is a copolymer of a crab 1 ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be 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.

To the first ethylenically unsaturated monomer may comprise from 5 parts by weight ^_0/0 to 50% by weight, such as 10 wt. ⁰ /. To 40% by weight relative to the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, (X-methylstyrene, vinylluene, vinylbenzylmethyl ether; methyl (meth) acrylate,

Ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxysabutyl (meth) acrylate, benzyl (meth) acrylate,

Unsaturated carboxylic acid ester compounds such as cyclonuclear chamber (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 binder resin include polybenzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate copolymer,

(Meth) acrylic acid / benzyl methacrylate / styrene copolymer,

(Meth) acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer,

(Meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc. are mentioned, It is not limited to these, These can also be used individually or in combination of 2 or more types.

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. have. When the weight average molecular weight of the binder resin is within the above range, the physical and chemical 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 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 is the photosensitive resin composition the total amount by weight of 1 ^_0/0 to 30 parts by weight ⁰ / with respect to the., For example, may be included in one weight ⁰ /. To 15% by weight. When the binder resin is included in the above range, it is excellent in developability and crosslinking property in the production of color filters to obtain excellent surface smoothness.

The photopolymerizable compound has at least one ethylenically unsaturated double bond

Monofunctional or polyfunctional esters of (meth) acrylic acid can be used.

The photopolymerizable compound may have an ethylenically unsaturated double bond, thereby causing sufficient polymerization during exposure in a pattern forming process to form a pattern having excellent heat resistance, light resistance, and chemical resistance.

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-nucleic acid diol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerytrie di (meth) acrylic Tetra (meth) acrylate as a pentaerythrite, tetra (meth) acrylate as a pentaerytrile, nucleus (meth) acrylate as a pentaerythrite, di (meth) acrylate, a dipentaeryte Tree to tree (meth) acrylate, dipentaerythr to penta (meth) acrylate,

Dipentaerythritol nucleated (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ^' ter (meth) acrylate, trimethyl propane

Tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, and noblepoxy (meth) acrylate.

Examples of commercially available products of the photopolymerizable compound are as follows. remind

Examples of monofunctional esters of (meth) acrylic acid include, but are not limited to, Aronix M-101® manufactured by Toagosei Kagaku Kogyo Co., Ltd., M-1 1 1®, M-1 14®, etc .; KAYARAD TC- 1 1 OS®, Copper TC-120S®, etc .; The V-158® and V-231 1® by Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the difunctional ester of (meth) acrylic acid include, but are not limited to, Aronix M-210®, M-240®, M-6200®, manufactured by Toagosei Chemical Industries, Ltd .; KAYARAD HDDA® from Nihon Kayak Co., Ltd., HX-220®, R-604®, etc .; The V-260®, V-312®, and V-335 HP® by Osaka Yuki Chemical Co., Ltd. are mentioned. Trifunctionality of the (meth) acrylic acid

Examples of the ester include Aronix M-309®, M-400®, M-405®, M-450®, M-710®, and M-8030 from Toagosei Kagaku Kogyo Co., Ltd. ®, M-8060®, etc .; Nihon

KAYARAD TMPTA®, Copper DPCA-20®, Copper -30®, Copper -60®, Copper -120®, etc. manufactured by Kayaku Co., Ltd .;

And V-295®, copper -300®, copper -360®, copper -GPT®, copper -3PA®, and copper-400® by Osaka Yuki Kayaku High School Co., Ltd. The above products can be used alone or in combination of two or more.

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

The photopolymerizable compounds may be included as one weight ^_0/0 to 15 parts by weight ^_0/0, for example, increase of 5 ^_0/0 to 10 parts by weight ⁰ /. Relative to the total 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.

The photopolymerization initiator is generally used in the photosensitive resin composition

As an initiator, an acetophenone type compound, a benzophenone type compound, a thioxanthone type compound, a benzoin type compound, a triazine type compound, an oxime type compound, or a combination thereof can be used, for example.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibuoxy acetophenone, 2-hydroxy-2-methylpropiophenone, and ρ-t-butyltrichloro Acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholine Nopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like.

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

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 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'-methoxinaphthyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-lryl) -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-methoxy-naphtho-1-yl) eu ^4, 6-bis (trichloromethyl) -S- triazine, ^2-4-bis (Trichloromethyl) -6-piperonyl-S-triazine, 2-4-bis (trichloromethyl) -6- (4-mesoxystyryl) -S-triazine, etc. are mentioned. Examples of the oxime compounds include 0-acyl oxime compounds, 2- ( ₀ -benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ( ₀ -acetyl oxime ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-

3-yl] ethanone, 0-ethoxycarbonyl-α-oxyamino-1-phenylpropane-1-one and the like can be used. Specific examples of the 0-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-dione 2-oxime-0-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione 2 -Oxime-0-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oxime-0-acetate and 1-(4-phenylsulfanylphenyl)-butane-1-silver oxime-0- Acetate and the like.

The photopolymerization initiator is a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound,

A biimidazole type compound etc. can be used.

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

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate and pentaerythritol with tetrakis-3-mercapto propionate and dipentaerythryl tetrakis- 3-mercapto propionate, etc. are mentioned.

The photopolymerization initiator is a photosensitive resin composition, a total amount of 0.01% by weight to 10 parts by weight ⁰ / with respect to the., For example, 0.1 can be included in a weight ⁰ /. To 5% by weight. 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, The fall of the transmittance | permeability can be prevented.

The solvent may be a compound having a compatibility with the compound, the pigment, the binder resin, the photopolymerizable compound, and the photopolymerization initiator according to one embodiment, but does not react.

Examples of the solvent include alcohols such as methanol and ethanol; Dichloroethyl ether, ^η -butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, etc.

Ethers; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl salosolve acetate and diethyl cellosolve acetate; Carbyols, such as methyl ethyl carbyol and diethyl carbyl, such as 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 methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Methyl ethyl ketone, cyclonucleanone, 4-hydroxy-

Ketones such as 4-methyl-2-pentanone, methyl -η-propyl ketone, methyl -η-butyl ketone, methyl -η-amyl ketone and 2-heptanone; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, -η-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-hydroxy 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-methoxy 2-alkoxy propionic acid alkyl esters such as methyl propionate, ethyl 2-methoxy propionate, ethyl 2-ethoxy propionate and methyl 2-propyne propionate; 2-oxy-2-methyl propionic acid esters, such as 2-oxy-2-methyl propionate methyl and 2-oxy-2-methyl propionate, 2-methoxy-2-methyl propionate methyl, 2-ethoxy- Monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl propionic acid alkyls such as 2-methyl ethyl propionate; Esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethyl hydroxy acetate, and 2-hydroxy-3-methyl butanoate; Ketone acid esters such as ethyl pyruvate, and the like; Ν-methylformamide, Ν, Ν-dimethylformamide, N-methylformanile, Ν-methylacetamide, Ν, Ν-dimethylacetamide , N-methylpyridone, dimethyl sulfoxide, benzyl ethyl ether, dinucleosil ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octane, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate;

Among these, ethylene glycol is preferably considered in consideration of compatibility and reactivity.

Glycol ethers such as monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxy ethyl propionate; Carbyls such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate, propylene glycol propylether acetate, etc. may be used.

The solvent may be included in a balance, such as 30 weight% ^{0. °} to 90 weight% 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 is excellent in manufacturing a color filter.

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

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

The epoxy compound may be included in an amount of 0.01 to 20 parts by weight, such as 0.1 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. Epoxy When the compound is included in the above range, the adhesiveness, shelf life 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. 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-glycol. Propyl trimethoxysilane, β- (3,4-epoxycyclonuclear chamber) ethyltrimethoxysilane, and the like may be cited when used. These may be used alone or in combination of two or more thereof.

The silane coupling agent may be included in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included in the above range, it is excellent in adhesion and storage property.

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

Examples of the surfactant include, but are not limited to, BM-1000®, BM-1 100® by BM Chemie, Inc .; Dainippon ingki Kagaku Kogyo Co., Ltd. Mechanical pack社F 142D®, copper F 172®, 173® F copper, copper F _183®. Etc; Prorad FC-135®, Copper FC-170C®, Copper FC-430®, Copper FC- from Sumitomo 3M Co., Ltd.

431® and the like; Asahi Grass Co., Ltd. Saffron S-1 12®, copper S-1 13®, copper S-131®, copper S-141®, copper

S-145® and the like; Toray Silicone Co., Ltd. commercially available fluorine-based surfactants such as SH-28PA®, copper -190®, copper -193®, SZ-6032® and SF-8428® can be used.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight with respect to 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the above range, coating uniformity may be secured, stains may not occur, and wetting of the glass substrate may be performed. ) 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.

'' The photosensitive resin composition is spin-coated, slat coated, inkjet onto a supporting substrate Coating by printing or the like; Drying the coated photosensitive resin composition to form a photosensitive resin composition film; Exposing the photosensitive resin composition film; The exposed photosensitive resin composition film is developed with an aqueous alkali solution to be photosensitive.

Manufacturing a 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.

[Form for implementation of invention]

(Example)

Synthesis Example

Synthesis Example 1

(1) Under a nitrogen atmosphere, ^{4, 4'-dichlorobenzophenone (10g,} 39.8mmol),

Pd ₂ (dba) ₃ (220 mg, 0.002 mol%), XPhos (230 mg, 0.005 mol%) and sodium t-butoxide (l 1.48 g, 1 19.5 mmol) were added to a round bottom flask and 50 g of toluene was added thereto. After stirring for 10 minutes at room temperature, 2,6-difluoroaniline (10.3 g, 79.6 mmol) is added thereto. Stirring for 2 hours while gradually raising the temperature of the reaction product to 80 ^° C. When the reaction was completed, the silver content of the reaction product was lowered to room temperature, and then 50 g of isopropanol was added thereto, followed by stirring. The precipitate is filtered off using a filter, washed with water and then added to acetonkrile and stirred at 80 ^° C for 30 minutes. After lowering the silver to room temperature, the precipitate was filtered and dried to synthesize a compound (15 g, 86%) represented by the following Chemical Formula S-1.

[Formula s-1]

NMR (solvent: DMSO-d6): 8.54 (s, 2H), 7.60 (d, 4H), 7.35-7.15 (m, 6H), 6.73 (d, 4H). GC-MS: 436 m / z.

(2) A compound represented by the following Chemical Formula S-2 was synthesized in the same manner as in (1) of Synthesis Example 1 except that 2,6-dimethylaniline was used instead of 2,6-difluoroaniline. S-2]

NMR (solvent: DMSO-d6): 8.05 (s, 2H), 7.53 (d, 4H), 7.17-7.08 (m, 6H), 6.43 (d, 4H) _: 2.14 (s, 12H).

GC-MS: 420 mix.

3, except for using 2,6-difluoroaniline instead of 2, ⁶ -diisopropylanilme, in the same way as in the (1) in Synthesis Example 1, and the product was synthesized with the compound represented by the general formula S-3.

Formula S-3]

'H NMR (solvent: CDC13): 7.66 (d, 4H), 7.35-7.30 (m, 2H), 7.23 (t, 4H), 6.47-6.45 (m, 4H), 5.50 (s, 2H), 3.21- 3.12 (m, 4 H), 1.14 (d, 24 H).

GC-MS: 532 m / z.

(4) A compound represented by the following formula (S-4) was synthesized in the same manner as in (1) of Synthesis Example 1 except that N-isopropylaniline was used instead of 2,6-difluoroaniline.

[s-4]

NMR (solvent: CDC1 ₃ ): 7.63 (d, 4H), 7.46-7.40 (m, 4H), 7.36-7.30 (m, 2H), 12 (d 4H), 6.54 (d, 4H), 4.46- 4.33 (m, 2 H), 1.17 (d, 12 H).

GC-MS: 420 m / z. Synthesis Example 2

(1) In a nitrogen atmosphere, 10 g (23 mmol) of the compound represented by Chemical Formula S-1 was placed in a round bottom flask, and 30 g of DMF was added thereto, followed by stirring to lower the temperature to 10 ^° C. Sodium t-butoxide (7.71g, 68.7mmo]) and iodoethane (10.7g, 68.7mmol) were added to the counter aunge, respectively. Then, the temperature was gradually raised to room temperature and stirred for 2 hours.

After the reaction was completed, 30 g of water was added and stirred for 10 minutes, and then the precipitate was filtered using a filter, washed with water, and then added to acetonitrile. The mixture was stirred at 8 (C for 30 minutes. After cooling to room temperature, the precipitate was filtered. After drying, the compound represented by the following Chemical Formula S-5 (8.2 g, 736%) was synthesized.

[S-5]

H NMR (solvent: DMSO-d6): 7.54 (d, 4H), 7.53-7.48 (m, 2H), 7.46 (t, 4H), 6.65 (d, 4H) _: 3.71 (q, 4H), 1.16 (t , 6H).

GC-Mass: 492 m / z.

(2) Except for using the compound represented by the formula (S-2) instead of the compound represented by the formula (S-1), in the same manner as in (1) of Synthesis Example 2, represented by the formula (S-6) Compounds were synthesized.

S-6]

'H NMR (solvent: CDC1 ₃ ): 7.68 (s, 4H), 7.15 (s, 6H), 3.65 (q, 4H), 2.1 1 (s, 12H), 1.24 (t,

6H).

GC-MS: 476 m / z.

(3) In the same manner as in (1) of Synthesis Example 2, except that the compound represented by Chemical Formula S-3 was used instead of the compound represented by Chemical Formula S-1, The compound represented by S-7 was synthesize | combined.

s-7]

NMR (solvent: CDC1 ₃ ): 7.65 (bs, 4H), 7.35 (dd, 2H), 7.27 (d, 4H), 6.82 (bs, 2H) _:

6.24 (bs, 2H), 3.66 (q, 4H), 2.96-2.87 (m, 4H), 1.29 (t, 3H), 1.20 (d, 12H), 1.01 (d, 12H).

GC-MS: 588 m / z. Synthesis Example 3

scheme]

(1) Put sodium ethoxide (75.5 g, 1.1 lmol) and ethanol 250 g in the back-bottom flask, stir at room temperature for 30 minutes, and add ethyl cyanoacetate (100 g, 0.887 mol) to it.

Slowly add to the reaction and then mix for 30 minutes at room temperature. PhenylisotWocyanate (100g _: 0.73mol) is slowly added dropwise to the reaction product, and the temperature is reduced to 80 ^° C and stirred for 3 hours. When the reaction is completed, the temperature is lowered, the solvent is removed, and then extracted with dichloromethane, and washed with 10% HC1 and water, respectively. After removing the organic solvent, 200 g of MeOH was added to the resulting solid compound, stirred at 0 ^° C. for 30 minutes, and then filtered, thereby synthesizing the compound represented by the following Chemical Formula S-8 (125 g, 68%).

[S-8]

NMR (solvent: CDC1 ₃ ): 1 1.7 (bs, 1H), 7.48-7.39 (m, 3H), 7.28-7.25 (m, 2H), 4.71 (sl), 4.27 (q, 2H), 1.35 ( t, 3H).

GC-MS: 248 m / z. (2) After adding NaOH (80.5g, 2.01mol) and 300g of water to a round bottom flask, the mixture was stirred at 0 ^° C. for 30 minutes and then the compound represented by Chemical Formula S-8 synthesized in (1) of Synthesis Example 3 ( 50 g, 0.201 mol) is added, and the reaction product is stirred at 80 ^° C for 3 hours. When the reaction is terminated, the temperature is lowered to 0 ^° C and then conc. Acidify the reaction product with HCl (pH: about 6). The resulting precipitate was filtered through a filter, washed with water and dried to synthesize a compound (29 g, 82%) represented by the following Chemical Formula S-9.

[S-9]

NMR (solvent: CDC1 ₃ ): 9.42 (s, 1H), 7.65 (d, 2H), 7.49-7.40 (m, 2H), 7.34-7.26 (m, 1H), 4.05 (s, 2H).

GC-MS: 176 m / z.

(3) KOH (7.26g, 0.129mol) and 200g of MeOH were added to an isometric bottom flask and stirred at room temperature for 30 minutes, followed by the compound represented by the above formula (S-9) (19g, 108mol) and phenacyl bromide (21.5). g, 0.108 mol) were added, followed by stirring for 2 hours at actual weight. After the reaction was completed, 200 g of water was added, and the resultant was stirred at room temperature for 1 hour, and the resultant

The precipitate was filtered through a filter, washed with MeOH and dried to synthesize a compound (27 g, 90%) represented by Chemical Formula S-10.

[Formula S-10]

MR NMR (solvent: CDC1 ₃ ): 7.6 l (d, 2H), 7.46-7.36 (m, 5H), 7.27 (d, 2H), 7.13 (t, 1H),

6.98 (bs, 1 H), 6.50 (s, 1 H).

GC-MS: 276 m / z.

(4) KOH (5.8 g, 0.103 mol), acetone 170 g, and 80 g of water were added to an isometric bottom flask, followed by stirring at room temperature. Compound represented by S-10 (25 g,

86.1mmol) and iodoethane (16.1g, 0.l03mol) were added, and then stirred at 50 ^° C. for 3 hours. After the reaction, the acetone is removed by distillation and dichloromethane is removed. Extracted with 10% HC1 and sat. Clean with sodium thiosulfate. The organic solvent was removed and dried to synthesize a compound (21 g, 80%) represented by the following formula S-11.

[Formula S-1 1]

'H NMR (solvent: CDC1 ₃ ): 7.61 (d, 2H), 7.59-7.36 (m, 5H), 7.24-7.18 (m, 3H), 6.65 (s, 1H), 4.01 (q, 2H), 1.39 (t, 3H).

GC-MS: 304 m / z. Synthesis Example 4

(l) A compound represented by the following Chemical Formula S-12 was synthesized in the same manner as in (3) of Synthesis Example 3, except that 2-fluorophenacyl bromide was used instead of phenacyl bromide.

[s-12]

NMR (solvent: CDC1 ₃ ): 7.58 (t, 1H), 7.44-7.37 (m, 3H), 7.29 (d, 2H), 7.25-7.13 (m, 3H), 6.97 (bs, 1H), 6.63 ( s, 1 H).

GC-MS: 294 m / z.

(2) In the same manner as in (4) of Synthesis Example 3, except that the compound represented by Formula S-12 was used instead of the compound represented by Formula S-10, the compound represented by Formula S-13 Compounds were synthesized. [S-13]

NMR (solvent: CDC1 ₃ ): 7.52 (t, IH), 7.49-7.35 (m 3H), 7.24-7.17 (m, 5H), 6.70 (s, IH) 4.02 (q, 2H), 1.38 (t, 3H).

GC-MS: 322 m / z.

(3) A compound represented by the following Chemical Formula S-14 was synthesized in the same manner as in (3) of Synthesis Example 3, except that 2-chlorophenacyl bromide ¾- was used instead of phenacyl bromide.

[S-1 ⁴ ]

H NMR (solvent: CDC1 ₃ ): 7.51-7.48 (m, IH), 7.43-7.3.2 (m, 5H), 7.28 (d, IH), 7.13 (t, lH), 6.92 (bs, lH), 6.53 (s, IH).

GC-MS: 310 m / z.

(4) Except for using the compound represented by the formula S-14 instead of the compound represented by the formula S-10, in the same manner as in (4) of Synthesis Example 3, represented by the following formula S-15 Compounds were synthesized.

[Formula S-15]

'H NMR (solvent: CDC1 ₃ ): 7.48-7.32 (m, 6H), 7.31-7.18 (m, 3H), 6.58 (s, IH), 4.00 (q, 2H), 1.36 (t, 3H).

GC-MS: 338 m / z.

(5) A compound represented by the following Chemical Formula S-16 was synthesized in the same manner as in (3) of Synthesis Example 3 except that 4-chlorophenacyl bromide was used instead of phenacyl bromide.

[Formula s-16]

'H NMR (solvent: CDC1 ₃ ): 7.54 (d, 2H), 7.43-7.37 (m, 4H), 7.27 (d, 2H), 7.15 (t, IH), 6.98 (bs, IH), 6.48 (s , IH).

GC-MS: 310 m / z.

(6) Except for using the compound represented by the formula (S-16) instead of the compound represented by the formula (S-10), in the same manner as in (4) of Synthesis Example 3, represented by the formula (S-17) Compounds were synthesized.

[Formula S-17]

H NMR (solvent: CDCI ₃ ): 7.47 (d, 2H), 7.46-7.35 (m, 4H), 7.24-7.18 (m, 3H), 6.54 (s, IH), 3.96 (q, 2H), 1.34 ( t, 3H).

GC-MS: 338 m / z.

(7) A compound represented by the following Chemical Formula S-18 was synthesized in the same manner as in (1) of Synthesis Example 3 except that o-tolylisothiocyanate was used instead of Phenylisothiocyanate. [S-18]

NMR (solvent: CDC1 ₃ ): 11.5 (bs, IH), 7.36-7.22 (m, 4H), 4.61 (s, IH), 4.29 (q, 2H), 1.37 (t, 3H).

GC-MS: 262 m / z.

(8) Except for using the compound represented by the formula (S-18) instead of the compound represented by the formula (S-8), in the same manner as in (2) of Synthesis Example 3, represented by the formula (S-19) Compounds were synthesized.

[S-19]

'H NMR (solvent: CDC1 ₃ ): 9.24 (bs, IH), 7.43-7.28 (m, 4H), 4.08 (s, 2H).

GC-MS: 190 m / z.

(9) In the same manner as in (3) of Synthesis Example 3, except that the compound represented by the formula S-19 was used instead of the compound represented by the formula S-9, the compound represented by the following formula S-20 Compounds were synthesized.

Formula S-20

'H NMR (solvent: CDCI ₃ ): 7.61 (d, 2H), 7.47-7.38 (m, 4H), 7.29-7.24 (m, 2H), 7.14 (t IH), 6.62 (bs, IH), 6.46 ( s, IH), 2.36 (s, 3H).

GC-MS: 290 m / z.

(10) In the same manner as in (4) of Synthesis Example 3, except that the compound represented by Formula S-20 was used instead of the compound represented by Formula S-10, A compound represented by the following formula S-21 was synthesized.

[-21]

NMR (solvent: CDC1 ₃ ): 7.5 l (d, 2H), 7.41-7.23 (m, 7H), 6.27 (s, IH), 3.95 (q, 2H), 2.28 (s, 3H), 1.34 (t , 3H).

GC-MS: 318 m / z.

(11) The same as in (1) of Synthesis Example 3 except that o-tolylisothiocyanate was used instead of Phenylisothiocyanate, except that 2-fluorophenacyl bromide was used instead of phenacyl bromide, (3) and In the same manner, a compound represented by the following chemical formula S-22 was synthesized.

S-22]

NMR (solvent: CDC1 ₃ ): 7.55 (t, IH), 7.46 (d, IH), 7.43-7.10 (m, 6H), 6.62 (s, 1H) _; 6.56 (s, IH), 2.36 (s, 3H).

GC-MS: 308 m / z.

(12) Except for using the compound represented by the formula (S-22) instead of the compound represented by the formula (S-10), in the same manner as in (4) of Synthesis Example 3, represented by the formula (S-23) Compounds were synthesized. [S-23]

NMR (solvent: CDC1 ₃ ): 7.42 (t, 1H), 7.34-7.25 (m, 5H), 7.18-7.09 (m, 2H), 6.35 (s, 1H) _: .95 (q, 2H), 2.28 (s, 3 H), 1.34 (t, 3 H).

GC-MS: 336 m / z. Synthesis Example 5

[Overall scheme]

(1) Ammonium acetate (U .6g, 0.15mol) and malononitrile (20.8g _: 0.315mol) were added to the isometric bottom flask, 12 g of AcOH and 180 g of toluene were added thereto and stirred at room temperature. ), And then proceed with Dean-Stark reaction for 5 hours at 120 ^° C. After the reaction is completed, lower the temperature to room temperature and use ethyl acetate.

Extract and wash with 10% HC1 and water. After removing the organic solvent, recrystallized with hexane and dried to synthesize a compound represented by the following formula (S-24) (42g, 83%).

[Formula S-2 ⁴ ]

H NMR (solvent: CDC1 ₃ ): 7.55-7.50 (m, 5H), 2.64 (s, 3H).

GC-MS: 168 m / z. (2) A compound (33.6 g, 0.2 mol) and sulfur powder (7.1 g, 0.22 mol) represented by Chemical Formula S-24 were added to a round bottom flask, and stirred with addition of 20 g of ethanol, followed by triethylamine (22.2). g, 0.22 mol) is added, and the reaction is heated to 80 ^° C. and stirred for 2 hours. When the reaction is complete, lower the temperature and remove the solvent by distillation.

Extract with dichloromethane, wash with 10% HC1 and water, remove solvent, and then use column chromatography (ethyl acetate: hexane = l / 3) ¾- to give the compound represented by the following formula S-25 (35.7g, 81% ) Was synthesized.

Formula S-25

NMR (solvent: CDC1 ₃ ): 7.56 (d, 2H), 7.44-7.32 (m, 3H), 6.35 (s, 1H), 4.90 (s, 1H).

GC-MS: 200 m / z.

(3) A compound (20g, O.lmol) and KOH (8.45g, 0.15mol) represented by Chemical Formula S-25 was added to a round bottom flask, and stirred with addition of 100 g of DMF, followed by 2-fluoronitrobenzene (21.2). g, 0.15 mol) is added and stirred for 15 hours at actual weight. When the reaction is complete, the mixture is extracted with ethyl acetate, washed with 10% HC1 and water, and then the solvent is removed. Recrystallization using Hexane and drying to synthesize a compound represented by the following formula S-26 (21g, 65%).

[Formula S-26]

NMR (solvent: CDC1 ₃ ): 10.0 (s, 1H), 8.31 (d, 1H), 7.68-7.64 (m, 3H), 7.61-7.41 (m _: 3H), 7.08-7.02 (m, 2H).

GC-MS: 321 m / z.

(4) to the compound of Formula S-26 instead of the compound of the formula S-10 Except for using the compound represented, the compound represented by the following formula (S-27) was synthesized in the same manner as in (4) of Synthesis Example 3.

[Formula s-27]

NMR (solvent: CDC1 ₃ ): 8.05 (d, 1H), 7.69 (t, 1H), 7.54-7.48 (m, 4H), 7.42-7.34 (m _; 3H), 6.52 (s, 1H), 3.93 ( q, 2H), 1.39 (t, 3H).

GC-MS: 349 m / z. Synthesis Example 6

(1) represented by the above formula (S-5) in an isometric bottom flask under nitrogen

After adding compound (1.03 g, 2.1 mmol) and compound represented by the above formula (S-8) (0.64 g, 2.1 mmol), 5 g of toluene and POCl ₃ (L29 g, 8.4 mmol) were added, and then the temperature was gradually decreased to 110 ^°. Raise to C and stir for 5 hours. When the reaction was completed, lower the temperature with silver, extract with methyl ethyl ketone (MEK), wash with 10% NaCl, water and 10% HC1, respectively. After the organic layer was removed and dried, Lithium bis (trifuloromethane) sulfon imide (L2g, 4.2mmol) was added thereto, and 10 g of DMSO was added thereto and stirred at room temperature for 30 minutes (anion exchange process). The reaction is dropped into water to form a precipitate, which is obtained by separating through a filter. The solid compound obtained through the filter was dissolved in 40 g of acetonitrile, and then 3 g of activated carbon was added thereto and stirred for 30 minutes. Activated carbon was removed through a filter, and the filtrate was removed through distillation and dried to obtain a compound (L82g, 83%) represented by the following Chemical Formula P-1. pi]

'H NMR (solvent: CDC1 ₃ ): 7.57-7.51 (m, 3H), 7.45-7.26 (m, 8H), 7.10-7.05 (m, 9H) 6.50 (bs, 4H), 4.13 (q, 2H), 3.75 (q, 4H), 1.41 (t, 3H), 1.24 (t, 6H).

(2)

scheme]

Except having used the compound, it carried out similarly to (1) of the said synthesis example 6, and synthesize | combined the compound represented by following formula (P-2).

p ᅳ ₂ ]

NMR (solvent: CDC1 ₃ ): 7.57-7.41 (m, 7H), 7.26-6.87 (m, 15H), 5.89 (d, 2H), 4.10 (q _; 2H), 3.72 (d, 4H), 2.05 ( s, 12H), 1.40 (t, 3H), 1.24 (t, 6H).

(3) In the same manner as in (1) of Synthesis Example 6, except that the compound represented by Chemical Formula S-24 was used instead of the compound represented by Chemical Formula S-8, ^{- ζ 'ί' (HI '} 1) 69' /, '(HI' V) -L '(. H ¾58 "/' ( 'P) S1' 8 :( CK) - \ u3A \ os) H

[漏 ips [^^]

^" (H9 ¾9Γΐ '(Η £ εε · Ι' (Ht ⁷ FE '(HZ:' b) 00 '(Ht ⁷ ' sq) ^' 9' (H6 ') 907 Π' (Η9 ^ ZZ ^' L-£ VL '(HI' ^ O L- L \ HZ 'UI ^' / '(HI' Ρ) 8Γ8 :( ^ε ΚΧ ^' -lu ^ jos) ¾ N

609CT0 / Sl0ZaM / X3d .Ϊ98Ϊ0 / .Ϊ0Ζ OAV 7.45 (m, 6H), 7.23-7.22 (m, 4H), 7.1-7.04 (m, 9H), 6.45 (d, 4H), 4.51-4.41 (m, 2H), 3.95 (q, 2H) 1.32 (t , 3H), 1.18 (d, 12H).

(5)

[Overall scheme]

H NMR (solvent: CDC1 ₃ ): 7.51-7.38 (m, 12H), 7.20-7.03 (m, 12H), 6.42 (d, 4H), 4.52- 4.45 (m, 2H), 4.08 (q, 2H), 1.38 (t, 3 H), 1.17 (d, 12 H).

(6)

[Overall scheme]

With reference to the synthesis method, etc., a compound represented by the following Chemical Formula P-6 was synthesized according to the overall scheme.

NMR (solvent: CDC1 ₃ ): 7.58-7.41 (m, 12H), 7.24-7.05 (m, 1 IH), 6.98 (t, IH), 6.79 (1 IH), 6.47 (d, 4H), 4.55- 4.48 (m, 2H), 4.10 (q, 2H), 1.41 (t, 3H), 1.20 (d, 12H).

(7)

scheme]

'H NMR (solvent: CDC1 ₃ ): 7.61-7.53 (m, 3H), 7.49-7.28 (m, 8H), 7.19-7.09 (m, 6H) 6.96 (t, lH), 6.76 (t, IH), 6.56 (bs, 4H), 4.15 (q, 2H), 3.78 (q, 4H), 1.43 (t, 3H), 1.27 (t, 6H).

(8) scheme]

By referring to the synthesis method, etc., a compound represented by the following Chemical Formula P-8 was synthesized according to the overall scheme.

P-8]

NMR (solvent: CDC1 ₃ ): 7.60-7.43 (m, 7H), 7.28-7.17 (m, 7H), 7.01-6.94 (m, 6H) 6.77 (t, 1H), 5.9 l (d, 2H), 4.12 (q, 2H), 3.76 (q, 4H), 2.07 (s, 12H), 1.42 (t, 3H), 1.27 (ΐ, 6H).

(9)

scheme]

By referring to the synthesis method, etc., a compound represented by the following Chemical Formula P-9 was synthesized according to the overall scheme. P-9]

MR NMR (solvent: CDC1 ₃ ): 7.58-7.40 (m, 1 1H), 7.22-7.03 (m, 12H), 6.45 (d, 4H), 4.53- 4.44 (m, 2H), 4.09 (q, 2H) , 1.39 (t, 3 H), 1.18 (d, 12 H).

10

scheme]

With reference to the synthesis method, etc., according to the overall scheme, a compound represented by the following formula P-10 was synthesized.

P-10]

NMR (solvent: CDC1 ₃ ): 7.59-7.36 (m, 8H), 7.30-7.26 (m, 3H), 7.20-7.07 (m, 8H), 6.53 (bs, 4H), 4.14 (q, 2H), 3.76 (q, 4H), 1.42 (t, 3H), 1.26 (t, 6H).

(Photosensitive resin composition production)

Example 1

Examples 1 to 10 and Comparative Examples, with the composition shown in Table 1 and Table 2 1 to 4, a photosensitive resin composition according to Comparative Example 4 was prepared. Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours. Binder resin and photopolymerizable monomer were added here, and it stirred at room temperature for 2 hours. To this, after the dye was added (optionally, a pigment dispersion), the mixture was stirred at room temperature for 1 hour, other additives (surfactant) were added, and the mixture was stirred at room temperature for 1 hour. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

TABLE 1

(Unit: weight%)

Conduct Conduct Conduct Conduct Conduct Conduct Conduct Conduct Conduct Conduct

Examples Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9

10 binder

10 10 10 10 10 10 10 10 10 10 Resin

Photopolymerizable

6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Compound

Photopolymerization

0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Initiator

Wh

Ryo 5--------

One

Wh

Ryo-5-------Coloring

2

My :

Wh

Ryo--5-------3

Wh

-. --5------ 4

Wh

Ryo--―-5--―--5

Wh

Ryo-----5----6

in

Ryo ―-----5---

7

Wh

Ryo------― 5--8

ᄋ ³

Wh

Fee - - ^'- - - - - - 5-9

Wh

Ryo----ᅳ----5

10

ᄋ 3

Wh

Ryo-― ᅳ-------

1 1

within

Ryo---------ᅳ

One

Solvent 77.8 77.8 77.8 77.8 77.8 77.8 77.8 77.8 77.8 77.8 Other

0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Additive

Total 100.0 100.0 100.0 100.0 100.0 100.0 100,0 100.0 100.0 100.0 TABLE 2

(Unit: weight ^_0/0)

Binder resin

Acrylic binder resin (methacrylic acid / benzyl methacrylate ==. 15/85 (w / w), weight average molecular weight = 22,000 g / mol, acid value = 100 mgKOH / g)

coloring agent

(Dye 1) Compound represented by Chemical Formula P-1

(Dye 2) a compound represented by the general formula P-2 ^'

(Dye 3) Compound represented by Chemical Formula P-3

(Dye 4) Compound represented by Chemical Formula P-4

(Dye 5) Compound represented by Chemical Formula P-5

(Dye 6) Compound represented by Chemical Formula P-6

(Dye 7) Compound represented by Chemical Formula P-7

(Dye 8) Compound represented by the formula (P-8)

(Dye 9) Compound represented by Chemical Formula P-9

(Dye 10) Compound represented by Chemical Formula P-10

(Dye 1 11) A compound represented by the following Chemical Formula P-11 (Win-chemical, Brilliant Blue

FG) [Formula Pl]

Pigment 1 B 15: 6 Pigment Dispersion (Sanyo)

Photopolymerizable compound

Dipentaerythritol Nuclear Acrylate (DPHA)

Photopolymerization initiator

Oxime initiator (BASF, OXE-01)

menstruum

Propylene Glycol Monomethyl Ether Acetate (PGMEA)

Other additives

Fluorinated Surfactant (DIC, F-554, using 10% diluent) (Evaluation)

Evaluation 1: evaluation of coloring power

Compounds represented by the above formulas P-1 to P-1 1 were measured in a maximum absorption wavelength (ληΐίΐχ) by UV-1800 UV-Vis Spectrometer equipment, and are shown in Table 2 below. Further, 20 mg of the compound is dissolved in Anone (Cyclohexanone) to make 20 g of a thick solution, and then 0.1 g of the concentrated solution is diluted to 10 g again to form a 0.001% by weight dilute solution. After measuring the spectroscopy of the 0.001% by weight of the solution at room temperature, the molar extinction coefficient was calculated from Equation 1 below, and is shown in Table 3 below. [Equation 1]

A = eel

(A: maximum absorbance, e: molar extinction coefficient, c: molar concentration, 1: optical path length)

TABLE 3

From Table 3, the compound represented by the formula (P-1 to P-10) is a compound according to an embodiment, the maximum absorption wavelength and the compound represented by the formula (P-1 1)

Even similar, it can be confirmed that it has a better coloring power. Evaluation 2: Contrast Ratio ί Contrast

The photosensitive resin composition prepared in Examples 1 to 10 and Comparative Examples 1 to 4 was applied to a glass substrate having a thickness of 1 mm, degreased, and washed for 2 minutes on a hot plate at 90 ^° C. Drying to give a coating. Subsequently, the coating film was exposed by using a high pressure mercury lamp having a dominant wavelength of 365 nm. Obtained by drying in a hot air circulation drying furnace of 200 ^° C for 5 minutes. The pixel layer was measured using a spectrophotometer (MCPD3000, Otsuka electronic Co., Ltd.) and the results are shown in Table 4 below.

TABLE 4

Contrast Ratio

Example 1 20970

Example 2 21023

Example 3 19231

Example 4 18929

Example 5 21000

Example 6 20568

Example 7 21533

Example 8 19984

Example 9 20631

Example 10 18530

Comparative Example 1 1821 1

Comparative Example 2 18190

Comparative Example 3 18210

Comparative Example 4 18015 From Table 4, the photosensitive resin composition of Examples 1 to 10 containing the compound according to one embodiment as a dye shows an excellent contrast ratio than the photosensitive resin composition of Comparative Examples 1 to 4 not containing the compound You can check it. As mentioned above, although this invention was demonstrated, this invention is not limited to this, A various deformation | transformation is possible in the range of a claim, the detailed description of an invention, and the attached drawing, and also this is within the scope of this invention. It is natural to belong.

Claims

Claims [Claim 1] Contains a cation and an anionic silver, wherein the cation is represented by the following formula (1)

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C20 heteroaryl group in C2,

R ⁷ is a substituted or unsubstituted C6 to C20 aryl group,

X is -0-, -S- or — NR ^8- (R ⁸ is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group).

[Claim 2]

The method of claim 1,

X is -0- or -S-.

[Claim 3]

The method of claim 1,

R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.

[Claim 4] The method of claim 1,

The cation is a compound represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted C1 to C20 alkyl group, and R ⁱⁱ and are each independently a hydrogen atom, a substituted or unsubstituted ci to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group ego,

R ¹³ is a substituted or unsubstituted C6 to C20 aryl group,

X is -0- or -S-.

[Claim 5]

The method of claim 1,

The cation is a compound represented by any one selected from the group consisting of Formula 3 to Formula 7. [Formula 3]

(In Chemical Formula 3,

1 ⁸ , ¹⁹ and R ²¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ²² is a halogen atom,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-)

[Formula 4]

(In Chemical Formula 4) R ¹⁸ to R ²¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ²² is a halogen atom,

R ²³ to R ²⁰ are each independently a halogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-)

[Formula 5]

(In Chemical Formula 5,

R ⁱ s and R ^ig are each independently a substituted or unsubstituted C1 to C20 alkyl group, R ²² is a halogen atom,

R ²⁷ is a substituted or unsubstituted C6 to C20 aryl group,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-)

[Formula 6]

(In Chemical Formula 6,

R ²⁷ and R ²⁸ are each independently a substituted or unsubstituted C6 to C20 aryl group and m is an integer of 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-)

[Formula 7]

(In Chemical Formula 7, R ¹⁸ , R ¹⁹ and R ²¹ are each independently a substituted or unsubstituted C1 internal C20 alkyl group,

R ²² is a halogen atom,

R ²⁸ is a substituted or unsubstituted C6 to C20 aryl group,

m is an integer from 0 to 2,

n5 to n8 are each independently an integer of 0 or 1,

X is -0- or -S-)

[Claim 6]

The method of claim 1,

The cation may be represented by the following Chemical Formulas 5-3, 5-4, 5-5, 5-6, 7-6, 7-8, 7-10, 7-12, and 7-17. A compound represented by any one selected from the group consisting of 7-23.

[Formula 5-3]

90

[Formula 7-12]

[7-22]

[7-23]

[Claim Port]

The method of claim 1,

The anion is a compound represented by any one selected from the group consisting of Formula A to Formula F.

[Formula A]

[Formula B] 95

[Formula C]

PW ₁₂ O ₄₀ ^{3 "}

[Formula D]

SiW ₁₂ O ₄₀ ^{4 "}

[Formula E]

CF3SO3 ^"

Formula F]

C10 ₄ ^"

[Claim 8]

The method of claim 1,

The compound is a dye.

[Claim 9]

According to claim 18,

The dye is a blue dye.

[Claim 10]

The method of claim 1,

The compound has a maximum absorbance (λ _Χ ) in the wavelength range of 600 nm to 700 nm.

[Claim 1 11]

The method of claim 1,

The compound has a compound in the wavelength range of 400 nm to 500 nm.

[Claim 12]

The photosensitive resin composition containing the compound of any one of Claims 1-1.

[Claim 13]

The method of claim 12, The photosensitive resin composition further comprises a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent.

[Claim 14]

The method of claim 13,

The photosensitive resin composition is a photosensitive resin composition further comprises a pigment. [Claim 15]

The color filter manufactured using the photosensitive resin composition of Claim 12.