KR20180059183A - Photosensitive resin composition and photosensitive resin layer using the same and color filter - Google Patents

Abstract

A photosensitive resin composition and a color filter manufactured using the same are provided. The photosensitive resin composition comprises: (A1) a first acrylic binder resin; (A2) a second acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; and (E) a solvent. The photosensitive resin composition of the present invention can enhance the flowability of patterns as well as the brightness.

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.

Recently, as the spread of the large-screen liquid crystal display device has expanded, a demand for a new performance enhancement for the liquid crystal display device has been increasing. Among the components of the liquid crystal display device, the color filter is the most important color realizing device. Research is continuing.

In addition, in the case of a large-screen liquid crystal display device, the colorant concentration of the photosensitive resin composition is increased in manufacturing a color filter in order to increase the color purity. In order to increase productivity and yield in the production process, a photosensitive resin composition having a low developing speed and excellent sensitivity .

The color filter using the photosensitive resin composition can be produced by coating three or more kinds of hues on a transparent substrate mainly by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method and the like. Recently, a pigment dispersion method is widely used.

On the other hand, in a color filter made of a pigment type photosensitive resin composition, there is a limit in that the luminance and the contrast ratio are lowered due to the pigment particle size and the aggregation of the pigment particles. In order to overcome such limitations, attempts have been made to use a dye-type photosensitive resin composition which does not form particles or has a dye having a very small primary particle diameter relative to the pigment dispersion. However, the dye-type photosensitive resin composition is difficult to commercialize due to its weak heat resistance, light resistance and chemical resistance.

One embodiment is to provide a photosensitive resin composition capable of improving the brightness together with the occurrence of water stains and the flow of the pattern.

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 (A1) a first acrylic binder resin comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3) ; (A2) a polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (5), a repeating unit represented by the following formula (6), a repeating unit represented by the following formula A second acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 1 to 8,

R ¹ is a substituted or unsubstituted C 1 to C 10 alkyl group

R ² to R ⁵ and R ⁷ to R ⁹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ⁶ is a substituted or unsubstituted C 11 to C 20 alkyl group.

The repeating unit represented by Formula 1 is contained in an amount of 15 to 25% by weight based on the total amount of the first acrylic binder resin, the repeating unit represented by Formula 2 is contained in an amount of 15 to 25% by weight, The repeating unit represented by Formula 3 may be contained in an amount of 10 to 20% by weight, and the repeating unit represented by Formula 4 may be contained in an amount of 40 to 50% by weight.

The repeating unit represented by Formula 1 is contained in an amount of 15 to 25% by weight based on the total amount of the second acrylic binder resin, the repeating unit represented by Formula 5 is contained in an amount of 5 to 15% by weight, The repeating unit represented by Formula 6 is contained in an amount of 15 to 25% by weight, the repeating unit represented by Formula 7 is contained in an amount of 35 to 45% by weight, and the repeating unit represented by Formula 8 is 5 By weight to 15% by weight.

The first acrylic binder resin may have a weight average molecular weight of 2,000 g / mol to 9,000 g / mol.

The first acrylic binder resin may have an acid value of 100 mgKOH / g to 120 mgKOH / g.

The second acrylic binder resin may have a weight average molecular weight of 10,000 g / mol to 17,000 g / mol.

The second acrylic binder resin may have an acid value of 80 mgKOH / g to 99 mgKOH / g.

The first acrylic binder resin may be contained in a smaller amount than the second acrylic binder resin.

The photosensitive resin composition may further comprise (A3) an epoxy binder resin.

The photopolymerizable monomer may include a compound represented by the following general formula (9).

[Chemical Formula 9]

In the above formula (9)

R ¹⁰ to R ¹⁵ each independently represent the following formula (10)

[Chemical formula 10]

In Formula 10,

n is an integer of 1 or 2;

The n may be an integer of 2.

The colorant may include a dye and a pigment represented by the following general formula (11).

(11)

In Formula 11,

Y ¹ to Y ¹² are each independently Cl or Br,

Each of R ¹⁶ to R ¹⁹ independently represents a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C6 to C20 Lt; / RTI >

At least one of R ¹⁶ to R ¹⁹ is represented by the following general formula (12)

[Chemical Formula 12]

In Formula 12,

R ²⁰ and R ²¹ are each independently a C1 to C10 alkyl group substituted or unsubstituted with a C1 to C5 alkyl group,

o and p are each independently an integer of 0 to 5, provided that 1?? o + p?? 5.

The dye represented by the formula (11) may be represented by any one selected from the group consisting of the following formulas (11-1) to (11-8).

[Formula 11-1]

[Formula 11-2]

[Formula 11-3]

[Formula 11-4]

[Formula 11-5]

[Formula 11-6]

[Formula 11-7]

[Formula 11-8]

The pigments may include green pigments and yellow pigments.

The photopolymerization initiator may include a compound represented by the following general formula (13).

[Chemical Formula 13]

In Formula 13,

R ²² and R ²³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group.

Wherein the photosensitive resin composition comprises 1 to 10% by weight of the (A1) acrylic binder resin, based on the total amount of the photosensitive resin composition; 5 to 15% by weight of the acrylic binder resin (A2); 1 to 10% by weight of the photopolymerizable monomer (B); 0.1 to 5% by weight of the photopolymerization initiator (C); 30% to 55% by weight of (D) the colorant; And (E) the solvent balance.

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof.

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 photosensitive resin composition according to one embodiment can improve the heat resistance, the luminance, the surface wrinkles, the unevenness of the developing object, etc., and can be usefully used for a color filter.

1 and 2 are photographs showing patterns of a photosensitive resin film produced using the photosensitive resin composition according to Example 1, respectively.
FIGS. 3 and 4 are photographs showing patterns of the photosensitive resin film prepared using the photosensitive resin composition according to Example 2, respectively.
5 and 6 are photographs showing patterns of the photosensitive resin film produced using the photosensitive resin composition according to Example 3, respectively.
Figs. 7 and 8 are photographs showing patterns of the photosensitive resin film produced using the photosensitive resin composition according to Example 4, respectively. Fig.
Figs. 9 and 10 are photographs showing patterns of the photosensitive resin film produced using the photosensitive resin composition according to Comparative Example 1 independently of each other. Fig.
Figs. 11 and 12 are photographs showing patterns of the photosensitive resin film prepared using the photosensitive resin composition according to Comparative Example 2 independently of each other.
13 and 14 are photographs showing patterns of the photosensitive resin film produced using the photosensitive resin composition according to Comparative Example 3 independently of each other.
15 is a photograph showing a taper shape and an angle of a photosensitive resin film produced using the photosensitive resin composition according to Example 1. Fig.
16 is a photograph showing the taper shape and the angle of the photosensitive resin film produced using the photosensitive resin composition according to Example 2. Fig.
17 is a photograph showing a taper shape and an angle of a photosensitive resin film produced using the photosensitive resin composition according to Example 3. Fig.
18 is a photograph showing the taper shape and the angle of the photosensitive resin film produced using the photosensitive resin composition according to Example 4. Fig.
19 is a photograph showing the taper shape and the angle of the photosensitive resin film produced using the photosensitive resin composition according to Comparative Example 1. Fig.
20 is a photograph showing a taper shape and an angle of a photosensitive resin film produced using the photosensitive resin composition according to Comparative Example 2. Fig.
21 is a photograph showing the taper shape and the angle of the photosensitive resin film produced using the photosensitive resin composition according to Comparative Example 3. Fig.

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, Cl, Br 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, Refers to a C 2 to C 20 alkenyl group, specifically, a C 2 to C 18 alkenyl group, and the "alkylene group" refers to 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.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.

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

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.

Also, unless otherwise specified herein, " * " means the same or different atom or moiety connected to the formula.

The photosensitive resin composition according to one embodiment contains (A1) a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3) A first acrylic binder resin; (A2) a polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (5), a repeating unit represented by the following formula (6), a repeating unit represented by the following formula A second acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 1 to 8,

R ¹ is a substituted or unsubstituted C 1 to C 10 alkyl group

R ² to R ⁵ and R ⁷ to R ⁹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ⁶ is a substituted or unsubstituted C 11 to C 20 alkyl group.

In order to improve the color characteristics (for example, luminance and the like) and the pattern properties (for example, pattern wrinkles and water stains) of the color filter, it is common to improve the pigment in the photosensitive resin composition. However, when the pigment is improved, the conventional process can not be used as it is, and even when the conventional process is used as it is, the effect of improving the color characteristic is insignificant.

However, the acrylic binder resin in the photosensitive resin composition according to one embodiment contains the repeating units represented by the above Chemical Formulas 1 to 8 to control the developability of the pattern while ensuring high heat resistance, pattern surface characteristics, high luminance characteristics, and adhesion Further, the characteristics can be improved more effectively by further including a photopolymerizable monomer represented by a specific formula, a photopolymerization initiator, and a dye.

Each component will be described in detail below.

(A) Acrylic binder resin

The photosensitive resin composition according to one embodiment includes a first acrylic-based resin composition comprising a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), a repeating unit represented by the formula (3) And a binder resin (A1).

For example, in the above Chemical Formulas 1 to 4,

R ¹ to R ⁴ each independently may be a C ¹ to C 5 alkyl group, R ⁵ may be a hydrogen atom, and R ⁶ may be a substituted or unsubstituted C 11 to C 18 alkyl group.

The photosensitive resin composition according to one embodiment may further contain a repeating unit represented by the formula (1), a repeating unit represented by the formula (5), a repeating unit represented by the formula (6), a repeating unit represented by the formula (7) And a second acrylic binder resin (A2) containing a repeating unit represented by the following formula (1).

For example, in the above Chemical Formulas 5 to 8,

R ¹ to R ⁴ each independently may be a C ¹ to C 5 alkyl group, and R ⁷ to R ⁹ may each independently be a hydrogen atom.

Since the photosensitive resin composition according to one embodiment includes the first acrylic binder resin, the heat resistance can be enhanced to improve the brightness. When the second acrylic binder resin is included in the photosensitive resin composition, the generation of the surface wrinkles can be controlled So that the luminance can be further improved.

The repeating unit represented by Formula 1 is contained in an amount of 15 to 25% by weight based on the total amount of the first acrylic binder resin, the repeating unit represented by Formula 2 is contained in an amount of 15 to 25% by weight, The repeating unit represented by Formula 3 may be contained in an amount of 10 to 20% by weight, and the repeating unit represented by Formula 4 may be contained in an amount of 40 to 50% by weight.

Particularly, when the content of the repeating unit represented by the formula (2) is less than 15% by weight or more than 25% by weight based on the total amount of the first acrylic binder resin, the surface characteristics are deteriorated and the improvement of the brightness is limited.

The first acrylic binder resin may be included in an amount of 1 wt% to 10 wt%, for example, 1 wt% to 5 wt% with respect to the total amount of the photosensitive resin composition. The second acrylic binder resin may be included in an amount of 5% by weight to 15% by weight, for example, 5% by weight to 10% by weight based on the total amount of the photosensitive resin composition. When the first acrylic binder resin and the second acrylic binder resin are contained within the above ranges, excellent brightness, heat resistance, developability and crosslinkability can be obtained during production of a color filter, and excellent surface smoothness can be obtained.

The repeating unit represented by the formula (1) is contained in an amount of 15 to 25% by weight based on the total amount of the second acrylic binder resin, and the repeating unit represented by the formula (5) is contained in an amount of 5 to 15% , The repeating unit represented by Formula 6 is contained in an amount of 15 to 25 wt%, the repeating unit represented by Formula 7 is contained in an amount of 35 to 45 wt%, the repeating unit represented by Formula 8 May range from 5% to 15% by weight.

When the first acrylic binder resin and the second acrylic binder resin each contain the repeating units represented by the above formulas (1) to (8) within the above range, the pattern surface characteristics can be further improved.

The first acrylic binder resin may have a weight average molecular weight of 2,000 g / mol to 9,000 g / mol and an acid value of 100 mgKOH / g to 120 mgKOH / g. The second acrylic binder resin may have a weight average molecular weight of 10,000 g / mol to 17,000 g / mol and an acid value of 80 mgKOH / g to 99 mgKOH / g.

When the first acrylic binder resin and the second acrylic binder resin each have a weight average molecular weight and an acid value in the above range, the developing performance and the adhesion of the formed pattern are improved when the pattern is realized.

The first acrylic binder resin may be contained in a smaller amount than the second acrylic binder resin. When the first acrylic binder resin contains the same amount of the second acrylic binder resin (or the first acrylic binder resin contains more content than the second acrylic binder resin), there is a problem that developability is lowered.

The photosensitive resin composition may further comprise an epoxy binder resin (A3).

The heat-resistant property of the photosensitive resin composition according to one embodiment can be improved by further including an epoxy binder resin. Examples of the epoxy binder resin include phenol novolac epoxy resin, tetramethylbiphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, and combinations thereof. It is not.

Furthermore, the epoxy binder resin assures dispersion stability of dyes and pigments to be described later, and also helps to form a pixel of a desired resolution in a developing process.

The epoxy equivalent weight of the epoxy binder resin may be from 150 g / eq to 200 g / eq. When an epoxy binder resin having an epoxy equivalent within the above range is contained in the binder resin, there is an advantageous effect in improving the curing of the formed pattern and fixing the dye in the patterned structure.

The epoxy binder resin may be contained 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.

(B) Photopolymerization  Monomer

The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond, and the monofunctional or polyfunctional ester may be used in combination.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as 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 tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol Furnace there may be mentioned methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acrylate such as oxyethyl phosphate, novolak epoxy (meth) acrylate, or a combination thereof.

A commercially available product of the photopolymerizable monomer is exemplified as follows. The (meth) acrylic acid is one example of a polyfunctional ester, doah Gosei Kagaku Kogyo's (primary)社Aronix ^M-101? , Dong M-111 ^? , M-114 ^? Etc; KAYARAD TC-110S from Nihon Kayaku Co., Ltd. ^? , The TC-120S ^? Etc; V-158 of Osaka Yuzagaku Kogyo Co., Ltd. ^? , V-2311 ^? And the like. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo's Aronix M-210 (Note) ^社? , M-240 ^? , M-6200 ^? Etc; KAYARAD HDDA of Nihon Kayaku Co., Ltd. ^? , Dong HX-220 ^? , R-604 ^? Etc; V-260 of Osaka Yuzagaku Kogyo Co., Ltd. ^? , V-312 ^? , V-335 HP ^? And the like. The (meth) three examples of the polyfunctional ester of acrylic acid, doah Gosei are Aronix M-309 of Kagaku Kogyo (Note) ^社? , M-400 ^? , Dong M-405 ^? , Dong M-450 ^? , M-7100 ^? , M-8030 ^? , M-8060 ^? Etc; KAYARAD TMPTA of Nihon Kayaku Co., Ltd. ^? , DPCA-20 ^? , -30 ^? , Dong-60 ^? , -120 ^? Etc; V-295 from Osaka Yukigaya Kogyo Co., Ltd. ^? , -300 ^? , -360 ^? , Dong-GPT ^? , Dong-3PA ^? , -400 ^? And the like. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.

The photopolymerizable monomer may further contain a compound represented by the following general formula (9) together with the monofunctional or polyfunctional ester.

[Chemical Formula 9]

In the above formula (9)

R ¹⁰ to R ¹⁵ each independently represent the following formula (10)

[Chemical formula 10]

In Formula 10,

n is an integer of 1 or 2;

For example, n may be an integer of 2.

In general, a photosensitive resin composition for a culler filter uses dipentaerythritol hexaacrylate alone as a photopolymerizable monomer. However, such a photosensitive resin composition is coated on a substrate, exposed, developed and cured (post baking) In the case of producing a photosensitive resin film, water stains are formed on the pattern of the photosensitive resin film, and a solution to solve the water staining problem to date has not been proposed yet.

However, the photosensitive resin composition according to one embodiment can reliably solve the water stain problem by including the compound represented by the above formula (9) as a photopolymerizable monomer.

The photopolymerizable monomer may be contained in an amount of 1 wt% to 10 wt%, for example, 5 wt% to 10 wt% based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern formation step, is excellent in reliability, and is excellent in developability in an alkaline developer.

(C) Light curing Initiator

The photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

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

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, 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) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (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- -9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- -1-one, 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime- 1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butan-1-one oxime -O-acetate, and the like can be used.

For example, the photopolymerization initiator may include a oxime compound represented by the following general formula (13).

[Chemical Formula 13]

In Formula 13,

R ²² and R ²³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group.

When the photopolymerization initiator in the photosensitive resin composition according to an embodiment includes the compound represented by the above formula (13), excellent adhesion can be obtained.

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, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and the decrease of the transmittance due to the unreacted initiator can be prevented.

(D) Colorant

The photosensitive resin composition according to one embodiment includes a colorant, and the colorant may include a pigment, a dye, or a combination thereof. For example, the colorant may include a dye and a pigment represented by the following general formula (11).

(11)

In Formula 11,

Y ¹ to Y ¹² are each independently Cl or Br,

Each of R ¹⁶ to R ¹⁹ independently represents a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C6 to C20 Lt; / RTI >

At least one of R ¹⁶ to R ¹⁹ is represented by the following general formula (12)

[Chemical Formula 12]

In Formula 12,

R ²⁰ and R ²¹ are each independently a C1 to C10 alkyl group substituted or unsubstituted with a C1 to C5 alkyl group,

o and p are each independently an integer of 0 to 5, provided that 1?? o + p?? 5.

The compound represented by Formula 11 has excellent green spectral characteristics and high luminance. Furthermore, the compound represented by Formula 11 includes an aryloxy group represented by Formula 12, wherein the aryloxy group includes an alkyl group as a substituent, and the alkyl group is unsubstituted or substituted only with an alkyl group, Solubility can be obtained.

Each of R ²⁰ and R ²¹ may independently be a substituent including an isopropyl group or a t-butyl group such as a t-butyl group at the terminal. The terminal of the alkyl group, which is a substituent of the aryloxy group represented by the general formula (12), includes an isopropyl group or a t-butyl group such as a t-butyl group, thereby increasing solubility in an organic solvent and improving brightness.

Each of o and p may independently be an integer of 1. The aryloxy group represented by the general formula (12) has two alkyl groups substituted or unsubstituted with an alkyl group as a substituent, so that the aryloxy group represented by the general formula (12) can have an excellent solubility in an organic solvent as compared with the case where one is substituted.

For example, the formula (12) may be represented by the following formula (12-1).

[Formula 12-1]

In Formula 3,

R ²⁰ and R ²¹ are each independently a C1 to C10 alkyl group substituted or unsubstituted with an alkyl group.

The R ²⁰ is present at the ortho position with respect to the oxygen atom constituting the aryloxy group, and the R ²¹ may exist at the para position with respect to the oxygen atom constituting the aryloxy group. When the alkyl substituents for the oxygen atoms constituting the aryloxy group are present at the ortho and para positions, respectively, there is an advantageous effect on the solubility and the luminance.

For example, at least two or more of R ¹⁶ to R ¹⁹ , for example, at least three or more of R ¹⁶ to R ¹⁹ may be represented by the formula (12). For example, R ¹⁶ to R ¹⁹ may be represented by the general formula (12).

The greater the number of substituents represented by the above formula (12), the better the solubility of the compound according to one embodiment in the organic solvent.

The compound represented by Formula 11 may be represented by any one of the following Formulas 11-1 to 11-8.

[Formula 11-1]

[Formula 11-2]

[Formula 11-3]

[Formula 11-4]

[Formula 11-5]

[Formula 11-6]

[Formula 11-7]

[Formula 11-8]

The pigments may include organic pigments such as red pigments, green pigments, blue pigments, yellow pigments, and the like. For example, the pigment may include a green pigment, a yellow pigment, or a combination thereof.

Examples of the red pigment include C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 89 and the like.

Examples of the green pigment include C.I. Green pigment 58, C.I. Green pigment 59, C.I. Green pigment 36, C.I. Halogen-substituted copper phthalocyanine pigments such as green pigment 7 and the like.

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, and the like.

Examples of the yellow pigments include C.I. Yellow pigments 139 and the like, C.I. Quinophthalone-based pigments such as yellow pigment 138 and the like, C.I. And yellow complex pigments such as yellow pigment 150 and the like.

These pigments can be used singly or in combination of two or more thereof, but are not limited to these examples.

A dispersant may be used together with the photosensitive resin composition to disperse the pigment. Specifically, the pigment may be surface-treated beforehand with a dispersant, or a dispersant may be added together with the pigment when the photosensitive resin composition is prepared.

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-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160, DISPERBYK-130, 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 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.

The dispersant may be contained in an amount of 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is contained within the above range, the dispersibility of the photosensitive resin composition is excellent, and therefore, the stability, developability and patternability of the light-shielding layer are excellent.

The pigment may be used by pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used in the pretreatment, the primary particle size of the pigment can be reduced.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be carried out at a temperature of 40 to 100 DEG C, and the filtration and washing may be performed by washing the inorganic salt with water, etc., followed by filtration.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent acts as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed to easily pulverize the pigment. Examples of the wetting agent include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like Alkylene glycol monoalkyl ethers; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol and the like. These may be used singly or in combination of two or more thereof.

The pigment after the kneading step may have an average particle diameter of 30 nm to 100 nm. When the average particle diameter of the pigment is within the above range, it is possible to effectively form a fine pattern with excellent heat resistance and light resistance.

Specifically, the pigment may be used in the form of a pigment dispersion including the dispersant and a solvent described later, and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. The solid pigment may be included in an amount of 10% by weight to 15% by weight based on the total amount of the pigment dispersion.

The colorant may be contained in an amount of 30 wt% to 55 wt%, for example, 30 wt% to 50 wt% with respect to the total amount of the photosensitive resin composition. When the colorant is contained within the above range, the brightness, color reproducibility, pattern curability, heat resistance, and adhesion are excellent.

(E) Solvent

The solvent may be a material that has compatibility with the binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the colorant 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 methyl ether, ethylene glycol ethyl ether and propylene glycol methyl 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 methyl 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 alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol 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 an amount of 30% by weight to 60% by weight, such as 30% by weight to 50% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, a coating film excellent in coating property of the photosensitive resin composition and excellent in flatness can be obtained.

(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; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof, and the like.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly or in combination of two or more.

Examples of the fluorine-based surfactant include BM-1000 ^? , BM-1100 ^? Etc; Dai Nippon Ink Kagaku Kogyo Co., Ltd. Mecha Pack F 142D ^? F 172 ^? F 173 ^? F 183 ^? Etc; Prorad FC-135 from Sumitomo Sri M Co., Ltd. ^? , FC-170C ^? , FC-430 ^? , FC-431 ^? Etc; Sapron S-112 of Asahi Glass Co., Ltd. ^? , S-113 ^? , S-131 ^? , S-141 ^? , S-145 ^? Etc; SH-28PA of Toray Silicone Co., Ltd. ^? , -190 ^? , -193 ^? , SZ-6032 ^? , SF-8428 ^? And the like.

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

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

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

A method of manufacturing the color filter is as follows.

The above-mentioned photosensitive resin composition is coated on the glass substrate by a suitable method such as spin coating, roller coating, spray coating or the like to a thickness of 0.5 占 퐉 to 10 占 퐉, for example, to form a resin composition layer.

Then, light is irradiated to form a pattern necessary for the color filter on the substrate on which the resin composition layer is formed. As the light source used for the irradiation, UV, electron beam or X-ray can be used. For example, UV of 190 nm to 450 nm, specifically 200 nm to 400 nm, can be irradiated. A photoresist mask may be further used in the above irradiation step. After the step of irradiating in this manner, the resin composition layer irradiated with the light source is treated with a developing solution. At this time, the non-exposed portions in the resin composition layer are dissolved to form a pattern necessary for the color filter. By repeating such a process according to the number of necessary colors, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above step is heated again or cured by actinic ray irradiation or the like, crack resistance, solvent resistance and the like can be improved.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

(Preparation of acrylic binder resin)

Synthetic example  1 to Synthetic example  4

After adding 2 g of AIBN as a initiator to a 100 ml beaker, the polymerization monomers listed in Table 1 were added in the ratio shown in Table 1 so that the sum of the polymerization monomers was 40 g, and the mixture was stirred for 30 minutes. Thereafter, 70 g of PGMEA was charged into a 250 ml glass reactor equipped with a condenser, and the temperature of the system was elevated to 85 캜. The prepared monomer solution was added dropwise to the reactor for 3 hours. After further reaction at the same temperature for 6 hours, the temperature was lowered to room temperature and the reaction was terminated. The reaction was carried out under a nitrogen atmosphere.

(Unit: wt%) The monomer for polymerization Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Methacrylic acid 20 20 20 20 Isobonyl acrylate 20 - 10 30 N-Phenyl maleimide 15 - 25 5 Lauryl acrylate 45 - 45 45 Methyl Methacrylic acid - 10 - - Cyclohexyl methacrylate - 20 - - Cyclohexyl maleimide - 40 - - Tricyclodecanyl methacrylate - 10 - - Weight average molecular weight
(Mw, g / mol) 8,500 11,000 8,900 7,600 Acid value
(mgKOH / g) 110 90 120 101

(Preparation of photosensitive resin composition)

Example  1 to Example  7 and Comparative Example  1 to Comparative Example  3

The photosensitive resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 3 were prepared with the compositions shown in Table 2 below using the following components.

Specifically, the content of the photopolymerization initiator was precisely measured, the solvent was then added, and the mixture was sufficiently stirred (more than 30 minutes) until the photopolymerization initiator was sufficiently dissolved. To this, an acrylic binder resin, an epoxy binder resin and a photopolymerizable monomer were sequentially added, followed by stirring for about 1 hour. Then, a colorant was added, other additives were added, and the entire composition was finally stirred for 2 hours or more to prepare a photosensitive resin composition.

The specifications of each component used in the production of the photosensitive resin composition are as follows.

(A) Binder resin

(A-1) The acrylic binder resin of Synthesis Example 1

(A-2) The acrylic binder resin of Synthesis Example 2

(A-3) Epoxy binder resin (epoxy equivalent: 177 g / eq) (EHPE-3150, manufactured by DAICEL CHEMICAL)

(A-4) The acrylic binder resin of Synthesis Example 3

(A-5) The acrylic binder resin of Synthesis Example 4

(A-6) Acrylic binder resin (SKY-095, Samsung SDI)

(A-7) Acrylic binder resin (SKY-141, Samsung SDI)

(A-8) Acrylic binder resin (BX-04, Nippon Shokubai Co., Ltd.)

(B) Photopolymerization  Monomer

(B-1) KAYARAD DPCA-120 (Nippon Kayaku Co., Ltd.)

(B-2) DPHA (Nippon Kayakusho)

(B-3) Viscoat 1000 (OSAKA YUKI)

(C) Light curing Initiator

(C-1) oxime type initiator (NCI-930, ADEKA)

(C-2) oxime type initiator (OXE-02, BASF)

(D) Colorant

(D-1) a green dye represented by the following formula (11-1)

[Formula 11-1]

(D-2) Green pigment dispersion (G58, ENF)

(D-3) Green pigment dispersion (G59, ENF)

(D-4) Yellow pigment dispersion for coloring (SC-P541-2236 Yellow-M, TOYO)

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA)

(F) Other additives

Fluorine-based surfactant (F-554 (using 10% diluent), DIC)

(Unit: wt%) Kinds Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Binder resin A-1 4.19 4.19 4.19 4.19 - - 6.09 - - - A-2 6.09 6.09 6.09 6.09 6.09 6.09 4.19 - - - A-3 0.44 0.44 0.44 0.44 0.44 0.44 0.44 - - - A-4 - - - - 4.19 - - - - A-5 - - - - 4.19 - - - - A-6 - - - - - - - 10.70 - - A-7 - - - - - - - - 10.70 - A-8 - - - - - - - - - 10.70 (B) a photopolymerizable monomer B-1 - 1.30 - 1.30 - - - - - - B-2 6.10 4.80 6.10 4.80 6.10 6.10 6.10 6.10 6.10 6.10 B-3 0.42 0.42 0.42 0.42 0.42 0.42 0.42 0.42 0.42 0.42 (C) a photopolymerization initiator C-1 - - 0.17 0.17 - - - - - - C-2 0.33 0.33 0.16 0.16 0.33 0.33 0.33 0.33 0.33 0.33 (D) Colorant D-1 11.38 11.38 11.38 11.38 11.38 11.38 11.38 11.38 11.38 11.38 D-2 13.16 13.16 13.16 13.16 13.16 13.16 13.16 13.16 13.16 13.16 D-3 8.81 8.81 8.81 8.81 8.81 8.81 8.81 8.81 8.81 8.81 D-4 13.05 13.05 13.05 13.05 13.05 13.05 13.05 13.05 13.05 13.05 (E) Solvent 36.01 36.01 36.01 36.01 36.01 36.01 36.01 36.03 36.03 36.03 (F) Other additives 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Total 100 100 100 100 100 100 100 100 100 100

Rating 1: Color characteristics  evaluation

Coating was carried out at rpm at which a predetermined thickness could be exhibited for each of the photosensitive resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 using a coating machine (Mikasa, Opticoat MS-A150) Pre-baking was carried out on a hot-plate. Thereafter, the entire surface was exposed using an exposure machine (Ushio, HB-50110AA) under an exposure condition of 50 mj / cm ² , and baking was performed at 230 캜 for 20 minutes in an oven condition to complete the preparation of the test piece. The color characteristics (chromaticity coordinates, luminance (Y), and contrast ratio (CR)) were measured using an MCPD 3000 apparatus before and after the oven baking, and the results are shown in Table 3 below.

Gx Gy Luminance (Y) Contrast Ratio (CR) Example 1 0.2840 0.649 55.70 12415 Example 2 0.2840 0.649 55.73 12225 Example 3 0.2841 0.649 55.72 12315 Example 4 0.2841 0.649 55.78 12921 Example 5 0.2840 0.649 55.55 12185 Example 6 0.2841 0.649 55.60 12235 Example 7 0.2841 0.649 55.61 12312 Comparative Example 1 0.2841 0.649 55.33 12133 Comparative Example 2 0.2841 0.649 55.42 12284 Comparative Example 3 0.2838 0.649 55.42 12484

Evaluation 2: Pattern wrinkles, water stains, adhesion, Taper  evaluation

Coating was carried out at rpm which can exhibit a certain thickness for each of the photosensitive resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 by using a coating machine (Mikasa, Opticoat MS-A150) (15 DEG C to 25 DEG C) for 30 minutes. Subsequently, pattern exposure was carried out using a pattern mask under an exposure condition of 50 mj / cm ^{2 using} an exposure machine (Ushio, HB-50110AA), and development was carried out with Na ₂ CO ₃ diluted (X20) developer at a pressure of 1.5 kgf, And the wrinkles, water stains, adhesion, and taper of the pattern were observed by an optical microscope through an optical microscope. The results are shown in Table 4 and Figs. 1 to 21.

Pattern Wrinkle Evaluation Criteria

○: Pattern wrinkles were not observed

x: pattern wrinkles observed

Pattern Water Stain Evaluation Criteria

○: No pattern water stain observed

△: pattern water stain slightly observed

x: pattern water stain is observed very much

Pattern wrinkles Pattern water stain Adhesion (㎛) Taper angle (°) Example 1 ○ △ 14 54.14 Example 2 ○ ○ 14 50.25 Example 3 ○ △ 12 61.53 Example 4 ○ ○ 12 48.10 Example 5 △ △ 15 55.44 Example 6 △ △ 15 54.35 Example 7 ○ △ 16 58.12 Comparative Example 1 x x 18 - Comparative Example 2 x x 18 - Comparative Example 3 x x 18 -

As shown in Tables 3, 4 and 1 to 21, in the case of the photosensitive resin compositions of Examples 1 to 7, as compared with the photosensitive resin compositions of Comparative Examples 1 to 3, But it is also excellent in developability, adhesion, pattern characteristics, and taper characteristics. Particularly, when the content of the repeating unit represented by the general formula (2) is in the range of 15 wt% to 25 wt% with respect to the total amount of the first acrylic binder resin, it is confirmed that the brightness and adhesion are more excellent and the pattern wrinkle is more effective have.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (19)

(A1) a first acrylic binder resin comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (4)
(A2) a polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (5), a repeating unit represented by the following formula (6), a repeating unit represented by the following formula A second acrylic binder resin;
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) a colorant; And
(E) Solvent
: ≪ EMI ID =
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 1 to 8,
R ¹ is a substituted or unsubstituted C 1 to C 10 alkyl group
R ² to R ⁵ and R ⁷ to R ⁹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R ⁶ is a substituted or unsubstituted C 11 to C 20 alkyl group.
The method according to claim 1,
Based on the total amount of the first acrylic binder resin,
The repeating unit represented by Formula 1 is contained in an amount of 15 to 25% by weight,
The repeating unit represented by Formula 2 is contained in an amount of 15 wt% to 25 wt%
The repeating unit represented by the above formula (3) is contained in an amount of 10 to 20% by weight,
The repeating unit represented by the general formula (4) is contained in an amount of 40% by weight to 50% by weight
.
The method according to claim 1,
Based on the total amount of the second acrylic binder resin,
The repeating unit represented by Formula 1 is contained in an amount of 15 to 25% by weight,
The repeating unit represented by the formula (5) is contained in an amount of 5 to 15% by weight,
The repeating unit represented by Formula 6 is contained in an amount of 15 to 25% by weight,
The repeating unit represented by the formula (7) is contained in an amount of 35 to 45% by weight,
The repeating unit represented by the formula (8) is contained in an amount of 5 wt% to 15 wt%
.
The method according to claim 1,
Wherein the first acrylic binder resin has a weight average molecular weight of 2,000 g / mol to 9,000 g / mol.
The method according to claim 1,
Wherein the first acrylic binder resin has an acid value of 100 mgKOH / g to 120 mgKOH / g.
The method according to claim 1,
And the second acrylic binder resin has a weight average molecular weight of 10,000 g / mol to 17,000 g / mol.
The method according to claim 1,
And the second acrylic binder resin has an acid value of 80 mgKOH / g to 99 mgKOH / g.
The method according to claim 1,
Wherein the first acrylic binder resin is contained in an amount less than that of the second acrylic binder resin.
The method according to claim 1,
Wherein the photosensitive resin composition further comprises (A3) an epoxy binder resin.
The method according to claim 1,
Wherein the photopolymerizable monomer comprises a compound represented by the following general formula (9): < EMI ID =
[Chemical Formula 9]

In the above formula (9)
R ¹⁰ to R ¹⁵ each independently represent the following formula (10)
[Chemical formula 10]

In Formula 10,
n is an integer of 1 or 2;
11. The method of claim 10,
Wherein n is an integer of 2.
The method according to claim 1,
Wherein the colorant comprises a dye represented by the following formula (11) and a pigment:
(11)

In Formula 11,
Y ¹ to Y ¹² are each independently Cl or Br,
Each of R ¹⁶ to R ¹⁹ independently represents a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C6 to C20 Lt; / RTI >
At least one of R ¹⁶ to R ¹⁹ is represented by the following general formula (12)
[Chemical Formula 12]

In Formula 12,
R ²⁰ and R ²¹ are each independently a C1 to C10 alkyl group substituted or unsubstituted with a C1 to C5 alkyl group,
o and p are each independently an integer of 0 to 5, provided that 1?? o + p?? 5.
13. The method of claim 12,
Wherein the dye represented by Formula 11 is represented by any one of the following Formulas 11-1 to 11-8.
[Formula 11-1]

[Formula 11-2]

[Formula 11-3]

[Formula 11-4]

[Formula 11-5]

[Formula 11-6]

[Formula 11-7]

[Formula 11-8]

13. The method of claim 12,
Wherein the pigment comprises a green pigment and a yellow pigment.
The method according to claim 1,
Wherein the photopolymerization initiator comprises a compound represented by the following formula (13): < EMI ID =
[Chemical Formula 13]

In Formula 13,
R ²² and R ²³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ is a substituted or unsubstituted C1 to C10 alkylene group.
The method according to claim 1,
The photosensitive resin composition
1 to 10% by weight of the above-mentioned (A1) acrylic binder resin;
5 to 15% by weight of the acrylic binder resin (A2);
1 to 10% by weight of the photopolymerizable monomer (B);
0.1 to 5% by weight of the photopolymerization initiator (C);
30% to 55% by weight of (D) the colorant; And
The amount of the solvent (E)
.
The method according to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof. ≪ / RTI >
A photosensitive resin film produced by using the photosensitive resin composition of any one of claims 1 to 17.
A color filter comprising the photosensitive resin film of claim 18.

Images