KR101995097B1 - Colored photosensitive resin composition, color filter and image display device using the same - Google Patents

Abstract

The present invention includes a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E); The colorant (A) is a colorant. Pigment Green 59, and at least one selected from pigments and dyes, a color filter manufactured using the colored photosensitive resin composition, and an image display device including the color filter.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter formed using the same, and an image display device. [0002]

The present invention relates to a colored photosensitive resin composition, a colored pattern formed of the resin composition, a color filter including the colored pattern, and an image display device having the same.

BACKGROUND ART [0002] Color filters are widely used in various display devices such as an image pickup device and a liquid crystal display (LCD), and their application range is rapidly expanding. The color filter used in the image pickup device or the liquid crystal display device may be a color pattern of three colors of red, green and blue or a color pattern of three colors of yellow, magenta and cyan Cyan).

The coloring pattern of each of the color filters is generally formed using a colored photosensitive resin composition comprising a colorant such as pigment or dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is usually performed by a lithography process.

2. Description of the Related Art In recent years, various display devices including a solid-state image sensor such as a digital camera and a color filter for a liquid crystal display (LCD) have been required to have high brightness and high coloring property in order to improve the processability and quality.

Korean Patent Laid-Open Publication No. 2013-0134494 discloses that C.I. Pigment Green 7 and C.I. Discloses a resin composition using Pigment Yellow 185, but has a problem that it can not simultaneously satisfy high brightness and high coloring property.

Korea Patent Publication No. 2013-0134494

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art,

It is an object of the present invention to provide a colored photosensitive resin composition which is excellent in luminance, coloring property and adhesion property, and can form a pixel having a high light transmittance and a high contrast ratio.

It is another object of the present invention to provide a color filter including the colored photosensitive resin composition and an image display device including the color filter.

According to the present invention,

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E);

The colorant (A) is a colorant. Pigment Green 59, and at least one selected from pigments and dyestuffs.

In addition,

And a pattern formed of the colored photosensitive resin composition.

In addition,

And an image display device including the color filter.

The colored photosensitive resin composition of the present invention has characteristics of high brightness, high color intensity and high sensitivity, and can have excellent heat resistance and developability.

In addition, a pixel having excellent light transmittance and contrast ratio can be formed, reliability can be improved by increasing the degree of curing, and an effect of reducing reverse taper can be provided.

Further, it is possible to provide a color filter and an image display device manufactured using the colored photosensitive resin composition.

1 is a graph showing a transmission spectrum when a colorant containing each pigment is used.

According to the present invention,

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E);

The colorant (A) comprises a compound represented by the following formula (1), and at least one selected from a pigment and a dye.

[Chemical Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br, or H, 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br.

Each component constituting the colored photosensitive resin composition of the present invention will be described below. However, the present invention is not limited to these components.

(A) Colorant

The colorant (A) according to the present invention is a component capable of expressing hues such as red, green or blue so as to produce a pattern having a desired hue.

The pigment (a1)

The colorant (A) contained in the colored photosensitive resin composition of the present invention is characterized by containing a compound represented by the following general formula (1) as the pigment (a1). The compound represented by the following formula (1) has a structure of ZnPc (Zinc Phthalocyanine). When the colorant (A) of the present invention comprises a compound represented by the following formula (1) There are advantages of high color reproduction.

[Chemical Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br, or H, 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br.

Preferable examples of the compound represented by the above formula (1) include C.I. Pigment Green 59 (hereinafter also referred to as " G59 "). In this case, the effect of the present invention is advantageously maximized.

C.I. Pigment Green 58 (G58) has an advantage of high brightness, but in order to realize high coloring property, the pigment content is increased. When the pigment is contained in a large amount in the composition, the development is poor and the pattern formed by the composition And sensitivity may be lowered.

However, by using the pigment represented by the above formula (1), particularly G59 as a coloring agent, the present invention can design a resist of high color reproduction even if the content of pigment is small.

On the other hand, C.I. When Pigment Green 7 (G7) is included in the resin composition, it can exhibit high coloring property even if the pigment content is reduced, which is advantageous for use, but has a problem of low luminance. However, the compound of the formula (1), particularly G59, contained in the colored photosensitive resin composition of the present invention is not limited to C.I. Exhibits a transmission spectrum and color coordinates similar to those of Pigment Green 7, but also functions to exhibit excellent luminance included in the colored photosensitive resin composition. As can be seen in Fig. 1, C.I. Pigment Green 59 is C.I. Similar to Pigment Green 7, it has a transmission spectrum at a wavelength of 400 nm to 610 nm.

In the present specification, Tmax means the wavelength at which the transmittance of the pigment is maximum, and T50 _% means the wavelength at which the pigment transmittance is 50% or more of the maximum value.

In one embodiment of the present invention, the C.I. The Tmax of Pigment Green 59 may be 500 to 530 nm, and in this case, it is preferable from the standpoint of excellent coloring property.

Further, in another embodiment of the present invention, the T _50% of the CI Pigment Green 59 may be 445 to 580 nm, and in this case, it is preferable in terms of excellent coloring property.

The compound of Formula 1 is preferably contained in an amount of 0.05 to 50% by weight, more preferably 0.1 to 25% by weight, and more preferably 0.5 to 20% by weight based on the total weight of the colored photosensitive resin composition of the present invention. Is more preferable. When the compound of formula (1) is contained within the range of 0.05 to 50% by weight based on the above standard, it is preferable because it has high light transmittance and high contrast ratio and is excellent in developability.

The colorant (A) according to the present invention is a component capable of expressing hues such as red, green or blue in addition to the compound represented by the above formula (1) so that a pattern having a desired hue can be produced. Characterized in that it comprises at least one selected from pigments and dyes, and can be produced in the form of a mill base.

In the composition of the present invention, the compound represented by Formula 1 and at least one selected from pigments and dyes are preferably used in a ratio of 1: 0.050 to 1: 18.0, more preferably 1: 0.1 to 1: 9, By weight in a weight ratio of 1: 0.2 to 1: 4. If it is contained in the above-mentioned weight ratio, it is advantageous because it has advantages of high coloring property and high brightness, and has an advantage of improving process margin and sensitivity.

In this case, the colorant containing the compound of Formula 1 according to the present invention as a pigment may have a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more in the XYZ color system.

On the other hand, when G58 is used as an example, x = about 0.2 to 0.35 color coordinates can be obtained when y = 0.6 or more in the XYZ color system. At this time, in order to have a value near x = 0.1 by using G58, it is necessary to perform color matching with blue. In this case, there is a problem of a decrease in luminance, which is not preferable.

As another example, in the case of using G7, there is a problem that the area where color can be emitted is wide, but the luminance is low.

The pigment (a1) includes an organic pigment and an inorganic pigment, and they may be used alone or in combination of two or more. The use of an organic pigment may be more preferable in view of excellent heat resistance and color development. The organic pigment may be a synthetic pigment or a natural pigment.

The organic pigment may optionally be rosin treated; Surface treatment using a pigment derivative in which an acidic group or a basic group is introduced; Graft treatment on the surface of a pigment using a polymer compound or the like; Microparticulation treatment by sulfuric acid microparticle formation method or the like; Or cleaning treatment with an organic solvent or water to remove impurities; .

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts, and inorganic salts of barium sulfate (extender pigments). More specifically, the metal compounds include iron, cobalt, aluminum, cadmium, lead, , Oxides or complex metal oxides of metals such as magnesium, chromium, zinc, antimony and carbon black.

More specific examples of the pigment (a1) include compounds classified as pigments in the Color Index (The Society of Dyers and Colourists), and more specifically, the following color indexes CI). However, the present invention is not limited thereto, and at least one selected from the pigments may be covalently dispersed using a binder resin, a dispersant, or the like to suit the desired chromaticity.

C.I. Specific examples of pigment yellow include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214;

C.I. Specific examples of pigment oranges include C.I. Pigment Orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

C.I. Specific examples of Pigment Red include C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264 and 265 Have;

C.I. Specific examples of the pigment blue include C.I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 22, 28 and 60;

C.I. Specific examples of pigment violet include C.I. Pigment Violet 14, 19, 23, 29, 32 and 177, and the like,

C.I. Specific examples of pigment greens include C.I. Pigment Green 7, 36 and 58, and the like.

Among the pigments exemplified above, C.I. Pigment Yellow 138, C.I. Pigment Yellow 129, C.I. Pigment Yellow 150 and C.I. And Pigment Yellow 185 may be more preferable.

The dye (a2)

The dye (a2) which may be contained in the colorant (A) of the present invention can be used without limitation as long as it has solubility in an organic solvent or can be dispersed. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance. In the case of a dye having no solubility in an organic solvent, it may be dispersed and used.

As the dye (a2), at least one selected from an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide form of an acidic dye or the like and derivatives thereof may be used. In addition, azo dyes, xanthan dyes, phthalocyanine acid dyes and derivatives thereof may be selected.

As the dye (a2), a compound classified as a dye in the color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn) can be mentioned.

Specific examples of the dye (a2)

C.I. Solvent Yellow (Solvent Yellow) No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent Yellow No. 135;

C.I. Solvent Orange (Solvent Orange) No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent Orange No. 63;

C.I. Solvent Red (Solvent Red) No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red 91: 1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent Red No. 197;

C.I. Solvent Violet (Solvent Purple) No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No. 28, C.I. Solvent Purple No. 31, C.I. Solvent Purple No. 59;

C.I. Solvent Blue (Solvent Blue) No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent Blue No. 70;

C.I. Solvent Green (Solvent Green) No. 3, C.I. Solvent Green No. 5, C.I. Solvent Green No. 7, and the like.

The colorant (A) may be contained in an amount of preferably 5 to 85% by weight, more preferably 10 to 50% by weight based on the solid content in the colored photosensitive resin composition. When the content of the colorant (A) is less than 5% by weight, the color-separating ability of the formed pattern may be deteriorated. When the content of the colorant (A) exceeds 85% by weight, lithography performance may be deteriorated,

The solid content in the colored photosensitive resin composition in the present invention means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.

(B) binder resin

The binder resin (B) contained in the colored photosensitive resin composition of the present invention is a component that imparts solubility to the alkali developing solution used in the developing process. It is also a component soluble in a developing solution (particularly preferably an alkali developing solution) used in a developing treatment step when forming a colored layer, acting as a binder with respect to the pigment.

In the present invention, the binder resin (B) preferably contains at least one selected from the following copolymer (B1), polymer (B2) and copolymer (B3).

The copolymer (B1) is a copolymer of (meth) acrylic acid (b1); N-substituted maleimide (b2); (Meth) acrylates such as styrene,? -Methylstyrene, p-hydroxy-? -Methylstyrene, methyl (meth) acrylate, n-butyl (Meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, mono [2- (meth) acryloyloxyethyl], omega-carboxypolycaprolactone mono At least one unsaturated compound (b3) (hereinafter also referred to as "unsaturated compound (b3)" or "(b3)") selected from the group consisting of methacrylate, methacrylate, polystyrene macromonomer and polymethylmethacrylate macromonomer; (Hereinafter also referred to as "copolymer (B1)").

The polystyrene macromonomer, polymethylmethacrylate macromonomer, may be a monomer which is a polymer of polystyrene or polymethylmethacrylate, respectively.

Examples of the N-substituted maleimide (b2) include N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N- , N-cyclohexylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, Imidyl-3-maleimide propionate, N- (acridinyl) maleimide, and the like.

Among these N-substituted maleimides, N-phenylmaleimide and N-cyclohexylmaleimide are preferable, and N-phenylmaleimide and N-benzylmaleimide are more preferable. The N-substituted maleimide may be used alone or in combination of two or more.

Examples of the unsaturated compound (b3) include styrene, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, glycerol mono (meth) acrylate, mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate. More preferably, 2-ethylhexyl (meth) acrylate and / or omega-carboxypolycaprolactone mono (meth) acrylate can be selected and used.

In the present invention, the binder resin (B) may further contain, in addition to the above-mentioned (meth) acrylic acid (b1), the N-substituted maleimide (b2) and the unsaturated compound (b3), another unsaturated monomer (b4) ≪ / RTI >

Herein, the unsaturated monomer (b4) does not include the components (b1), (b2) and (b3).

As specific preferred examples of the copolymer (B1) thus obtained,

(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / Nm-hydroxyphenylmaleimide / styrene / benzyl (Meth) acrylic acid / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / N- (Meth) acrylic acid / N-phenylmaleimide / styrene / n-butyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenyl (Meth) acrylic acid / N-phenylmaleimide / p-hydroxy- alpha -methylstyrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / Acrylic acid / N-phenylmaleimide / styrene / n-butyl (meth) acrylate copolymer, (Meth) acrylic acid / N-phenylmaleimide / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide / styrene / (Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / Np-hydroxyphenylmaleimide (Meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono / Polystyrene macromonomer copolymer, (meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, ) Acrylic acid / N-phenylmaleimide / styrene (Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / n-butyl (meth) acrylate / (meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / 2-ethylhexyl (meth) acrylate / glycerol mono (Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / 2-ethylhexyl (meth) acrylate / glycerol mono (meth) acrylate copolymer Styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / (Meth) acryloyloxyethyl] / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate Styrene / allyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2 (meth) acryloyloxyethyl] / N-phenylmaleimide / (Meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer, mono [2- (meth) acryloyloxyethyl] / N (Meth) acrylate / mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / n-butyl (meta) acrylate copolymer (Meth) acrylic acid / mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl Acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / mono [2- (meth) acryloyloxyethyl] (Meth) acrylate / mono [2- (meth) acryloyloxyethyl] / N (meth) acrylate / styrene / 2-ethylhexyl (Meth) acrylate / ω-carboxypolycaprolactone mono (meth) acrylate / Nm-hydroxyphenyl (meth) acrylate / styrene / 2-ethylhexyl (Meth) acrylic acid /? -Carboxypolycaprolactone mono (meth) acrylate / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer, (Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, - carboxypolycaprolactone mono (meth) (Meth) acrylate / ω-carboxypolycaprolactone mono (meth) acrylate / N-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (Meth) acrylic acid /? -Carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / n-butyl (Meth) acrylic acid /? - carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / 2-methylstyrene / n-butyl (meth) acrylate / glycerol mono (Meth) acrylate / N-phenylmaleimide / styrene / 2-hydroxyethyl (meth) acrylate copolymer, Ethylhexyl (meth) acrylate / glycerol No (meth) acrylate and the like, but a copolymer, is not limited to this.

That is, the copolymer contained in the binder resin (B) can be prepared by copolymerizing (meth) acrylic acid (b1), N-substituted maleimide (b2) and unsaturated compound (b3) (b4) may be further copolymerized.

At this time, the proportion of the constituent components derived from the above-mentioned (b1), (b2), (b3) and (b4) is preferably within the following range with respect to the total weight of the copolymer component.

(b1): 5 to 40% by weight, more preferably 10 to 30% by weight;

(b2): 5 to 40% by weight, more preferably 10 to 30% by weight;

(b3): 30 to 80% by weight, more preferably 30 to 75% by weight;

(b4): 0 to 30% by weight, more preferably 0 to 20% by weight.

In the present invention, when the composition ratio of the binder resin is within the above range, a colored photosensitive resin composition exhibiting high light transmittance and contrast ratio and exhibiting excellent developability can be obtained.

The polymer (B2) is at least one repeating unit selected from the following formulas (2) and (3).

(2)

In Formula 2, R ₁ , R ₂ , R ₃ , and R ₄ are each independently an organic residue having 1 to 20 carbon atoms which may contain a hydrogen atom, a halogen atom, or an oxygen atom.

(3)

In Formula 3, R ₅ , R ₆ , R ₇ , and R ₈ are each independently an organic residue having 1 to 20 carbon atoms which may contain a hydrogen atom, a halogen atom, or an oxygen atom.

In the description of the above formulas 2 and 3, the organic residue may be an aromatic organic residue, an aliphatic organic residue, an alicyclic organic residue, a heterocyclic organic residue or an aliphatic organic residue having an aromatic ring in the chain, an alicyclic organic residue or a heterocycle May be an organic residue.

The amount of the polymer (B2) is preferably 1 to 99% by weight, more preferably 1 to 50% by weight, and still more preferably 1 to 30% by weight based on the total weight of the binder resin (B) . Within the above-mentioned range, the degree of curing can be improved, and even a composition having a high pigment content is preferable because the pattern upon development is accurately formed.

The present invention may further include a copolymer of a carboxyl group-containing monomer and another monomer capable of copolymerizing with the monomer, in addition to the repeating unit of the above formula (2) or (3).

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated tricarboxylic acid and the like .

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. have.

The carboxyl group-containing monomers may be used alone or in combination of two or more.

The copolymer (B3) is obtained by copolymerizing an aromatic vinyl compound (B'1), a compound (B'2) having an unsaturated bond and an epoxy group in one molecule, and a compound (B'3) do.

More specifically, the copolymer (B3) is obtained by copolymerizing an aromatic vinyl compound (B'1) and a compound (B'2) having an unsaturated bond and an epoxy group in one molecule, with a compound (B ' 3). ≪ / RTI >

[Chemical Formula 4]

In Formula 4,

R ₁ and R ₂ are each independently a C1 to C6 alkyl group which is unsubstituted or substituted with at least one member selected from a halogen, a ketone group, an ester group and a thiol group,

A is an aliphatic polycyclic group substituted or unsubstituted with at least one member selected from the group consisting of a halogen atom, a methoxy group and an ethoxy group; Allyl group; halogen; Methoxy group; Ethoxy group; And C1 to C8 alkoxy groups; Or an unsubstituted or substituted aromatic polycyclic group;

n and m are 0 or 1, respectively.

Specific examples of the aromatic vinyl compound (B'1, hereinafter also simply referred to as 'B'1') include vinyl toluene, styrene, a-methylstyrene, a-chlorostyrene, vinylpyrrolidone, But they are not limited thereto, and they may be used alone or in combination of two or more. It is more preferable to use vinyl toluene as the aromatic vinyl compound (B'1), considering ease of manufacture and reliability. Particularly, the colored photosensitive resin composition containing the binder resin (B) prepared by containing vinyl toluene as the aromatic vinyl compound has an advantage of being excellent in the effect of reducing outgas generation and the like.

Specific examples of the compound (B'2, hereinafter also simply referred to as 'B'2') having an unsaturated bond and an epoxy group in one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and methylglycidyl (meth) acrylate, but are not limited thereto, and they may be used alone or in combination of two or more . In particular, glycidyl (meth) acrylate is excellent in ease of manufacture and reliability and can be more preferably used.

In the present invention, (meth) acrylate means acrylate and / or methacrylate.

The compound (B'3, hereinafter, also simply referred to as 'B'3') of the above formula (4) is not particularly limited, but preferably at least one compound selected from compounds represented by the following formulas It is good to do.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

According to the present invention, the binder resin (B) has a weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") in terms of polystyrene measured by gel permeation chromatography (GPC, tetrahydrofuran as an elution solvent) To 100,000, and more preferably from 3,000 to 50,000. When the weight average molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the storage stability is excellent, the solubility of the non-exposed portion in the developer is excellent and the resolution tends to be improved.

The weight average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) relative to the number average molecular weight of the binder resin (B) is preferably 1.5 to 6.0, 4.0 is preferable in terms of developability and storage stability.

The acid value of the binder resin (B) is preferably 30 to 170 mgKOH / g, more preferably 50 to 150 mgKOH / g, based on solids. When the acid value of the binder resin (B) is less than 30 mgKOH / g, it is difficult to secure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 170 mgKOH / g, the adhesion with the substrate is decreased, And there is a problem in compatibility with the coloring agent, so that the coloring agent in the colored photosensitive resin composition is precipitated, or the storage stability of the colored photosensitive resin composition is lowered and the viscosity is increased, which is not preferable.

The binder resin (B) is preferably contained in an amount of 1 to 85% by weight, more preferably 10 to 70% by weight, based on the solid content in the colored photosensitive resin composition of the present invention. When the content of the binder resin (B) is 1 to 85% by weight on the basis of the above-mentioned criteria, solubility in a developing solution is sufficient and development residue is hardly generated on the substrate of the non-pixel portion, It is preferable to prevent the reduction of the non-pixel portion because the non-pixel portion tends to have a good dropout.

(C) Photopolymerization  compound

The photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention is a compound which can be polymerized by an active radical or an acid generated from a photopolymerization initiator (D) described below by light irradiation, Is not particularly limited. Preferably, monofunctional monomers, bifunctional monomers or trifunctional or more polyfunctional monomers can be used, and at least one monomer selected therefrom can be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- Examples of commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), and Viscot 158 (Osaka Yuki Kagaku Kogyo). It is not.

Specific examples of the bifunctional monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (Acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, propylene glycol dimethacrylate, urethane (meth) acrylate, AH-600, AT-1, and K-KAARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo Co., Ltd.) 600 or UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.), but the present invention is not limited thereto.

Specific examples of the trifunctional or higher functional polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, penta (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta (meth) acrylate, ethoxylated (Meth) acrylate such as dipropylene glycol dimethacrylate, dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products include Aronix M-309 , TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku), but the present invention is not limited thereto .

Among the photopolymerizable compounds exemplified above, it is more preferable to use a multifunctional monomer having three or more functional groups. Since the (meth) acrylates and the urethane (meth) acrylates have excellent polymerizability and can improve the strength, desirable.

The photopolymerizable compound (C) is contained in an amount of preferably 1 to 50% by weight, more preferably 10 to 35% by weight based on the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound (C) is in the range of 1 to 50% by weight based on the above-mentioned criteria, the strength and smoothness of the pixel portion are preferably improved.

(D) Light curing Initiator

The photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention initiates the polymerization of the photopolymerizable compound (C) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X- Radicals and the like.

The photopolymerization initiator is not particularly limited as long as it does not impair the object of the present invention and is usually used in the art and is capable of polymerizing the binder resin and the photopolymerizable compound. Typical examples include oxime compounds, acetophenone compounds, benzoin compounds, benzophenone compounds, nonimidazole compounds, triazine compounds, thioxanthone compounds, and anthracene compounds. And it is possible to select at least one of them. Among them, when the polymerization characteristics, the initiation efficiency and the absorption wavelength are considered, it is more preferable to use an oxime compound.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, (Z) -2- (benzoyloxy) (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) 1 - ((1- (6- (4 - ((2,2-dimethyl-1,3-dioxolane- Methoxy) -2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl) ethylidene) amino) oxy) ethanone OXE-01 " and " OXE-02 " from BASF.

[Chemical formula 10]

(11)

[Chemical Formula 12]

The content of the photopolymerization initiator (D) is not particularly limited, but is preferably from 0.1 to 40% by weight, and more preferably from 1 to 30% by weight based on the total weight of the solid components in the colored photosensitive resin composition. When the content of the photopolymerization initiator is within the above-mentioned range, the colored photosensitive resin composition is highly sensitized and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. It is also preferable that the strength of the pixel portion formed using the colored photosensitive resin composition of the present invention and the smoothness on the surface of the pixel portion can be improved.

Meanwhile, according to one embodiment of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiator (d1) to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary agent, whereby the sensitivity can be further increased and the productivity can be improved.

As the photopolymerization initiation assistant (d1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, an organic sulfur compound having a thiol group, and an alkoxyanthracene compound is preferably used, but not limited thereto .

(E) Solvent

The solvent (E) according to the present invention is not particularly limited so long as it is effective in dissolving the other components contained in the colored photosensitive resin composition. Specific examples of the solvent include, but are not limited to, ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

Specific examples of the ether solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; And the like.

Examples of the acetate solvents include alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate ;

Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; And the like.

Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Specific examples of the ketone solvent include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Specific examples of the alcohol solvents include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Specific examples of the ester solvents include cyclic esters such as? -Butyrolactone;

Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and the like.

Specific examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

The solvent (E) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coatability and dryness, more preferably alkylene glycol alkyl ether acetates; Ketones; Ethoxypropionate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionic acid Ethyl, 3-methoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The amount of the solvent (E) contained in the colored photosensitive resin composition of the present invention is preferably 30 to 95% by weight, more preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition of the present invention, ≪ / RTI > When the solvent (E) is contained in the above-mentioned range, when the solvent (E) is coated by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater Effect can be provided.

(F) Additive

The colored photosensitive resin composition of the present invention may contain other additives such as fillers, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, anti-aggregation agents, pigment dispersants, And an additive (F) such as an ultraviolet absorber.

The surfactant may be used to further improve the film-forming property of the photosensitive resin composition. As specific examples of the surfactant, a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4400, TSF- TSF-4460, and TSF-4452.

The above-exemplified surfactants may be used alone or in combination of two or more.

The pigment dispersant is a component that can be added for deaggregation and stability of the pigment (a1). As an example of a method for uniformly dispersing the particle diameter of the pigment (a1), there is a method of adding a pigment dispersant to disperse the pigment dispersion. Thus, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

The pigment dispersant may be any of those generally used in the art.

The process for producing the colored photosensitive resin composition of the present invention will be described as follows.

First, the pigment (a1) in the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant, the binder resin (B), or the dye (a2) may be mixed with the solvent (E) to dissolve or disperse it.

The dye (a2), the remainder of the binder resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D) and, if necessary, the additive (F) and the solvent (E) To prepare a colored photosensitive resin composition according to the present invention.

Further, the present invention includes a coloring pattern made of the colored photosensitive resin composition. The coloring pattern can be produced by applying the colored photosensitive resin composition of the present invention on a substrate, and photo-curing and developing. The thickness of the coloring pattern is not particularly limited, and may be, for example, 1 to 6 탆.

<Color filter>

The present invention also provides a color filter comprising a coloring pattern made of the colored photosensitive resin composition. The color filter of the present invention comprises a substrate and a coloring pattern made of the colored photosensitive resin composition of the present invention on the substrate. The substrate may be made of a transparent material having sufficient strength and supporting force for the stability of the color filter. Preferably, a glass having excellent chemical stability and high strength can be used.

The color filter may be manufactured by a conventional method well known in the art.

<Image Display Device>

The present invention also provides an image display device including the color filter. Specific examples of the image display device include a liquid crystal display (LCD), an organic EL display (organic EL display), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, A display device such as a display device for car navigation, and the like, and a color display device is particularly suitable.

The image display device includes a configuration known to those skilled in the art, except that the color filter is provided. That is, the present invention includes an image display device to which the color filter of the present invention can be applied .

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it should be understood that the following examples are illustrative of the present invention, and the present invention is not limited by the following examples, and various modifications and changes may be made without departing from the scope of the present invention. The scope of the present invention will be determined by the technical idea of the following claims.

In the following Production Examples, Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

< Synthetic example >

< Synthetic example  1 to 6>

150 parts by weight of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen introducing tube, the atmosphere in the flask was changed to nitrogen in air, and the temperature was raised to 100 占 폚. Thereafter, binder resins were synthesized according to the following Synthesis Examples 1 to 6, respectively.

Synthetic example  One. Binder resin  B-1

15 parts by weight of methacrylic acid, 25 parts by weight of N-phenylmaleimide, 35 parts by weight of benzylmethacrylate, 10 parts by weight of glycerol monomethacrylate, 15 parts by weight of styrene, 2.5 parts by weight of? -Methylstyrene dimer (chain transfer agent) , A solution prepared by adding 1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping funnel Stirring was continued at 100 &lt; 0 &gt; C for additional 5 hours.

To obtain a resin solution (solid concentration = 30 wt%) B-1 having a solid acid value of 97 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 24,000 and the molecular weight distribution (Mw / Mn) was 2.3.

Synthetic example  2. Binder resin  B-2

15 parts by weight of methacrylic acid, 25 parts by weight of N-benzylmaleimide, 35 parts by weight of benzylmethacrylate, 10 parts by weight of glycerol monomethacrylate, 15 parts by weight of styrene, 2.5 parts by weight of? -Methylstyrene dimer (chain transfer agent) , A solution prepared by adding 1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping funnel Stirring was continued at 100 &lt; 0 &gt; C for additional 5 hours.

A resin solution (solid concentration = 30 wt%) B-2 having a solid acid value of 95 mgKOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 25,000 and the molecular weight distribution (Mw / Mn) was 2.2.

Synthetic example  3. Binder resin  B-3

15 parts by weight of methacrylic acid, 10 parts by weight of? -Carboxylic dicaprolactone monoacrylate, 25 parts by weight of N-phenylmaleimide, 35 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 15 parts by weight of styrene , 2.5 parts by weight of? -methylstyrene dimer (chain transfer agent) were added, and then 1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 50 parts by weight of propylene glycol monomethyl ether acetate The solution was dropped from the dropping funnel into the flask over 2 hours, and stirring was further continued at 100 캜 for 5 hours.

To obtain a resin solution (solid concentration = 30 wt%) B-3 having a solid acid value of 100 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 22,000 and the molecular weight distribution (Mw / Mn) was 2.2.

Synthetic example  4. Binder resin  B-4

15 parts by weight of methacrylic acid, 10 parts by weight of mono (2-methacryloyloxyethyl) succinate, 25 parts by weight of N-phenylmaleimide, 25 parts by weight of benzyl methacrylate, 25 parts by weight of styrene, (Chain transfer agent) was added, and then a solution prepared by adding 1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate was added from a dropping funnel to 2 Over a period of time, and stirring was further continued at 100 ° C for 3 hours.

A resin solution (solid concentration = 30 wt%) B-4 having a solid acid value of 105 mgKOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 15,000 and the molecular weight distribution (Mw / Mn) was 2.5.

Synthetic example  5. Binder resin  B-5

15 parts by weight of methacrylic acid, 25 parts by weight of N-phenylmaleimide, 10 parts by weight of benzyl methacrylate, 20 parts by weight of n-butyl methacrylate, 15 parts by weight of styrene, 15 parts by weight of 2-hydroxyethyl methacrylate , 2.5 parts by weight of? -methylstyrene dimer (chain transfer agent) were added, and then 1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 50 parts by weight of propylene glycol monomethyl ether acetate The solution was dropped from the dropping funnel over 2 hours into the flask, and stirring was further continued at 100 캜 for 3 hours.

A resin solution (solid concentration = 30 wt%) B-5 having a solid acid value of 94 mgKOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 12,000 and the molecular weight distribution (Mw / Mn) was 2.4.

Synthetic example  6. Binder resin  B-6

15 parts by weight of methacrylic acid, 10 parts by weight of? -Carboxylic dicaprolactone monoacrylate, 15 parts by weight of N-phenylmaleimide, 33 parts by weight of 2-ethylhexyl methacrylate, 12 parts by weight of styrene, , And 2.5 parts by weight of? -Methylstyrene dimer (chain transfer agent) were added to 50 parts by weight of propylene glycol monomethyl ether acetate, 1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) Was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 占 폚 for 3 hours.

To obtain a resin solution (solid concentration = 30 wt%) B-6 having a solid acid value of 103 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 15,300 and the molecular weight distribution (Mw / Mn) was 2.3.

Synthetic example  7. Binder Resin B-7

23.3 g of methyl-2- (bromomethyl) -acrylate (manufactured by Aldrich), 15.8 g of triethylamine (manufactured by Aldrich), 15 g of propylene glycol methyl Ether (manufactured by TCI) was added and the inside of the four-necked flask was replaced with nitrogen. Next, the flask was heated to 90 占 폚 and then 15.1 g of methyl-2- (hydroxymethyl) -acrylate (manufactured by Aldrich), 3.2 g of 2,2'-azobisisobutyronitrile (manufactured by Wako) And 110.0 g of glycol methyl ether (manufactured by TCI) was added dropwise over 1 hour and the polymerization reaction was carried out for 0.5 hour to produce a pyran-containing polymer. Next, a mixed solution of 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 225.0 g of propylene glycol methyl ether and 3.2 g of 2,2'-azobisisobutyronitrile (manufactured by Wako Co.) was slowly added dropwise over 1 hour And polymerization was carried out for 8 hours, followed by cooling to room temperature.

After replacing the inside of the four-necked flask with nitrogen, 61.5 g of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co.), 3.6 g of tetra-n-butylammonium bromide (manufactured by TCI) and 0.1 g of methoquinone g, and the reaction was carried out at 80 DEG C for 12 hours. Glycidyl methacrylate (GMA) was added to the carboxyl group of the copolymer to obtain a binder resin B-7.

The weight average molecular weight of the binder resin B-7 measured by GPC was 23,000.

Synthetic example  8. Binder Resin B-8

37.5 g of methacrylic acid (manufactured by Kyoeisha Chemical Co., Ltd.), 19.0 g of methyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 2.5 g of 2,5-dihydrofuran (manufactured by TCI Corporation) Product) and 225.0 g of propylene glycol methyl ether (manufactured by TCI), and the inside of the four-necked flask was replaced with nitrogen. Next, the flask was heated to 70 캜, and then 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 9.1 g of 2,5-dihydrofuran, 225.0 g of propylene glycol methyl ether and 2,2'-azobisisobutylo Nitrile (manufactured by Wako Co., Ltd.) was gradually added dropwise over 1 hour. After polymerization for 8 hours, the resultant was cooled to room temperature, and then the interior of the four-necked flask was replaced with nitrogen. To the flask, 61.5 g of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.) and 10 g of tetra- And glycidyl methacrylate (GMA) was added to the carboxyl group of the copolymer to obtain a binder resin B-8 (manufactured by Kasei Kogyo Co., Ltd.) and 0.15 g of methoquinone &Lt; / RTI &gt;

The weight average molecular weight of the binder resin B-8 measured by GPC was 17,000.

Synthetic example  9. Binder Resin B-9

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, the atmosphere in the flask was changed to nitrogen in air, and after the temperature was raised to 80 ° C, glycidyl methacrylate A solution in which 3.6 g of azobisisobutyronitrile was added to a mixture containing 85.2 g (0.6 mol) of the rate, 23.6 g (0.2 mol) of vinyltoluene and 136 g of propylene glycol monomethyl ether acetate was added to the flask And stirring was further continued at 80 ° C for 5 hours. Subsequently, 29.6 g (0.6 mol (33.33 mol% based on the epoxy group of the glycidyl methacrylate used in the present reaction) of the compound of the formula (6)), 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone was charged into the flask, and the reaction was continued at 110 캜 for 4 hours to obtain a binder resin B-9. The weight average molecular weight measured by GPC in terms of polystyrene was 17,000 and the molecular weight distribution (Mw / Mn) was 2.3.

Synthetic example  10-13. Binder resins B-10 to B-13

A binder resin was prepared in the same manner as in Synthesis Example 9 except that each component and its content were changed as shown in Table 1 below.

Synthesis Example 9 Synthesis Example 10 Synthesis Example 11 Synthesis Example 12 Synthesis Example 13 B-9 B-10 B-11 B-12 B-13 B'1 vinyl
23.6 g of toluene
(0.2 mole) vinyl
23.6 g of toluene
(0.2 mole) vinyl
22.2 g of pyrrolidone
(0.2 mole) vinyl
23.6 g of toluene
(0.2 mole) vinyl
23.6 g of toluene
(0.2 mole) B'2 Glycidyl
Methacrylate
85.2 g (0.6 mol) Glycidyl
56.8 g (0.4 mol) of methacrylate, Glycidyl
85.2 g (0.6 mol) of methacrylate, Glycidyl
56.8 g (0.4 mol) of methacrylate, Glycidyl
56.8 g (0.4 mol) of methacrylate, B'3 6
Compound 29.6 g
(0.2 mole) (7)
59.2 g of the compound
(0.4 mol) 39.2 g (0.2 mol) of the compound of the formula (5) 29.6 g (0.2 mol) of the compound of the formula (7) 29.6 g (0.2 mol) of the compound of the formula (7) Other
Monomer - - - benzyl
35.2 g (0.2 mol) of methacrylate, benzyl
74.8 g (0.2 mol) of maleimide, Weight average
Molecular weight (MW) 17,000 18,000 19,000 19,000 18,500 Molecular Weight
Distribution
(Mw / Mn) 2.3 2.3 2.3 2.4 2.4

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder polymer were measured by the GPC method under the following conditions.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Preparation of colored photosensitive resin composition

A colored photosensitive resin composition having the compositions and contents described in the following Examples 1 to 18 and Comparative Examples 1 to 5 was prepared.

< Example  1 to 9 and Comparative Example  1 to 2>

Example  One.

Preparation of liquid composition (G1)

C.I. Pigment Green 59 (manufactured by DIC Corporation) and C.I. 40 parts by weight of a 60/40 (by weight) mixture of Pigment Yellow 185 and 24 parts by weight (about 10.8 parts by weight in terms of solid content) of BYK2001 (Dispersive: BYK) And 136 parts by weight of propylene glycol methyl ether acetate was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion.

Subsequently, 400 parts by weight of the obtained pigment dispersion, 200 parts by weight of a resin solution (B-1) as a binder resin, 60 parts by weight of dipentaerythritol hexaacrylate as a photopolymerizable compound, 2 parts by weight of 2-benzyl- 40 parts by weight of 1- (4-morpholinophenyl) butanone and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (G1).

Example  2 to 6.

Preparation of liquid compositions (G2 to G6)

200 parts by weight of the resin solution (B-2) (Example 2) and 200 parts by weight of the resin solution (B-3) were used in place of 200 parts by weight of the resin solution (B- 200 parts by weight of the resin solution (B-3), 200 parts by weight of the resin solution (B-4) (Example 4), 200 parts by weight of the resin solution (B- (G2 to G6) were prepared in the same manner as in Example 1. The liquid compositions

Example  7.

Preparation of liquid composition (G7)

In Example 1, C.I. Pigment Yellow 185 instead of C.I. A liquid composition (G7) was prepared in the same manner as in Example 1, except that Pigment Yellow 150 was used.

Example  8.

Preparation of liquid composition (G8)

A liquid composition (G8) was prepared in the same manner as in Example 7, except that 200 parts by weight of the resin solution (B-4) was used instead of 200 parts by weight of the resin solution (B-1) .

Example  9.

Preparation of liquid composition (G9)

A liquid composition (G9) was prepared in the same manner as in Example 7, except that 200 parts by weight of the resin solution (B-6) was used instead of 200 parts by weight of the resin solution (B-1) .

Comparative Example  One.

Preparation of liquid composition (g1)

In Example 1 above, C.I. Pigment Green 59 (manufactured by DIC Corporation) and C.I. Instead of 40 parts by weight of a 60/40 (by weight) mixture of Pigment Yellow 185, C.I. Pigment Green 7 and C.I. Except that 40 parts by weight of a mixture of a pigment and a pigment 185 (weight ratio 56: 44) was used.

Comparative Example  2.

Preparation of liquid composition (g2)

In Example 7, the pigment was prepared by using C.I. Pigment Green 59 and C.I. Instead of 40 parts by weight of a 60/40 (by weight) mixture of Pigment Yellow 150, C.I. Pigment Green 7 and C.I. (Weight ratio 55: 45) was used in place of 40 parts by weight of Pigment Yellow 150, to thereby prepare a liquid composition (g2).

< Example  10 to 18 and Comparative Example  3-5>

(Parts by weight) division Example 10 Example 11 Example 12 Example 13 Comparative Example 3 Comparative Example 4 The colorant (A) a-1 3.1 3.1 3.1 3.1 - - a-2 1.5 1.5 1.5 1.5 4.6 4.6 a-3 2.9 2.9 2.9 2.9 2.9 2.9 The binder resin (B) B-7 5.5 3.7 1.8 - 5.5 - B-8 - 1.8 3.7 5.5 - 5.5 The photopolymerizable compound (C) C-1 3.7 3.7 3.7 3.7 3.7 3.7 Photopolymerization initiator (D) D-1 1.1 1.1 1.1 1.1 1.1 1.1 Additive (F) F-1 0.1 0.1 0.1 0.1 0.1 0.1 Solvent (E) E-1 82 82 82 82 82 82 division Example 14 Example 15 Example 16 Example 17 Example 18 Comparative Example 5 coloring agent
(A) a-1 22.3 22.3 22.3 22.3 22.3 - a-2 12 12 12 12 12 31.7 a-3 23.5 23.5 23.5 23.5 23.5 26.1 Binder resin B-9 5.7 5.7 B-10 5.7 B-11 5.7 B-12 5.7 B-13 5.7 The photopolymerizable compound (C) C-1 3.8 3.8 3.8 3.8 3.8 3.8 Photopolymerization initiator (D) D-1 1.1 1.1 1.1 1.1 1.1 1.1 Additive (F) F-1 0.1 0.1 0.1 0.1 0.1 0.1 Solvent (E) E-1 31.6 31.6 31.6 31.6 31.6 31.6

F-1: 계면활성제 (SH-8400, 제조사: 도레이사)
E-1: 프로필렌글리콜모노메틸에테르아세테이트Colorant (A) (a-1): G59 (manufactured by DIC Corporation)
(a-2): G7 (manufactured by DIC Corporation)
(a-3): Y138 (manufacturer: BASF)
The binder resins (B-7 to B-13) synthesized in Synthesis Examples 7 to 13
C-1: dipentaerythritol hexaacrylate
D-1: oxime compound represented by the following formula (13)
[Chemical Formula 13]

F-1: Surfactant (SH-8400, manufactured by Doraisha)
E-1: Propylene glycol monomethyl ether acetate

< Experimental Example > Evaluation of colored photosensitive resin composition

< Experimental Example  1 to 3>

Formation of pixel pattern

A 2-inch square glass substrate (# 1737, manufactured by Corning Incorporated) was sequentially washed with a neutral detergent, water and alcohol, and then dried. When the composition of each of the compositions of Examples 1 to 9 and Comparative Examples 1 and 2 was exposed on this glass substrate at an exposure amount (365 nm) of 100 mJ / cm ² and the development step was omitted, the film thickness after the post- , And then preliminarily dried in a clean oven at 100 DEG C for 3 minutes. After cooling, the substrate coated with this colored photosensitive resin composition and the spacing of a quartz glass photomask (having a pattern for changing the transmittance in a stepwise manner in the range of 1 to 100% and a line / space pattern of 1 to 50 m) Was irradiated with light at an exposure dose (365 nm) of 100 mJ / cm &lt; ² &gt; in the atmosphere using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI CO., LTD.

Thereafter, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 DEG C for a predetermined time, developed, washed with water and dried at 220 DEG C for 30 minutes.

Experimental Example  1. Measurement of luminance

The luminance was measured using a micro-scopic spectrometer OSP-SP2000 and the luminance values in the same color coordinates are shown in Table 3 below.

Experimental Example  2. Color coordinates  evaluation

The color coordinates of the colored layer were measured using a microscopic spectrometer OSP-SP2000, and the results are shown in Table 3 below.

Experimental Example  3. Contrast ratio  evaluation

A maximum value and a minimum value of the light intensity were measured while irradiating a fluorescent lamp (wavelength range of 380 to 780 nm) from the rear side with the substrate obtained above being placed between two polarizing plates by using a Topcon CONS Contrast Meter BM-5A model, And the contrast ratio was evaluated by dividing the maximum value by the minimum value. The measurement standard was a standard of a contrast of 1/30000 on a glass substrate (before forming a colored layer).

Further, after storing for one month at 23 占 폚, the contrast ratio was similarly evaluated using each of the liquid compositions (G1 to G9, g1 to g2) and described in Table 3 below.

Color coordinates Luminance
(Y) Y (%)
(x = 0.256, y = 0.641) Y (%)
(x = 0.240, y = 0.606) Contrast ratio Early 23 &lt;
After a month's retention Example 1 (x = 0.256, y = 0.641) - 43.2 107% - 12,300 12,000 Example 2 43.1 107% 12,000 11,800 Example 3 43.4 108% 13,300 12,300 Example 4 43.3 108% 11,300 10,800 Example 5 43.6 108% 12,500 11,700 Example 6 43.6 108% 11,000 10,700 Example 7 - (x = 0.240, y = 0.606) 44.5 - 109% 22,800 22,200 Example 8 44.3 109% 22,300 22,000 Example 9 44.6 109% 23,000 22,650 Comparative Example 1 (x = 0.256, y = 0.641) - 40.2 100% - 11,000 10,200 Comparative Example 2 - (x = 0.240, y = 0.606) 40.8 - 100% 18,700 18,400

< Experimental Example  4 to 7>

Each of the photo-curable resin compositions prepared in Examples 10 to 13 and Comparative Examples 3 and 4 was subjected to a spin coater to adjust the number of rotations so that the film thickness after drying was 2.5 μm on a 50 mm × 50 mm glass substrate And dried in an oven at 100 ° C for 3 minutes.

The dried substrate was exposed so that the accumulated light quantity at a wavelength of 313 nm of the fusion lamp was 40 mJ at a distance of 300 mu m from the photomask to produce a color filter.

Then, each method described in Experimental Examples 4 to 7 was carried out.

Experimental Example  4. Sensitivity evaluation

Thereafter, the resultant was developed with a spray developing apparatus using a KOH aqueous solution having a pH of 10.5 for 1 minute, washed with water, and air-dried. And then cured in an oven at 230 ° C for 20 minutes to measure the pattern line width of the color filter and the degree of pattern peeling.

The degree of sensitivity was measured by checking the difference between the line width (X1) of the pattern and the line width (X2) of the photomask. The results are shown in Table 4 below.

<Evaluation Criteria of Line Width>

+5 or higher: Fit

-5 to +5: Good

Less than -5: Incompatible

<Evaluation Criteria for Pattern Peeling>

○: No pattern peeling

DELTA: pattern peeling 1 to 3

X: Pattern peeling 4 or more

Experimental Example  5. Solvent resistance  evaluation

Thereafter, the resultant was developed with a spray developing apparatus using a KOH aqueous solution having a pH of 10.5 for 1 minute, washed with water, and air-dried. It was then cured in a 230 ° C oven for 20 minutes. This substrate was immersed in a NMP solution at room temperature for 30 minutes, washed with ultrapure water and dried on a hot plate heated to 120 DEG C for 2 minutes, and the chromaticity before and after immersion was measured. The formula used here is calculated by the following equation (1) representing the color change in the three-dimensional colorimetry defined by L *, a *, b *, and a color filter with high reliability can be manufactured as the color change value becomes smaller. The results are shown in Table 4 below.

[Equation 1]

? Eab * = [(? L *) 2+ (? A *) 2+ (? B *) 2]

<Evaluation criteria for solvent resistance>

△ Eab * 3 or less: Fit

Above Eab * 3: Incompatible

Experimental Example  6. Evaluation of Inverse Taper Generation Level

Thereafter, the resultant was developed with a spray developing apparatus using a KOH aqueous solution having a pH of 10.5 for 1 minute, washed with water, and air-dried. After that, the end of the pattern produced by scanning electron microscope (HITACHI S4300) was measured and the reverse taper level was measured. Measurements were made by measuring the length of the part that ran into the pattern from the end of the pattern. The results are shown in Table 4 below.

Experimental Example  7. Luminance evaluation

Thereafter, the resultant was developed with a spray developing apparatus using a KOH aqueous solution having a pH of 10.5 for 1 minute, washed with water, and air-dried. It was then cured in a 230 ° C oven for 20 minutes. The luminance was measured using a microscopic spectrometer OSP-SP2000, and the luminance values at the same color coordinates (x = 0.260, y = 0.640) were expressed. The results are shown in Table 4 below.

Sensitivity Solvent resistance Reverse Taper Level
(um) Luminance Line width Pattern exfoliation Example 10 +13 ○ 1.9 0.7 48.8 Example 11 +11 ○ 2.1 0.9 48.7 Example 12 +10 ○ 2.1 1.0 48.9 Example 13 +8 ○ 2.6 1.3 48.6 Comparative Example 3 +8 △ 2.9 2.1 44.7 Comparative Example 4 -6 x 4.2 4.2 44.5

< Experimental Example  8 to 11>

The colored photosensitive resin compositions prepared in Examples 14 to 18 and Comparative Example 5 were applied on a glass substrate (# 1737, Corning) by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film .

Subsequently, a 1 kw high-pressure mercury lamp containing all of g, h and i rays as an ultraviolet light source was irradiated onto the thin film at an illuminance of 100 mJ / cm 2. No special optical filter was used at this time. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop.

The glass substrate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 캜 for 30 minutes to prepare a colored layer. The thickness of the produced colored layer was 1 to 5 mu m.

Experimental Example  8. Evaluation of heat resistance

After the pattern was finally formed, the color change (heat resistance) around 230 ° C / 2 hr was compared and evaluated. At this time, the computed variation range of Eab was excellent, less than 3, and more than 3, respectively.

(1), which represents a color change in a three-dimensional colorimetric system defined by L *, a *, b *, and a color filter with a high reliability can be manufactured as the color change value is small. Table 5 shows the results.

&Quot; (1) &quot;

? Eab * = [(? L *) 2+ (? A *) 2+ (? B *) 2] 1/2

Experimental Example  9. Developability  evaluation

The colored photosensitive resin compositions prepared in Examples 14 to 18 and Comparative Example 5 were applied on a glass substrate (# 1737, Corning) by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film . The dried substrate is immersed in a KOH aqueous solution having a pH of 10.5 and PGMEA (propylene glycol monomethyl ether acetate) solvent, and the time until dissolution is measured. The results are shown in Table 5 below.

&Lt; Development evaluation standard &

○: 2 minutes or less

?: More than 2 minutes to less than 4 minutes

X: Exceeding 4 minutes and peeling

Experimental Example  10. Development residue  evaluation

When there is no development residue on the substrate, it is indicated by 'O', and when the development residue is on the substrate, it is indicated by 'X'. The results are shown in Table 5 below.

Experimental Example  11. Luminance measurement

The luminance was measured using a microscopic spectrometer OSP-SP2000 and the luminance values at the same color coordinates (x = 0.262, y = 0.642) were indicated. The results are shown in Table 5 below.

Heat resistance Developability Development residue Luminance Example 14 Excellent (0.7) △ ○ 48.2 Example 15 Good (1.3) ○ ○ 48.4 Example 16 Excellent (0.9) △ ○ 48.1 Example 17 Good (1.6) ○ ○ 48.0 Example 18 Good (2.3) ○ ○ 48.2 Comparative Example 5 Good (0.8) ○ X 45.7

As shown in Table 3, based on the same color coordinates, C.I. It can be seen that the luminance Y, which is an index of the light transmittance, is improved by 7.0 to 8.0% when G59 is used, as compared with the case of using Pigment Green 7 (G7).

In addition, the contrast ratio is 300-3000 as compared with the comparative example having the same color coordinates, and it is confirmed that the contrast ratio is low and the high contrast ratio is maintained even after storing for one month at 23 DEG C, .

As can be seen from the results of Table 4, the colored photosensitive resin compositions of Examples 10 to 13, which are included in the scope of the present invention, are excellent in sensitivity, solvent resistance and luminance evaluation results, and have an inverse taper level of less than 1.5 μm . On the other hand, the colored photosensitive resin compositions of Comparative Examples 3 and 4 had poor sensitivity and solvent resistance, reverse taper and luminance evaluation results.

In Table 5, it was confirmed that the color filters formed from the colored photosensitive resin compositions of Examples 14 to 18 belonging to the scope of the present invention were excellent in heat resistance and developability and did not cause development residue. On the other hand, in the case of Comparative Example 5, it was confirmed that the evaluation results of luminance and residual residue were not particularly excellent.

That is, it can be confirmed that the colored photosensitive resin composition of the present invention is a composition having high brightness, high coloring property, high sensitivity, and excellent heat resistance and solvent resistance while having a desired color coordinate value.

Claims (16)

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E);
Wherein the colorant (A) comprises a CI pigment green 59, and further comprises a pigment. The method according to claim 1,
The binder resin (B) comprises at least one selected from the copolymer (B1), the polymer (B2) and the copolymer (B3)
The copolymer (B1) is a copolymer of (meth) acrylic acid (b1); N-substituted maleimide (b2); (Meth) acrylates such as styrene,? -Methylstyrene, p-hydroxy-? -Methylstyrene, methyl (meth) acrylate, n-butyl (Meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, mono [2- (meth) acryloyloxyethyl], omega-carboxypolycaprolactone mono At least one unsaturated compound (b3) selected from poly (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer; , &Lt; / RTI &gt;
The polymer (B2) is at least one repeating unit selected from the following formulas (2) and (3)
The copolymer (B3) is a copolymer obtained by copolymerizing an aromatic vinyl compound (B'1), a compound (B'2) having an unsaturated bond and an epoxy group in one molecule, and a compound (B'3) A colored photosensitive resin composition characterized by:
(2)

In Formula 2, R ₁ , R ₂ , R ₃ , and R ₄ are each independently an organic residue having 1 to 20 carbon atoms which may contain a hydrogen atom, a halogen atom, or an oxygen atom,
(3)

In Formula 3, R ₅ , R ₆ , R ₇ , and R ₈ are each independently an organic residue having 1 to 20 carbon atoms which may contain a hydrogen atom, a halogen atom, or an oxygen atom,
[Chemical Formula 4]

In Formula 4,
R ₁ and R ₂ are each independently a C1 to C6 alkyl group which is unsubstituted or substituted with at least one member selected from a halogen, a ketone group, an ester group and a thiol group,
A is an aliphatic polycyclic group substituted or unsubstituted with at least one member selected from the group consisting of a halogen atom, a methoxy group and an ethoxy group; Allyl group; halogen; Methoxy group; Ethoxy group; And C1 to C8 alkoxy groups; Or an unsubstituted or substituted aromatic polycyclic group;
n and m are 0 or 1, respectively. The method of claim 2,
The binder resin (B) comprises the copolymer (B1)
5 to 40% by weight of the component derived from the component (b1), based on the total weight of the copolymer (B1);
From 5 to 40% by weight of components derived from (b2); And
And 30 to 80% by weight of the component derived from the component (b3). The method of claim 2,
The binder resin (B) comprises the polymer (B2)
And the polymer (B2) is contained in an amount of 1 to 99% by weight based on the total weight of the binder resin. The method of claim 2,
Wherein the binder resin (B) comprises the copolymer (B3)
With respect to the total number of moles of the constituent units of the copolymer (B3)
The proportion of the constitutional unit derived from (B'1) is 20 to 60 mol%; And
And the proportion of the constituent unit derived from (B'2) is from 20 to 60 mol%. The method of claim 2,
Wherein the proportion of the structural unit derived from the compound (B'3) is 20 to 120 moles per 100 moles of the epoxy group of the compound (B'2). The method according to claim 1,
Wherein the binder resin (B) has a weight average molecular weight of 2,000 to 100,000. The method according to claim 1,
Wherein the CI Pigment Green 59 is contained in an amount of 0.05 to 50 wt% based on the total weight of the colored photosensitive resin composition. The method according to claim 1,
Wherein the CI Pigment Green 59 and the pigment are contained in a weight ratio of 1: 0.050 to 1: 18.0. The method according to claim 1,
Based on the solid content in the colored photosensitive resin composition,
5 to 85% by weight of colorant (A); And
And 1 to 85% by weight of a binder resin (B). The method according to claim 1,
Wherein the CI Pigment Green 59 has a Tmax of 500 to 530 nm. The method according to claim 1,
Wherein the T _50% of the CI Pigment Green 59 is 445 to 580 nm. The method according to claim 1,
And has a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more in the XYZ color system. The colored photosensitive resin composition according to claim 1, wherein the colorant (A) further comprises a dye. A color filter comprising a coloring pattern made of the colored photosensitive resin composition according to any one of claims 1 to 14. An image display device comprising the color filter of claim 15.

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