KR102023158B1 - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) binder resin; (B) a colorant including "a compound represented by the following formula (1) or an acrylic polymer formed by copolymerization of the compound with an ethylenically unsaturated monomer" and a "pigment dispersion"; (C) photopolymerizable compounds; The photosensitive resin composition containing (D) photoinitiator and (E) solvent, the photosensitive resin film manufactured using the said photosensitive resin composition, and the color filter containing the said photosensitive resin film are provided.
[Formula 1]

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

Description

Photosensitive resin composition, photosensitive resin film and color filter manufactured using the same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME AND COLOR FILTER}

The present substrate relates to a photosensitive resin composition, a photosensitive resin film prepared using the same, and a color filter including the photosensitive resin film.

The liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent bonding with an integrated circuit, and thus its use range is expanding for notebook computers, monitors, and TV images.

The liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, an active circuit unit consisting of a liquid crystal layer, a thin film transistor, and a capacitor layer, and an upper substrate on which an ITO pixel electrode is formed. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundary between pixels, and a plurality of colors (typically red (R), green (G), and blue (B) to form each pixel. The three primary colors) are arranged in a stacked order.

The pigment dispersion method, which is one of the methods for implementing a color filter, coats a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposes a pattern of a shape to be formed, and then removes a non-exposed area with a solvent. It is a method in which a colored thin film is formed by repeating a series of processes of thermosetting.

The colored photosensitive resin composition used for manufacturing the color filter according to the pigment dispersion method is generally composed of an alkali-soluble resin, a photopolymerization monomer, a photopolymerization initiator, a solvent and other additives, and may further include an epoxy resin or the like. Pigment dispersion methods as described above are actively applied to manufacture LCDs such as mobile phones, notebook computers, monitors, and TVs.

However, in recent years, even in the photosensitive resin composition for color filters using the pigment dispersion method having various advantages, it is difficult to refine the powder, and even if dispersed, various additives are required because the dispersed state must be stable in the dispersion. It is very demanding, and furthermore, the pigment dispersion has a disadvantage in that storage and transportation conditions are difficult because of maintaining an optimal quality state.

In addition, there is a limit in the brightness and contrast ratio resulting from the pigment particle size in the color filter made of the pigment-type photosensitive resin composition.

Accordingly, efforts have been made to develop dyes having heat resistance and chemical resistance similar to pigments in place of pigments, and to develop photosensitive resin compositions using the dyes as colorants.

One embodiment is to provide a photosensitive resin composition excellent in color properties, heat resistance, chemical resistance.

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

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

One embodiment includes (A) a binder resin; (B) a colorant comprising a compound represented by the following formula (1) and a pigment dispersion; (C) photopolymerizable compounds; It provides the photosensitive resin composition containing (D) photoinitiator and (E) solvent.

[Formula 1]

In Chemical Formula 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,

At least one of the R ¹ to R ⁴ is represented by the formula (2),

[Formula 2]

In Chemical Formula 2,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group,

L ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

R ⁵ is a substituent containing an ethylenically unsaturated double bond.

R ⁵ may be a substituted or unsubstituted acrylate group, a substituted or unsubstituted C2 to C20 alkenyl group, or a C6 to C20 aryl group including an ethylenically unsaturated double bond at the terminal.

R ⁵ may be represented by any one of the following Chemical Formulas 3 to 5.

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 3 to 5,

R ⁶ is a hydrogen atom or a substituted or unsubstituted C1 to C5 alkyl group.

At least two of R ¹ to R ⁴ may be represented by Chemical Formula 2.

R ¹ or R ² may be represented by Chemical Formula 2.

R ¹ or R ² may be represented by Formula 2, and at the same time, R ³ or R ⁴ may be represented by Formula 2.

The compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 6 to 15.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

The compound represented by Formula 1 may have a maximum absorbance in the wavelength range of 500nm to 600nm.

Another embodiment includes (A) a binder resin; (B) a colorant comprising an acrylic polymer and a pigment dispersion formed by copolymerizing a compound represented by Formula 1 with an ethylenically unsaturated monomer; (C) photopolymerizable compounds; It provides the photosensitive resin composition containing (D) photoinitiator and (E) solvent.

The acrylic polymer may have a maximum absorbance in the wavelength range of 500nm to 600nm.

The acrylic polymer and the pigment dispersion may be included in a weight ratio of 1: 2 to 1: 6.

The ethylenically unsaturated monomer may be selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid amino alkyl ester compounds, carboxylic acid vinyl ester compounds, unsaturated carboxylic acid glycidyl ester compounds, vinyl cyanide compounds, unsaturated amide compounds, and combinations thereof. It may be any one selected.

The pigment in the pigment dispersion may be a red pigment.

The said photosensitive resin composition is 1 weight%-10 weight% of said (A) binder resin with respect to the said photosensitive resin composition total amount; 50% to 75% by weight of the colorant (B); 1 wt% to 5 wt% of the (C) photopolymerizable compound; It may include 0.1% to 5% by weight of the photopolymerization initiator (D) and the balance of the solvent (E).

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; And at least one additive selected from radical polymerization initiators.

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

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

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

Compound and acrylic polymer according to an embodiment is excellent in solubility in an organic solvent, by using a photosensitive resin composition comprising a colorant comprising the compound or the acrylic polymer as a component, color characteristics, heat resistance, chemical resistance and the like An excellent color filter can be manufactured.

1 is a GPC graph of an acrylic polymer represented by Chemical Formula 16.

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 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 ), wherein 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 group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, And it means substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless 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" refers to 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 C18 aryl group, "alkenyl group" means C2 to C20 alkenyl group, specifically C2 to C18 alkenyl group, "alkylene group" means C1 to C20 alkylene group, specifically C1 To C18 alkylene group, an "arylene group" means a C6 to C20 arylene group, specifically, a C6 to C16 arylene group.

Unless stated otherwise in the present 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 the present specification, the cardo-based resin refers to a resin in which at least one functional group selected from the group consisting of Formulas 17-1 to 17-11 is included in the backbone of the resin.

Unless otherwise defined herein, "ethylenically unsaturated double bond" means "carbon-carbon double bond", and ethylenically unsaturated monomer means a monomer including the ethylenically unsaturated double bond.

In addition, "*" means a part connected with the same or different atoms or formulas unless otherwise defined herein.

One embodiment includes (A) a binder resin; (B) a colorant comprising "a compound represented by the following formula (1) or an acrylic polymer formed by copolymerization of the compound with an ethylenically unsaturated monomer" and a pigment dispersion; (C) photopolymerizable compounds; It provides the photosensitive resin composition containing (D) photoinitiator and (E) solvent.

[Formula 1]

In Chemical Formula 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,

At least one of the R ¹ to R ⁴ is represented by the formula (2),

[Formula 2]

In Chemical Formula 2,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group,

L ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

R ⁵ is a substituent containing an ethylenically unsaturated double bond.

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 brightness and contrast ratios by preparing a photosensitive resin composition suitable for dyes by introducing dyes which do not form particles instead of pigments.

In general, xanthene-based compounds are separated from the charge, the photosensitive resin composition comprising the same has a low solubility in organic solvents such as PGMEA, poor heat resistance and chemical resistance, there was a limit to use as a colorant in the photosensitive resin composition. However, the photosensitive resin composition according to an embodiment may include at least one substituent represented by Formula 1 (the at least one substituent represented by Formula 2) or a compound represented by Formula 1 (the substituent represented by Formula 2 at least And acrylic polymer formed by copolymerization of one or more ethylenically unsaturated monomers together with a pigment dispersion as a colorant, thereby improving solubility in an organic solvent, and thus using a photosensitive resin composition comprising the same. Color filters having improved heat resistance and chemical resistance can be manufactured.

Each component is demonstrated concretely below.

(B) colorant

The colorant includes an acrylic polymer formed by copolymerizing a compound represented by Chemical Formula 1 or a compound represented by Chemical Formula 1 with an ethylenically unsaturated monomer together with a pigment dispersion.

At least two of R ¹ to R ⁴ may be represented by Chemical Formula 2. When the compound represented by Formula 1 includes two or more substituents represented by Formula 2, the solubility in organic solvents and the brightness of the composition including the compound may be further improved. Synthesis method of a compound containing only one functional group represented by the formula (2), compared to the synthesis method of a compound containing at least two functional groups represented by the formula (2), only the content of the reactant is controlled, By looking at the synthesis method of the compound containing at least two functional groups represented by the formula (2), it is possible to easily synthesize a compound containing only one functional group represented by the formula (1).

For example, R ¹ or R ² may be represented by Chemical Formula 2.

For example, R ¹ or R ² may be represented by Formula 2, and at the same time, R ³ or R ⁴ may be represented by Formula 2.

R ⁵ may be a substituted or unsubstituted acrylate group, a substituted or unsubstituted C2 to C20 alkenyl group, or a C6 to C20 aryl group including an ethylenically unsaturated double bond at the terminal.

For example, the substituted or unsubstituted acrylate group may be represented by Formula 4 below, and the substituted or unsubstituted C2 to C20 alkenyl group may be represented by Formula 3 below, and includes an ethylenically unsaturated double bond at the terminal. The C6 to C20 aryl group may be represented by the following formula (5).

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 3 to 5,

R ⁶ is a hydrogen atom or a substituted or unsubstituted C1 to C5 alkyl group.

The compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 6 to 15, but is not limited thereto.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

The compound represented by Formula 1 may have a maximum absorbance in the wavelength range of 500nm to 600nm.

The acrylic polymer and the pigment dispersion may be included in a weight ratio of 1: 2 to 1: 6.

For example, the acrylic polymer may be included in 10 wt% to 20 wt% with respect to the total amount of the photosensitive resin composition.

For example, the pigment dispersion may be included in 30% by weight to 60% by weight, such as 40% by weight to 60% by weight, such as 50% by weight to 60% by weight based on the total amount of the photosensitive resin composition.

When the acrylic polymer and the pigment dispersion are included in the content range, it is possible to further improve the color characteristics, heat resistance and chemical resistance.

For example, the ethylenically unsaturated monomer may be an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid amino alkyl ester compound, a carboxylic acid vinyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a vinyl cyanide compound, an unsaturated amide compound, or a combination thereof. have.

For example, the ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethyl ether; (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl Unsaturated carboxylic ester compounds such as (meth) acrylate, benzyl (meth) acrylate, 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 or combinations thereof.

The acrylic polymer, which is a product of the polymerization reaction through copolymerization of the compound represented by Chemical Formula 1 and the ethylenically unsaturated monomer, has excellent heat resistance and processability, and thus may be very useful as a colorant in the photosensitive resin composition used for preparing color filters. have.

For example, the acrylic polymer formed by copolymerization of the compound represented by Formula 10 and methyl methacrylate may be a copolymer represented by Formula 16 below.

[Formula 16]

The compound represented by Formula 1 (or the acrylic polymer) may be a dye such as a red dye or a violet dye.

The colorant may further include an organic solvent soluble dye in addition to the compound represented by Chemical Formula 1 and / or the acrylic polymer.

Examples of the organic solvent soluble dyes include triarylmethane compounds, anthraquinone compounds, benzylidene compounds, cyanine compounds, phthalocyanine compounds, azapopyrine compounds, indigo compounds, and the like.

The colorant may further include a pigment in addition to the compound and / or the acrylic polymer.

The pigment may include a violet pigment, a red pigment, a green pigment, a yellow pigment, and the like. For example, the pigment may be a red pigment.

Examples of the blue pigment include C.I. Blue pigment 15: 6, C.I. Blue pigment 15, C.I. Blue pigment 15: 1, C.I. Blue pigment 15: 2, C.I. Blue pigment 15: 3, C.I. Blue pigment 15: 4, C.I. Blue pigment 15: 5, C.I. Blue pigment 16, C.I. Blue pigment 22, C.I. Blue pigment 60, C.I. Blue pigment 64, C.I. Blue pigment 80 or a combination thereof.

Examples of the violet pigment include C.I. Violet Pigment 1, C.I. Violet Pigment 19, C.I. Violet Pigment 23, C.I. Violet Pigment 27, C.I. Violet Pigment 29, C.I. Violet Pigment 30, C.I. Violet Pigment 32, C.I. Violet Pigment 37, C.I. Violet Pigment 40, C.I. Violet Pigment 42, C.I. Violet pigment 50 or a combination thereof.

Examples of the red pigments include perylene pigments, anthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, anthracene pigments, and the like. Specific examples of the red pigments include perylene pigments, quinacridone pigments, naphthol AS, cuminamine pigments, anthraquinones (sudan I, II, III, R), and vis azo. ), Benzopyran and the like.

Examples of the green pigment include C.I. Halogenated phthalocyanine-based pigments such as pigment green 58; and the like.

Examples of the yellow pigment include 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 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.

The solid pigment may be included in an amount of 40 wt% to 80 wt%, such as 50 wt% to 70 wt%, such as 55 wt% to 65 wt%, based on the total amount of the pigment dispersion.

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 thereof.

Examples of commercially available products of the dispersant include, for example, DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, and 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 wt% to 20 wt% based on 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.

Ethylene glycol acetate, ethyl cellosolve, propylene glycol (mono) methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. can be used as a solvent which forms the said pigment dispersion.

The colorant may be included in an amount of 50 wt% to 75 wt%, such as 60 wt% to 70 wt%, based on the total amount of the photosensitive resin composition. When the colorant is included in the above range, the coloring effect and the developing performance is excellent.

(A) binder resin

The binder resin may include an acrylic binder resin, a cardo binder resin, or a combination thereof. For example, the binder resin may be an acrylic binder resin.

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

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof may 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, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and 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 (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate. Methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination of two or more thereof. have.

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

The acid value of the acrylic binder resin may be 15 mgKOH / g to 60 mgKOH / g, such as 20 mgKOH / g to 50 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The cardo-based binder resin may include a repeating unit represented by Formula 17 below.

[Formula 17]

In Chemical Formula 17,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁵ R ¹⁶ , SiR ¹⁷ R ¹⁸ , wherein R ¹⁵ to R ¹⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, or Any one of the linking groups represented by Formula 17-1 to Formula 17-11,

[Formula 17-1]

[Formula 17-2]

[Formula 17-3]

[Formula 17-4]

[Formula 17-5]

(In Chemical Formula 17-5,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH = CH ₂ or a phenyl group.)

[Formula 17-6]

[Formula 17-7]

[Formula 17-8]

[Formula 17-9]

[Formula 17-10]

[Formula 17-11]

Z ² is an acid dianhydride residue,

m1 and m2 are each independently an integer of 0-4.

The cardo-based binder resin may include a functional group represented by Formula 18 at at least one of both ends.

[Formula 18]

In Chemical Formula 18,

Z ³ may be represented by the following Formula 18-1 to Formula 18-7.

[Formula 18-1]

(In Formula 18-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group.)

[Formula 18-2]

[Formula 18-3]

[Formula 18-4]

[Formula 18-5]

(In Formula 18-5, R ^d is O, S, NH, substituted or unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamine group or C2 to C20 alkenylamine group.)

[Formula 18-6]

[Formula 18-7]

The cardo-based binder resin may be, for example, a fluorene-containing compound such as 9,9-bis (4-oxyranylmethoxyphenyl) fluorene; Benzene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid anhydride, biphenyl tetracarboxylic acid anhydride, benzophenone tetracarboxylic acid anhydride, pyromellitic di anhydride, cyclobutanetetracarboxylic acid anhydride, perylene tetracarboxylic acid anhydride Anhydride compounds, such as tetrahydrofuran tetracarboxylic acid anhydride and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Solvent compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; And amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, and the like.

When the cardo-based binder resin is used together with the acrylic binder resin described above, it is possible to obtain a photosensitive resin composition having excellent adhesion and high resolution and high brightness characteristics.

The weight average molecular weight of the cardo-based binder resin may be 500 g / mol to 50,000 g / mol, for example, 3,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cardo-based binder resin is within the above range, the pattern is well formed without a residue when manufacturing the color filter, and there is no loss of film thickness during development, and a good pattern can be obtained.

The cardo-based binder resin may have an acid value of 100 mgKOH / g to 140 mgKOH / g.

The binder resin may be included in an amount of 1% by weight to 10% by weight based on the total amount of the photosensitive resin composition. 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.

(C) photopolymerizable compound

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 Latex, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monometh And butyl ether (meth) acrylate, trimethylol propane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, and novolac epoxy (meth) acrylate.

Examples of commercially available products of the photopolymerizable compound are as follows. 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 .; Nihon 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 by treating with an acid anhydride in order to impart better developability.

The photopolymerizable compound may be included in an amount of 1 wt% to 5 wt%, such as 1 wt% to 3 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.

(D) photoinitiator

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

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

Examples of the benzophenone-based 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- Chlorothioxanthone 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-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, and 1- (o-acetyloxime ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one Etc. can be used. Specific examples of the O-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-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butane-1-one oxime- O-acetate, etc. are mentioned.

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

The photopolymerization initiator may be used together with a photosensitizer which causes a chemical reaction by absorbing light and transferring 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 0.1 wt% to 5 wt%, such as 0.1 wt% to 3 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.

(E) solvent

The solvent may be used materials having compatibility with the colorant, the binder resin, the photopolymerizable compound, the photopolymerization initiator, and the like, but do not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; 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 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionic acid esters, such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate and 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl 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 them, 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 can be used.

The solvent may be included in a balance, such as 20 wt% to 40 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 is excellent in manufacturing a color filter.

(F) other additives

The photosensitive resin composition may be used to prevent stains or spots upon application, to improve leveling performance, and to prevent generation of residues due to undeveloped malonic acid; 3-amino-1,2-propanediol; Coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Surfactants; And at least one additive selected from radical polymerization initiators.

The additive can be easily adjusted according to the desired physical properties.

The coupling agent may be a silane coupling agent, and examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. It can be mixed and used.

The silane coupling agent may be used in an amount of 0.01 parts by weight to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

In addition, the photosensitive resin composition for a color filter may further include a surfactant, such as a fluorine-based surfactant, if necessary.

Examples of the fluorine-based surfactants include F-554, F-482, F-484, F-478, etc. of DIC Corporation, but are not limited thereto.

The surfactant is preferably included in an amount of 0.01% by weight to 5% by weight and more preferably 0.01% by weight to 2% by weight based on the total amount of the photosensitive resin composition. If it is out of the above range may cause a problem that foreign matter occurs after development is not preferable.

The photosensitive resin composition may further include an epoxy compound in order to improve adhesion to a substrate.

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 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 photosensitive resin film manufactured using the photosensitive resin composition is provided.

According to another embodiment, a color filter including the photosensitive resin film 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 Synthesis of Compound Represented by Chemical Formula 10

32 g of Compound A (CAS No. 77545-45-0) were charged to the reactor and dissolved in 300 g of 2-propanol. 28.2 g of 2-ethylamino ethanol were added, followed by stirring at 80 ° C for 8 hours. The reaction was cooled and 2 liters of water was added to form a precipitate. The precipitate obtained was suction filtered and further washed with water. The filtrate was dried to give 32 g (80% yield) of compound B.

10 g of Compound B was added to the reactor, 30 g of dimethylformamide and 7.0 g of methacryloyloxyethyl isocyanate were added, followed by stirring for 8 hours. 100 g of dichloromethane is added to the reaction and washed with water. The obtained organic layer was distilled under reduced pressure after filtration of silica. The distilled mixture was dissolved in 10 g of dichloromethane and precipitated by dropwise addition to 100 g of normal hexane. The precipitate obtained was suction filtered and further washed. The filtrate was dried to give 12.8 g (80% yield) of the compound represented by Chemical Formula 10.

Maldi-tof MS: 820.3 m / z

Synthesis Example 2 Synthesis of Compound Represented by Formula 11

10 g of compound A (CAS No. 77545-45-0) is charged to a reactor and dissolved with 100 g of 2-propanol. 9.4 g of 2-butylamino ethanol were added thereto, followed by stirring at 80 ° C. for 8 hours. The reaction was cooled and 800 mL of water was added to form a precipitate. The precipitate obtained was suction filtered and further washed with water. The filtrate was dried to give 10.9 g (78% yield) of compound C.

10 g of Compound B was added to the reactor, 30 g of dimethylformamide and 7.0 g of methacryloyloxyethyl isocyanate were added, followed by stirring for 8 hours. 100 g of dichloromethane is added to the reaction and washed with water. The obtained organic layer was distilled under reduced pressure after filtration of silica. The distilled mixture was dissolved in 10 g of dichloromethane and precipitated by dropwise addition to 100 g of normal hexane. The precipitate obtained was suction filtered and further washed. The filtrate was dried to obtain 11.6 g (75% yield) of the compound represented by Formula 11.

Maldi-tof MS: 876.4 m / z

Synthesis Example 3 Synthesis of Compound Represented by Formula 14

10 g of compound B was added to the reactor, 30 g of dimethylformamide and 6.4 g of acryloyloxyethyl isocyanate were added, followed by stirring for 8 hours. 100 g of dichloromethane is added to the reaction and washed with water. The obtained organic layer was distilled under reduced pressure after filtration of silica. The distilled mixture was dissolved in 10 g of dichloromethane and precipitated by dropwise addition to 100 g of normal hexane. The precipitate obtained was suction filtered and further washed. The filtrate was dried to give 13.2 g (85% yield) of the compound represented by the following formula (14).

[Formula 14]

Maldi-tof MS: 792.3 m / z

Synthesis Example 4 Synthesis of Compound Represented by Chemical Formula 15

10 g of Compound B was added to the reactor, 30 g of dimethylformamide and 9.1 g of 1- (1-isocyanato-1-methylethyl) -3-isopropylbenzene were added thereto, followed by stirring for 8 hours. 100 g of dichloromethane is added to the reaction and washed with water. The obtained organic layer was distilled under reduced pressure after filtration of silica. The distilled mixture was dissolved in 10 g of dichloromethane and precipitated by dropwise addition to 100 g of normal hexane. The precipitate obtained was suction filtered and further washed. The filtrate was dried to give 12.1 g (68% yield) of the compound represented by the following Formula 15.

[Formula 15]

Maldi-tof MS: 912.4 m / z

Synthesis Example 5 Synthesis of Acrylic Polymer of Formula 16

After adding 1.5 g of initiator V601 (Wako Co., Ltd.) to a 100 ml beaker, dye monomers were added sequentially. A monomer solution was prepared by adding 72 g of solvent and stirring for 30 minutes until the dye monomers and the initiator were completely dissolved. In order to proceed with the polymerization reaction, 54 g of solvent (diacetone alcohol) was added to a 250 ml three-necked glass reactor equipped with a cooler and a nitrogen tube, and then heated to 85 ° C., followed by nitrogen bubbling. Next, the monomer solution prepared above was added dropwise to the reactor for 3 hours, and the reaction was performed at the same temperature for 9 hours, and then the temperature was lowered to room temperature and the reaction was terminated. The polymerization reaction was performed under a nitrogen atmosphere to obtain an acrylic polymer represented by the following formula (16).

[Formula 16]

Comparative Synthesis Example 1 Synthesis of Compound Represented by Formula (X)

10 g of compound A (CAS No. 77545-45-0) is charged to a reactor and dissolved with 100 g of 2-propanol. 7.2 g of diethylamine was added thereto, and the resultant was stirred at 80 ° C for 8 hours. The reaction was cooled and 800 mL of water was added to form a precipitate. The precipitate obtained was suction filtered and further washed with water. The filtrate was dried to give 9.9 g (84% yield) of the compound represented by Chemical Formula X.

Maldi-tof MS: 478.2 m / z

(Synthesis of Photosensitive Resin Composition)

Examples 1 to 16, Comparative Example 1 and Comparative Example 2

The photosensitive resin compositions according to Examples 1 to 16, Comparative Example 1 and Comparative Example 2 were prepared by mixing the components mentioned below in the compositions shown in Tables 1 to 3 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 and a pigment (in the form of a pigment dispersion) represented by the following Chemical Formula 6 were added to the obtained reactant as a colorant, 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%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 (A) binder resin 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (B) colorant B-1 14.0 - - - - - - - B-2 - 14.0 - - - - - - B-3 - - 14.0 - - - - - B-4 - - - 14.0 - - - - B-5 - - - - 14.0 - - - B-6 - - - - - 14.0 - - B-7 - - - - - - 14.0 - B-8 - - - - - - - 14.0 B-9 - - - - - - - - B-10 - - - - - - - - B-11 - - - - - - - - B-12 - - - - - - - - B'-1 54.0 54.0 54.0 54.0 54.0 54.0 54.0 54.0 B'-2 - - - - - - - - (C) photopolymerizable compound 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (D) photoinitiator 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (E) solvent 28.4 28.4 28.4 28.4 28.4 28.4 28.4 28.4 (F) additive 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

(Unit: weight%) Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 (A) binder resin 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (B) colorant B-1 - - - - - - - - B-2 - - - - - - - - B-3 - - - - - - - - B-4 - - - - - - - - B-5 - - 9.0 9.0 9.0 9.0 - - B-6 - - - - - - - - B-7 - - - - - - - - B-8 - - - - - - - - B-9 14.0 - - - - - - - B-10 - 14.0 - - - - - - B-11 - - - - - - 14.0 14.0 B-12 - - - - - - - - B'-1 54.0 54.0 28.0 43.0 25.0 50.0 54.0 60.0 B'-2 - - - - - - - - (C) photopolymerizable compound 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (D) photoinitiator 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (E) solvent 28.4 28.4 59.4 44.4 62.4 37.4 28.4 22.4 (F) additive 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

(Unit: weight%) Comparative Example 1 Comparative Example 2 (A) binder resin 1.5 1.5 (B) colorant B-1 - - B-2 - - B-3 - - B-4 - - B-5 - - B-6 - - B-7 - - B-8 - - B-9 - - B-10 - - B-11 - - B-12 14.0 - B'-1 54.0 40.0 B'-2 - 28.0 (C) photopolymerizable compound 1.5 1.5 (D) photoinitiator 0.4 0.4 (E) solvent 28.4 28.4 (F) additive 0.2 0.2

(A) binder resin

Acrylic binder resin (T-82, Samsung SDI Co., Ltd.)

(B) colorant

(B-1) A compound represented by the formula (6)

(B-2) A compound represented by the formula (7)

(B-3) A compound represented by the formula (8)

(B-4) Compound represented by formula (9)

(B-5) A compound represented by the formula (10)

(B-6) A compound represented by the formula (11)

(B-7) Compound represented by Formula 12

(B-8) Compound represented by formula (13)

(B-9) A compound represented by formula (14)

(B-10) Compound represented by formula (15)

(B-11) Acrylic polymer represented by formula (16)

(B-12) A compound represented by the formula (X)

(B'-1) Red Pigment Dispersion (AE1391, SANYO)

(B'-2) Red Pigment Dispersion (SC-P541-4316R, TOYO Corporation)

(C) photopolymerizable compound

Dipentaerythritol hexaacrylate (DPHA)

(D) photoinitiator

Oxime compound (IRGARCURE OXE01, BASF Corporation)

(E) solvent

Propylene Glycol Monomethyl Ether Acetate (PGMEA)

(F) additive

Surfactant (F-554 (10%), DIC Corporation)

Evaluation: Determination of color properties, heat resistance and chemical resistance

The photosensitive resin composition prepared in Examples 1 to 16, Comparative Example 1 and Comparative Example 2 in a thickness of 1 μm to 3 μm on a glass substrate having a thickness of 1 mm by degreasing was washed on a glass substrate using a spin coater. After coating under the conditions of 250rpm to 350rpm, prebaking was performed on a hot plate at 90 ° C. After that, the entire exposure was performed under the condition of 50mJ / cm ² in the exposure machine, and then the developing history was performed by developing the washing solution / developing solution for 60 seconds and washing for 60 seconds using the 111 times KOH developer in the developing machine. Gave. After development, post-baking was carried out in an oven at 230 ° C./20 minutes to produce color chips.

How to measure color characteristics

The prepared color specimens were evaluated for C light source reference color characteristics using MCPD (Otsuka Co., Ltd.) equipment, and the results are shown in Table 4 by calculating luminance (RY) based on Rx 0.658.

How to measure heat resistance

After further processing the prepared color specimens 230 ℃ / 60 minutes using a convection oven, the color change before and after the treatment using the MCPD (Otsuka Co., Ltd.) equipment to evaluate the C light source reference color characteristics, the results ΔEab * value was calculated and shown in Table 4 below.

How to measure chemical resistance

After producing the prepared color specimens in a size of 1 cm × 5 cm, precipitated in NMP solution for 3 minutes at 80 ℃, the precipitated NMP using UV VIS ABS. The analysis was carried out. After calculating the ABS and the quantitative curve for each color specimen, the amount eluted was calculated and shown in Table 4 below.

Luminance Heat resistance Chemical (Elution) Resistance (ppm) Example 1 18.79 1.22 1.0 Example 2 18.82 1.04 1.2 Example 3 18.77 1.16 1.4 Example 4 18.77 1.32 2.3 Example 5 18.71 1.42 3.3 Example 6 18.81 1.33 3.1 Example 7 18.77 1.34 2.4 Example 8 18.75 1.08 2.8 Example 9 18.79 1.14 3.3 Example 10 18.80 1.19 3.4 Example 11 18.6 2.04 4.4 Example 12 18.6 2.11 4.8 Example 13 18.66 2.68 5.8 Example 14 18.7 2.55 5.4 Example 15 18.83 0.97 3.6 Example 16 18.79 1.16 3.1 Comparative Example 1 18.63 3.36 8.5 Comparative Example 2 17.76 1.04 0.9

From Table 4, Comparative Example 1 in which the photosensitive resin composition of Examples 1 to 16, which contains a compound or an acrylic polymer according to one embodiment as a dye and also contains a pigment, does not include the compound or the acrylic polymer. And it can be seen that the color properties, heat resistance and chemical resistance superior to the photosensitive resin composition of Comparative Example 2.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to this, It is possible to variously deform and implement within the range of a claim, a detailed description of an invention, and an accompanying drawing. Naturally, it belongs to the scope of the invention.

Claims (17)

(A) binder resin;
(B) a colorant comprising a compound represented by the following formula (1) and a pigment dispersion;
(C) photopolymerizable compounds;
(D) photoinitiator and
(E) solvent
Photosensitive resin composition comprising:
[Formula 1]

In Chemical Formula 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,
At least one of the R ¹ to R ⁴ is represented by the formula (2),
[Formula 2]

In Chemical Formula 2,
L ¹ is a substituted or unsubstituted C1 to C20 alkylene group,
L ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,
R ⁵ is a substituent containing an ethylenically unsaturated double bond.
The method of claim 1,
R ⁵ is a substituted or unsubstituted acrylate group, a substituted or unsubstituted C2 to C20 alkenyl group or a C6 to C20 aryl group containing an ethylenically unsaturated double bond at the terminal.
The method of claim 1,
R ⁵ is a photosensitive resin composition represented by any one of the following Formula 3 to Formula 5:
[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 3 to 5,
R ⁶ is a hydrogen atom or a substituted or unsubstituted C1 to C5 alkyl group.
The method of claim 1,
At least two of the R ¹ to R ⁴ are represented by the formula (2).
The method of claim 1,
The R ¹ or R ² is a photosensitive resin composition represented by the formula (2).
The method of claim 5,
R ³ or R ⁴ is a photosensitive resin composition represented by the formula (2).
The method of claim 1,
The compound represented by Formula 1 is a photosensitive resin composition represented by any one of the following formulas (6) to (15).
[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

The method of claim 1,
The compound represented by Formula 1 has a maximum absorbance in the wavelength range of 500nm to 600nm.
(A) binder resin;
(B) a colorant comprising an acrylic polymer and a pigment dispersion formed by copolymerizing a compound represented by the formula (1) with an ethylenically unsaturated monomer;
(C) photopolymerizable compounds;
(D) photoinitiator and
(E) solvent
Photosensitive resin composition comprising a.
The method of claim 9,
The acrylic polymer is a photosensitive resin composition having a maximum absorbance in the wavelength range of 500nm to 600nm.
The method of claim 9,
The acrylic polymer and the pigment dispersion are contained in a weight ratio of 1: 2 to 1: 6.
The method of claim 9,
The ethylenically unsaturated monomer is selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid amino alkyl ester compounds, carboxylic acid vinyl ester compounds, unsaturated carboxylic acid glycidyl ester compounds, vinyl cyanide compounds, unsaturated amide compounds, and combinations thereof. The photosensitive resin composition which is any one selected.
The method according to claim 1 or 9,
The pigment in the pigment dispersion is a red pigment photosensitive resin composition.
The method according to claim 1 or 9,
The said photosensitive resin composition is with respect to the said photosensitive resin composition total amount,
1 wt% to 10 wt% of the (A) binder resin;
50% to 75% by weight of the colorant (B);
1 wt% to 5 wt% of the (C) photopolymerizable compound;
0.1 wt% to 5 wt% of the photopolymerization initiator (D) and
Residual amount of the solvent (E)
Photosensitive resin composition comprising a.
The method according to claim 1 or 9,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; And at least one additive selected from radical polymerization initiators.
The photosensitive resin film manufactured using the photosensitive resin composition of Claim 1 or 9.
A color filter comprising the photosensitive resin film of claim 16.

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