KR20180039976A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

Provided are a photosensitive resin composition, a photosensitive resin film manufactured by using the photosensitive resin composition, and a color filter including the photosensitive resin film. The photosensitive resin composition comprises: (A) a binder resin; (B) a colorant including a compound represented by chemical formula 1 or an acrylic polymer formed by copolymerization of the compound and an ethylenically unsaturated monomer and a pigment dispersion; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent. In the chemical formula 1, each substituent is the same as defined in the specification.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film, and a color filter using the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition, a photosensitive resin film produced using the same, and a color filter comprising the photosensitive resin film.

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

Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and ITO pixel electrodes are formed, and an upper substrate on which an active circuit portion composed of a liquid crystal layer, a thin film transistor, and a capacitor layer and an ITO pixel electrode are formed. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate so as to shield the boundary between pixels and a plurality of colors (typically red (R), green (G), blue ) Are arrayed in a predetermined order, and the pixel portions are stacked in this order.

In the pigment dispersion method, which is one of the methods of implementing a color filter, a photopolymerizable composition containing a colorant is coated on a transparent substrate provided with a black matrix, a pattern of a pattern to be formed is exposed, And a coloring thin film is formed by repeating a series of processes of thermosetting.

The colored photosensitive resin composition used in the production of a color filter according to the pigment dispersion method generally comprises an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a solvent and other additives, and may further contain an epoxy resin or the like. The pigment dispersion method as described above is actively applied to manufacture LCDs for mobile phones, notebooks, monitors, TVs and the like.

However, even in a photosensitive resin composition for a color filter using a pigment dispersion method having various advantages in recent years, it is difficult to make the powder finer, and various additives are required because the dispersed state must be stable in the dispersion even when dispersed. And it is difficult to store and transport because the pigment dispersion must maintain an optimal quality state.

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

Accordingly, efforts have been made to develop dyes having heat resistance and chemical resistance similar to those of pigments instead 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 characteristics, heat resistance, and chemical resistance.

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

Another embodiment is to provide a color filter comprising 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) a photopolymerizable compound; (D) a photopolymerization initiator and (E) a solvent.

[Chemical Formula 1]

In 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 R ¹ to R ⁴ is represented by the following general formula (2)

(2)

In 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 group containing an ethylenically unsaturated double bond.

The 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 containing an ethylenically unsaturated double bond at the terminal.

The R ⁵ may be represented by any one of the following formulas (3) to (5).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above 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 the formula (2).

The R ¹ or R ² may be represented by the formula (2).

The R ¹ or R ² may be represented by the formula (2), and the R ³ or R ⁴ may be represented by the formula (2).

The compound represented by the formula (1) may be represented by any one of the following formulas (6) to (15).

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

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

Another embodiment includes (A) a binder resin; (B) a colorant comprising an acrylic polymer and a pigment dispersion formed by the copolymerization reaction between the compound represented by Formula 1 and an ethylenically unsaturated monomer; (C) a photopolymerizable compound; (D) a photopolymerization initiator and (E) a solvent.

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

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

Wherein the ethylenically unsaturated monomer is at least one selected from the group consisting of an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, a carboxylic acid vinyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a vinyl cyanide compound, an unsaturated amide compound, It can be any one selected.

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

Wherein the photosensitive resin composition comprises 1 to 10% by weight of the binder resin (A) relative to the total amount of the photosensitive resin composition; 50% to 75% by weight of (B) the colorant; 1% to 5% by weight of (C) the photopolymerizable compound; 0.1 to 5% by weight of the photopolymerization initiator (D) and the residual amount of the solvent (E).

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.

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

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

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

The compound according to one embodiment and the acrylic polymer are excellent in solubility in an organic solvent and can be obtained by using a photosensitive resin composition comprising the above compound or a colorant containing an acrylic polymer as a constituent, Excellent color filters can be manufactured.

1 is a GPC graph of an acrylic polymer represented by the formula (16).

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Means that at least one hydrogen atom of the functional group of the present invention is substituted with a halogen atom (F, Br, Cl or I), a hydroxyl group, a nitro group, a cyano group, an amino group NH _2, NH (R ^200), or N (R ²⁰¹⁾ (R ^202), wherein R ^200, R ²⁰¹ and R ²⁰² are the same or different, each independently being a C1 to C10 alkyl groups), amidino group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, And a substituted or unsubstituted heterocyclic group substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless otherwise specified in the specification, "alkyl group" means C1 to C20 alkyl group, specifically C1 to C15 alkyl group, "cycloalkyl group" means C3 to C20 cycloalkyl group, specifically C3 Refers to a C1 to C20 alkoxy group, specifically, a C1 to C18 alkoxy group, and an "aryl group" means a C6 to C20 aryl group, specifically, a C6 to C20 aryl group, Means a C 2 to C 20 alkenyl group, specifically, a C 2 to C 18 alkenyl group, and the "alkylene group" means a C 1 to C 20 alkylene group, specifically, a C1 Refers to a C6 to C20 arylene group, and specifically refers to a C6 to C16 arylene group.

(Meth) acrylate "refers to both" acrylic acid "and" methacrylic acid " It means both are possible.

As used herein, unless otherwise defined, "combination" means mixing or copolymerization. "Copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the present specification, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (17-1) to (17-11) is contained in the main backbone of the resin.

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

In addition, unless otherwise defined herein, "*" means the same or different atom or moiety connected to the formula.

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 reaction of said compound and an ethylenically unsaturated monomer, and a pigment dispersion; (C) a photopolymerizable compound; (D) a photopolymerization initiator and (E) a solvent.

[Chemical Formula 1]

In 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 R ¹ to R ⁴ is represented by the following general formula (2)

(2)

In 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 group containing an ethylenically unsaturated double bond.

In a color filter made of a pigment type photosensitive resin composition, there is a limit of luminance and contrast ratio resulting from the pigment particle size. Further, 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 a demand, attempts have been made to introduce a dye that does not form a particle instead of a pigment to produce a photosensitive resin composition suitable for a dye, thereby realizing a color filter having improved luminance and contrast ratio.

In general, the xanthene-based compound is separated from its charge, and the photosensitive resin composition containing the same has low solubility in an organic solvent such as PGMEA and has a low heat resistance and chemical resistance, and thus has limitations in use as a colorant in a photosensitive resin composition. However, the photosensitive resin composition according to one embodiment contains at least one compound represented by Formula 1 (including at least one substituent represented by Formula 2) or a compound represented by Formula 1 (the substituent represented by Formula 2 is at least And an ethylenically unsaturated monomer as a colorant together with the pigment dispersion to improve the solubility in an organic solvent. Accordingly, it is possible to improve the solubility of the acrylic polymer in an organic solvent, A color filter having improved heat resistance and chemical resistance can be produced.

Each component will be described in detail below.

(B) Colorant

The colorant includes an acrylic polymer formed by copolymerization reaction of the compound represented by Formula 1 or the compound represented by Formula 1 and an ethylenically unsaturated monomer together with a pigment dispersion.

At least two of R ¹ to R ⁴ may be represented by the formula (2). When the compound represented by the general formula (1) contains two or more substituents represented by the general formula (2), the solubility in an organic solvent and the brightness of a composition containing such a compound can be further improved. The method of synthesizing a compound containing only one functional group represented by the general formula (2) can be achieved by controlling the content of the reactant in comparison with the method of synthesizing a compound containing at least two functional groups represented by the general formula (2) Compounds containing at least one functional group represented by the general formula (1) can be easily synthesized by referring to a synthesis method of a compound containing at least two functional groups represented by the general formula (2).

For example, R ¹ or R ² may be represented by the formula (2).

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

The 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 containing an ethylenically unsaturated double bond at the terminal.

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

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above 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 the formula (1) may be represented by any one of the following formulas (6) to (15), but is not limited thereto.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

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

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

For example, the acrylic polymer may be included in an amount of 10% by weight to 20% by weight based on the total amount of the photosensitive resin composition.

For example, the pigment dispersion may be contained in an amount of 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 above-mentioned content range, color characteristics, heat resistance and chemical resistance can be further improved.

For example, the ethylenically unsaturated monomer may be an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, a carboxylic acid vinyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a vinyl cyanide compound, an unsaturated amide compound, have.

For example, the ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, 2- Unsaturated carboxylic acid ester compounds such as (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide, or combinations thereof.

The acrylic polymer, which is a product of the polymerisation reaction through the copolymerization of the compound represented by the formula (1) and the ethylenically unsaturated monomer, is excellent in heat resistance and processability and can be used as a colorant in a photosensitive resin composition 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.

[Chemical 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 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, azapphyrin compounds, and indigo compounds.

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

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

Examples of the blue pigments 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, sikomine pigments, anthraquinone (sudan I, II, III, R), vis azo ), Benzopyran and the like.

Examples of the green pigment include C.I. And halogenated phthalocyanine pigments such as Pigment Green 58.

Examples of the yellow pigments include C.I. Pigment yellow 139, C.I. Pigment yellow 138, C.I. Pigment yellow 150, etc. These may be used alone or in combination of two or more.

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

The pigment dispersion 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% by weight to 80% by weight, such as 50% by weight to 70% by weight, such as 55% by weight to 65% by weight, based on the total weight of the pigment dispersion.

As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid Salts, alkylamide alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more.

DISPERBYK-161, DISPERBYK-160, DISPERBYK-161, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160 and DISPERBYK-160 of BYK Co., -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 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.

The dispersing agent may be contained in an amount of 1 to 20% by weight based on the total amount of the pigment dispersion. When the dispersing agent is contained within the above range, the dispersibility of the photosensitive resin composition can be maintained because an appropriate viscosity can be maintained, so that optical, physical and chemical quality can be maintained when the product is applied.

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

The colorant may be contained in an amount of 50% by weight to 75% by weight, for example, 60% by weight to 70% by weight based on the total amount of the photosensitive resin composition. When the colorant is contained within the above range, the coloring effect and developing performance are excellent.

(A) Binder resin

The binder resin may include an acrylic binder resin, a cadmium 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 with the first ethylenically unsaturated monomer, and is a resin containing at least one acrylic repeating unit.

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

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

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two 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- Acrylate copolymer, a (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but not limited thereto, and they may be used alone or in combination have.

The weight average molecular weight of the acrylic binder resin may be from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 50,000 g / mol, such as from 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 photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate during the production of a color filter.

The acid value of the acrylic binder resin may be from 15 mgKOH / g to 60 mgKOH / g, such as from 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 cadmium-based binder resin may include a repeating unit represented by the following general formula (17).

[Chemical Formula 17]

In 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 C 1 to C 20 alkyl group) (17-1) to (17-11)

[Formula 17-1]

[Formula 17-2]

[Formula 17-3]

[Formula 17-4]

[Formula 17-5]

(In the above 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]

[Chemical Formula 17-10]

[Formula 17-11]

Z ² is an acid anhydride residue,

m1 and m2 are each independently an integer of 0 to 4;

The cadmium-based binder resin may include a functional group represented by the following formula (18) in at least one of the two terminals.

[Chemical Formula 18]

In Formula 18,

Z ³ can be represented by the following formulas (18-1) to (18-7).

[Formula 18-1]

(Wherein 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]

Wherein R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group or a C2 to C20 alkenylamine group.

[Formula 18-6]

[Formula 18-7]

Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride , Tetrahydrofuran tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride and the like; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, or the like.

When the cationic binder resin is used together with the acrylic binder resin described above, a photosensitive resin composition having excellent adhesion and high resolution and high brightness characteristics can be obtained.

The weight average molecular weight of the cationic binder resin may be from 500 g / mol to 50,000 g / mol, such as from 3,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cationic binder resin is within the above range, pattern formation is good without residue in the production of a color filter, no loss of film thickness during development, and good patterns can be obtained.

The cadmium binder resin may have an acid value of from 100 mgKOH / g to 140 mgKOH / g.

The binder resin may be contained 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 contained within the above range, the color filter is excellent in developing property and the crosslinking property is improved, whereby excellent surface smoothness can be obtained.

(C) Photopolymerizable compound

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

By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.

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, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethacrylate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate and the like.

Examples of commercially available products of photopolymerizable compounds are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -710 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable compound may be treated with an acid anhydride so as to give better developing properties.

The photopolymerizable compound may be contained in an amount of 1 wt% to 5 wt%, for example, 1 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the above-mentioned range, the pattern forming process sufficiently cures upon exposure to light, which is excellent in reliability and developability in an alkaline developer.

(D) a photopolymerization initiator

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

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

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

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.

Examples of the oxime compounds include O-acyloxime compounds, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Etc. may be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione -1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate, and the like.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

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

The photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, the photopolymerization initiator is sufficiently cured upon exposure in the pattern formation step to obtain excellent reliability, and the pattern is excellent in heat resistance, light resistance, chemical resistance, resolution and adhesion, It is possible to prevent the transmittance from being lowered.

(E) Solvent

The solvent may be a material that has compatibility with the colorant, the binder resin, the photopolymerizable compound, the photopolymerization initiator, and the like but does not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl 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 methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, glycol ethers such as ethylene glycol monoethyl ether and the like are preferably used in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in a residual amount, for example, 20% by weight to 40% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the color filter is excellent.

(F) Other additives

The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent spots and spots upon application, to improve the leveling performance, 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Surfactants; And at least one additive selected from a radical polymerization initiator.

The additive can be easily adjusted according to desired properties.

The coupling agent may be a silane coupling agent. Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and these may be used singly or in combination of two or more Can be mixed and used.

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

The photosensitive resin composition for a color filter may further contain a surfactant, for example, a fluorine-based surfactant, if necessary.

Examples of the fluorine-based surfactant include F-554, F-482, F-484 and F-478 of DIC Co., but are not limited thereto.

The amount of the surfactant is preferably 0.01 wt% to 5 wt%, more preferably 0.01 wt% to 2 wt% with respect to the total amount of the photosensitive resin composition. If it is out of the above range, a foreign matter may be generated after development, which is not preferable.

The photosensitive resin composition may further include an epoxy compound to improve adhesion with the substrate.

Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

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

The photosensitive resin composition may contain a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.

According to another embodiment, there is provided a photosensitive resin film produced using the photosensitive resin composition.

According to another embodiment, there is provided a color filter comprising the photosensitive resin film.

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 a step of heat-treating the photosensitive resin film. The process conditions and the like are well known in the art, and therefore, detailed description thereof will be omitted herein.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are only the preferred embodiments 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 Formula 10

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

10 g of the compound B was added to the reactor, and 30 g of dimethylformamide and 7.0 g of methacryloyloxyethyl isocyanate were added thereto, followed by stirring for 8 hours. 100 g of dichloromethane is added to the reaction mixture and the mixture is washed with water. The obtained organic layer was subjected to silica filtration and then vacuum distilled. The distilled mixture was dissolved in 10 g of dichloromethane and added dropwise to 100 g of normal hexane for precipitation. The resulting precipitate was suction filtered and further washed. The filtrate was dried to obtain 12.8 g (80% yield) of the compound represented by the above formula (10).

Mald-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) was charged to the reactor and dissolved in 100 g of 2-propanol. 9.4 g of 2-butylaminoethanol was added thereto, followed by stirring at 80 DEG C for 8 hours. The reaction was cooled and 800 mL of water was added to form a precipitate. The resulting precipitate was suction filtered and further washed with water. The filtrate was dried to obtain 10.9 g (78% yield) of Compound C.

10 g of the compound B was added to the reactor, and 30 g of dimethylformamide and 7.0 g of methacryloyloxyethyl isocyanate were added thereto, followed by stirring for 8 hours. 100 g of dichloromethane is added to the reaction mixture and the mixture is washed with water. The obtained organic layer was subjected to silica filtration and then vacuum distilled. The distilled mixture was dissolved in 10 g of dichloromethane and added dropwise to 100 g of normal hexane for precipitation. The resulting precipitate was suction filtered and further washed. The filtrate was dried to obtain 11.6 g (75% yield) of the compound represented by the above formula (11).

Mald-tof MS: 876.4 m / z

Synthesis Example 3: Synthesis of Compound Represented by Formula 14

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

[Chemical Formula 14]

Mald-tof MS: 792.3 m / z

Synthesis Example 4: Synthesis of Compound Represented by 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 and stirred for 8 hours. 100 g of dichloromethane is added to the reaction mixture and the mixture is washed with water. The obtained organic layer was subjected to silica filtration and then vacuum distilled. The distilled mixture was dissolved in 10 g of dichloromethane and added dropwise to 100 g of normal hexane for precipitation. The resulting precipitate was suction filtered and further washed. The filtrate was dried to obtain 12.1 g (68% yield) of a compound represented by the following formula (15).

[Chemical Formula 15]

Mald-tof MS: 912.4 m / z

Synthesis Example 5: Synthesis of acrylic polymer represented by formula (16)

After adding 1.5 g of initiator V601 (Wako) to a 100 ml beaker, the dye monomers were added in turn. 72 g of the solvent was added, and the monomer solution was prepared by stirring for 30 minutes until the dye monomers and the initiator completely melted. To proceed with the polymerization reaction, 54 g of diacetone alcohol was added to a 250 ml three-necked glass reactor equipped with a condenser and a nitrogen tube, and the mixture was heated to 85 ° C and bubbled with nitrogen. Next, the monomer solution prepared above was added dropwise to the reactor for 3 hours. After the reaction was carried out at the same temperature for 9 hours, the temperature was lowered to room temperature and the reaction was terminated. The polymerization reaction proceeded in a nitrogen atmosphere to obtain an acrylic polymer represented by the following formula (16).

[Chemical Formula 16]

Comparative Synthesis Example 1: Synthesis of Compound Represented by Formula X

10 g of Compound A (CAS No. 77545-45-0) was charged to the reactor and dissolved in 100 g of 2-propanol. 7.2 g of diethylamine was added thereto, followed by stirring at 80 DEG C for 8 hours. The reaction was cooled and 800 mL of water was added to form a precipitate. The resulting precipitate was suction filtered and further washed with water. The filtrate was dried to obtain 9.9 g (84% yield) of the compound represented by the above formula (X).

Mald-tof MS: 478.2 m / z

(Synthesis of photosensitive resin composition)

Examples 1 to 16, Comparative Examples 1 and 2

The following components were mixed in the compositions shown in Tables 1 to 3 to prepare the photosensitive resin compositions of Examples 1 to 16, Comparative Examples 1 and 2.

Specifically, a photopolymerization initiator was dissolved in a solvent, and the mixture was stirred at room temperature for 2 hours. Then, an alkali-soluble resin and a photopolymerizable compound were added thereto, followed by stirring at room temperature for 2 hours. Subsequently, a compound represented by the following formula (6) as a colorant and a pigment (in the form of a pigment dispersion) were added to the obtained reaction product, followed by stirring at room temperature for 1 hour. Then, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: wt%) 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) a photopolymerization initiator 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: wt%) 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) a photopolymerization initiator 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: wt%) 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) a photopolymerization initiator 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)

(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) a compound represented by the formula (9)

(B-5) Compound represented by formula (10)

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

(B-7) A compound represented by the formula (12)

(B-8) A compound represented by the formula (13)

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

(B-10) A compound represented by the formula (15)

(B-11) The acrylic polymer represented by the 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)

(C) Photopolymerizable compound

Dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)

(D) a photopolymerization initiator

Oxime compounds (IRGARCURE OXE01, BASF)

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA) (Kyowa Hakko)

(F) Additive

Surfactants (F-554 (10%), DIC)

Evaluation: Measurement of color characteristics, heat resistance and chemical resistance

The photosensitive resin composition prepared in Examples 1 to 16, Comparative Example 1 and Comparative Example 2 was coated on a glass substrate having a thickness of 1 mm to a thickness of 1 m to 3 m using a spin coater After coating at 250 rpm to 350 rpm, pre-baking was carried out on a hot plate at 90 ° C. Then, the entire exposure was carried out under the condition of 50 mJ / cm ² in the exposure machine, and then development was carried out in a development machine using 111-fold KOH developer under the condition of wash solution / developing solution = 1 / 0.8 for 60 seconds and 60 seconds, . After development, post-baking was performed in an oven at 230 ° C for 20 minutes to prepare a color chip.

How to measure color characteristics

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

How to measure heat resistance

The prepared color sample was further treated at 230 DEG C for 60 minutes using a convection oven, and the color change before and after the treatment was evaluated using the MCPD (Otsuka) Was calculated, and the results are shown in Table 4. < tb > < TABLE >

How to measure chemical resistance

The prepared color sample was made into a size of 1 cm x 5 cm and then precipitated in an NMP solution at 80 ° C for 3 minutes. And analyzed. ABS and quantitative curves of each color sample were obtained and the amount eluted was calculated and shown in Table 4 below.

Luminance Heat resistance Chemical (elution) property (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, it can be seen that the photosensitive resin compositions of Examples 1 to 16 containing the compound or acrylic polymer according to one embodiment as a dye and also including a pigment are the same as the compound or acrylic polymer of Comparative Example 1 And the photosensitive resin composition of Comparative Example 2 exhibited excellent color characteristics, heat resistance and chemical resistance.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (17)

(A) a binder resin;
(B) a colorant comprising a compound represented by the following formula (1) and a pigment dispersion;
(C) a photopolymerizable compound;
(D) a photopolymerization initiator and
(E) Solvent
: ≪ EMI ID =
[Chemical Formula 1]

In 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 R ¹ to R ⁴ is represented by the following general formula (2)
(2)

In 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 group containing an ethylenically unsaturated double bond.
The method according to claim 1,
Wherein 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 according to claim 1,
Wherein R ⁵ to the photosensitive resin composition is represented by one of Formula 3 to Formula 5:
(3)

[Chemical Formula 4]

[Chemical Formula 5]

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

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

The method according to claim 1,
Wherein the compound represented by Formula 1 has a maximum absorbance in a wavelength range of 500 nm to 600 nm.
(A) a binder resin;
(B) a colorant comprising an acrylic polymer and a pigment dispersion formed by the copolymerization reaction of the compound of claim 1 and an ethylenically unsaturated monomer;
(C) a photopolymerizable compound;
(D) a photopolymerization initiator and
(E) Solvent
.
10. The method of claim 9,
Wherein the acrylic polymer has a maximum absorbance in a wavelength range of 500 nm to 600 nm.
10. The method of claim 9,
Wherein the acrylic polymer and the pigment dispersion are contained in a weight ratio of 1: 2 to 1: 6.
10. The method of claim 9,
Wherein said ethylenically unsaturated monomer is at least one selected from the group consisting of an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, a carboxylic acid vinyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a vinyl cyanide compound, an unsaturated amide compound, Wherein the photosensitive resin composition is a photosensitive resin composition.
10. The method of claim 1 or 9,
Wherein the pigment in the pigment dispersion is a red pigment.
10. The method of claim 1 or 9,
The photosensitive resin composition preferably contains, relative to the total amount of the photosensitive resin composition,
1 to 10% by weight of the binder resin (A);
50% to 75% by weight of (B) the colorant;
1% to 5% by weight of (C) the photopolymerizable compound;
0.1 to 5% by weight of the photopolymerization initiator (D)
The amount of the solvent (E)
.
10. The method of claim 1 or 9,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.
A photosensitive resin film produced by 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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