TWI648352B - Colored photosensitive resin composition, color filter and image display device using the same - Google Patents

Abstract

The present invention relates to a coloring photosensitive resin composition comprising a coloring agent (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E); wherein the coloring agent ( A) includes CI Pigment Green 59, and one or more types selected from the group consisting of pigments and dyes; the present invention also relates to a color filter manufactured using the composition, and an image display device including the color filter .

Description

Coloring photosensitive resin composition, color filter, and image display device using the same Field of invention

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

Background of the invention

Color filters are widely used in various display devices such as imaging devices and liquid crystal display devices (LCDs), and the range of applications is rapidly increasing. A color filter used in an image forming apparatus, a liquid crystal display device, or the like is formed in a coloring pattern of three colors of red, green, and blue, or a coloring pattern of three colors of yellow, magenta, and cyan.

Each of the coloring patterns of the color filter is usually formed using a colored photosensitive resin composition including a colorant such as a pigment or a 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 carried out by photolithography.

Recently, in order to improve workability and product quality, color filters for various display devices including solid image devices such as digital cameras and liquid crystal display devices (LCDs) are required to have high brightness and high coloring properties.

In the meantime, Korean Patent Application Publication No. 2013-0134494 discloses a resin composition using C.I. Pigment Green 7 and C.I. Pigment Yellow 185, but the problem is that high brightness and high coloring properties cannot be simultaneously satisfied.

Prior art literature Patent literature

Korean Patent Application Publication No. 10-2013-0134494

Summary of invention

The present invention has been made in view of the above, and an object of the present invention is to provide a colored photosensitive resin composition which has excellent brightness, coloring property and adhesion, and is capable of forming a pixel having high light transmittance and high contrast.

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

One aspect of the present invention provides a colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), Wherein the colorant (A) comprises CI Pigment Green 59, and one or more types selected from the group consisting of pigments and dyes.

Another aspect of the present invention provides a color filter comprising a pattern formed using the colored photosensitive resin composition.

Yet another aspect of the present invention provides an image display including a color filter Device.

FIG. 1 is a graph showing a transmittance spectrum in the case of using a coloring agent including each pigment.

detailed description

The present invention includes a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the colorant (A) includes the following Chemical Formula 1 a compound, and one or more types selected from the group consisting of pigments and dyes.

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

Hereinafter, various components forming the coloring photosensitive resin composition of the present invention will be described. However, the invention is not limited to these components.

(A) colorant

The coloring agent (A) according to the present invention is a component capable of exhibiting a color such as red, green or blue in order to prepare a pattern having a target color.

Pigment (a1)

The coloring agent (A) included in the coloring photosensitive resin composition of the present invention includes a compound represented by the following Chemical Formula 1 as the pigment (a1). The compound represented by the following Chemical Formula 1 has a zinc phthalocyanine (ZnPc) structure. The coloring agent (A) of the present invention comprising the compound represented by the following Chemical Formula 1 has an advantage of high color reproduction.

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

Preferable examples of the compound represented by Chemical Formula 1 may include C.I. Pigment Green 59 (hereinafter, also referred to as 'G59'). This case is preferable in terms of maximizing the effects of the present invention.

CI Pigment Green 58 (G58) has the advantage of high brightness, however, in order to achieve high coloring properties, the pigment content is increased, and when such a large amount of the pigment is included in the composition, problems may occur, such as deterioration in developability, use The pattern formed by the composition has a risk of peeling and a decrease in sensitivity.

However, the present invention utilizes the pigment represented by Chemical Formula 1, in particular As a colorant, G59 can be designed as a resist which is highly color-reproducible even at a small pigment content.

Meanwhile, the inclusion of C.I. Pigment Green 7 (G7) in the resin composition is advantageous in use because it has a problem of low brightness even if high coloring properties can be obtained even at a low pigment content. However, the compound of Chemical Formula 1, particularly G59, included in the coloring photosensitive resin composition of the present invention functions to exhibit excellent brightness while being included in the colored photosensitive resin composition while exhibiting synergy with CI Pigment Green 7 Similar transmission spectra and color coordinates as pigments. As identified in Figure 1, the transmission spectrum of C.I. Pigment Green 59 at a wavelength of 400 nm to 610 nm is similar to C.I. Pigment Green 7.

In the present invention, Tmax means a wavelength at a point having a maximum pigment transmittance, and T _50% means a wavelength at a point where the pigment transmittance is 50% or more of the maximum value.

In one embodiment of the present invention, the C.I. Pigment Green 59 may have a Tmax of 500 nm to 530 nm, and it is preferable in terms of having excellent coloring properties.

In another embodiment of the present invention, the CI Pigment Green 59 may have a T _{50% of} 445 nm to 580 nm, and it is preferable in terms of having excellent coloring properties.

The compound of Chemical Formula 1 preferably accounts for 0.05% by weight to 50% by weight, more preferably 0.1% by weight to 25% by weight and still more preferably 0.5% by weight to 20% by weight based on the total weight of the coloring photosensitive resin composition of the present invention. The compound of Chemical Formula 1 is preferably in the range of from 0.05% by weight to 50% by weight based on the above criteria, because of high light transmittance, high contrast, and excellent developability.

The coloring agent (A) according to the present invention includes, in addition to the compound represented by Chemical Formula 1, one or more types selected from the group consisting of pigments and dyes, which are generally used in the art as being capable of exhibiting a color such as red, Green or blue is used in order to prepare a component having a pattern of a target color, and these can be prepared in the form of a color paste.

In the composition of the present invention, the compound represented by Chemical Formula 1 is preferably included in a weight ratio of 1:0.050 to 1:18.0, more preferably 1:0.1 to 1:9, and still more preferably 1:0.2 to 1:4. The one or more types selected from the group consisting of pigments and dyes. The above weight ratio is preferred due to the advantages of high coloring properties and high brightness, as well as improved processing margin and excellent sensitivity.

In this case, the coloring agent including the compound of Chemical 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 chromaticity system.

Meanwhile, when G58 is taken as an example, color coordinates of approximately x = 0.2 to 0.35 when y = 0.6 or higher in the XYZ chromaticity system can be obtained. Here, in order to utilize G58 having a value close to x=0.1, it is necessary to include a mixed color with blue, and this is not preferable because of a problem of a decrease in luminance.

When G7 is used as another example, the area where the color can be expressed may be large, but there is a problem that the brightness is low.

The pigment (a1) includes an organic pigment and an inorganic pigment, and these may be used singly or as a mixture of two or more types. The use of an organic pigment may be more preferable in terms of excellent heat resistance and color forming properties. The organic pigment may be a synthetic pigment or a natural pigment.

The organic pigment may be resin-treated as needed; Surface treatment of a pigment derivative into an acidic group or a basic group; graft treatment on a pigment surface by using a polymer compound or the like; atomization treatment by a sulfurization method such as sulfuric acid; or removal of impurities by using an organic solvent or water And the washing process.

As the inorganic pigment, a metal compound such as a metal oxide or a metal complex salt, an inorganic salt such as barium sulfate (base pigment), and more specific examples of the metal compound may include a metal such as iron, cobalt, aluminum, Oxides of cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black, or composite metal oxides, and the like.

Specific examples of the pigment (a1) may more preferably include a compound classified as a pigment in the Color Index (published by the Society of Dyers and Colourists), and more specifically including The following color index (CI) numbers illustrate the pigments. However, the pigment is not limited thereto, and one or more types selected therefrom may be co-dispersed with a binder resin, a dispersant, or the like for use, thereby obtaining a target chromaticity.

Specific examples of CI Pigment Yellow may include CI 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, 214, etc.; specific examples of CI Pigment Orange may include CI Pigment Orange 13, 31, 38 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.; specific examples of CI pigment red may include CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166 , 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; specific examples of CI pigment blue may include CI Pigment Blue 15:3, 15:4, 15:6, 16, 22, 28, 60, etc. Specific examples of CI Pigment Violet may include CI Pigment Violet 14, 19, 23, 29, 32, 177, etc., and specific examples of CI Pigment Green may include CI Pigment Green 7, 36, 58, and the like.

Among the pigments exemplified above, one or more types including a group selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 129, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185 may be more preferred.

Dye (a2)

The dye (a2) which may be included in the coloring agent (A) of the present invention can be used without limitation as long as it has solubility in an organic solvent or can be dispersed in an organic solvent. Preferably, a dye capable of ensuring reliability such as solubility to an alkali developing solution, heat resistance, and solvent resistance while having solubility in an organic solvent can be advantageously used. Dyes that do not have solubility in organic solvents can be dispersed for use.

As the dye (a2), one or more selected from the group consisting of an acid dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of a nitrogen-containing compound and an acid dye, a sulfonamide of an acid dye, and the like, and a derivative thereof can be used. Types of. In addition to these, the dye may also be selected from azo, oxonium and phthalocyanine acid dyes, and derivatives thereof.

The dye (a2) may preferably comprise a compound classified as a dye in the Color Index (published by the Society of Dyers) or a known dye described in Dyeing Note (Color and Dye Corporation). .

Specific examples of the dye (a2) may include CI Solvent Yellow 2, CI Solvent Yellow 14, CI Solvent Yellow 16, CI Solvent Yellow 33, CI Solvent Yellow 34, CI Solvent Yellow 44, CI Solvent Yellow 56, CI Solvent Yellow 82, CI solvent yellow 93, CI solvent yellow 94, CI solvent yellow 98, CI solvent yellow 116 and CI solvent yellow 135; CI solvent orange 1, CI solvent orange 3, CI solvent orange 7 and CI solvent orange 63; CI solvent red 1. CI solvent red 2, CI solvent red 3, CI solvent red 8, CI solvent red 18, CI solvent red 23, CI solvent red 24, CI solvent red 27, CI solvent red 35, CI solvent red 43, CI solvent red 45, CI solvent red 48, CI solvent red 49, CI solvent red 91: 1, CI solvent red 119, CI solvent red 135, CI solvent red 140, CI solvent red 196 and CI solvent red 197; CI solvent purple 8, CI Solvent violet 9, CI solvent violet 13, CI solvent violet 26, CI solvent violet 28, CI solvent violet 31 and CI solvent violet 59; CI solvent blue 4, CI solvent blue 5, CI solvent blue 25, CI solvent blue 35, CI Solvent Blue 36, CI Solvent Blue 38 and CI Solvent Blue 70; CI Solvent Green 3, CI Solvent Green 5 and CI Solvent Green 7, etc. But it is not limited thereto.

The colorant (A) may preferably account for 5% by weight to 85% by weight and more preferably 10% by weight to 50% by weight based on the solids in the colored photosensitive resin composition. When the content of the colorant (A) is less than 5% by weight, the formed pattern may have a decreased color separation ability, and when the content is more than 85% by weight, the lithography efficiency may be lowered, resulting in residue residue or the like. No development problems.

The solid content in the colored photosensitive resin composition of the present invention means The total content of components other than the solvent in the colored photosensitive resin composition.

(B) Adhesive resin

The binder resin (B) included in the coloring photosensitive resin composition of the present invention is a component which provides solubility to an alkaline developing solution used in development. Further, the binder resin serves as a pigment binder, and when forming a coloring layer, is a component having solubility to a developing solution (particularly preferably an alkaline developing solution) used in a color developing process.

In the present invention, the binder resin (B) preferably includes one or more types selected from the group consisting of the following copolymer (B1), the underlying polymer (B2), and the underlying copolymer (B3).

The copolymer (B1) includes a copolymer of (meth)acrylic acid (hereinafter also referred to as "copolymer (B1)") (b1); N-substituted maleimide (b2); and selected from the following One or more types of unsaturated compounds (b3) (hereinafter also referred to as "unsaturated compounds (b3)" or "(b3)"): styrene, α-methylstyrene, p-hydroxy-α-methyl Styrene, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate Ester, benzyl (meth) acrylate, glycerol mono(meth)acrylate, mono [2-(methyl) propylene methoxyethyl] succinate, ω-carboxy polycaprolactone mono (methyl) Acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer.

The polystyrene macromonomer and the polymethyl methacrylate macromonomer may refer to a monomer of a polymer of each polystyrene or polymethyl methacrylate.

Examples of N-substituted maleimide (b2) may include N-phenyl Malay Yttrium, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimine, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N - Amber quinone imine-6-maleimide caproate, N-amber succinimide-3-maleimide propionate, N-(acridinyl)maleimide, etc. .

Among these N-substituted maleimines, N-phenylmaleimide, N-cyclohexylmaleimide and the like are preferable, and N-phenylmaleimide, N-, more preferably Benzyl maleimide and the like. The N-substituted maleimide may be used singly or as a mixture of two or more types.

Examples of the unsaturated compound (b3) preferably include one or more types selected from the group consisting of styrene, n-butyl (meth)acrylate, ethylhexyl 2-(meth)acrylate, (methyl) 2-hydroxyethyl acrylate, benzyl (meth) acrylate, glycerol mono(meth)acrylate, mono [2-(methyl) propylene methoxyethyl] succinate and ω-carboxy polycaprolactone Mono (meth) acrylate. More preferably, 2-ethylhexyl (meth)acrylate and/or ω-carboxypolycaprolactone mono(meth)acrylate can be selected and used.

In addition to the (meth)acrylic acid (b1), the N-substituted maleimide (b2), and the unsaturated compound (b3), the binder resin (B) of the present invention may further include copolymerizable with these A copolymer copolymerized with another unsaturated monomer (b4).

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

Preferable specific examples of the copolymer (B1) obtained as above may include (meth)acrylic acid/N-phenylmaleimide/styrene/benzyl (meth)acrylate copolymer, (meth)acrylic acid/N-m-hydroxyphenylmaleimide/styrene/ Benzyl (meth)acrylate copolymer, (meth)acrylic acid/N-p-hydroxyphenylmaleimide/styrene/benzyl (meth)acrylate copolymer, (meth)acrylic acid/N-ring Hexylmalanimide/styrene/benzyl (meth)acrylate copolymer, (meth)acrylic acid/N-phenylmaleimide/α-methylstyrene/benzyl (meth)acrylate Copolymer, (meth)acrylic acid/N-phenylmaleimide/styrene/n-butyl (meth)acrylate copolymer, (meth)acrylic acid/N-phenylmaleimide/benzene 2-ethylhexyl copolymer of ethylene/(meth)acrylate, copolymerization of (meth)acrylic acid/N-phenylmaleimide/p-hydroxy-α-methylstyrene/benzyl (meth)acrylate , (meth)acrylic acid/N-phenylmaleimide/styrene/n-butyl (meth)acrylate copolymer, (meth)acrylic acid/N-phenylmaleimide/styrene /(2-ethylhexyl acrylate) copolymer, (meth)acrylic acid / N-phenylmaleimide / styrene / (methyl ) 2-hydroxyethyl acrylate / benzyl (meth) acrylate copolymer, (meth) acrylate / N-phenyl maleimide / styrene / benzyl (meth) acrylate / single (methyl) Glyceryl acrylate copolymer, (meth)acrylic acid / N-p-hydroxyphenyl maleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (methyl) Acrylic acid / N-phenyl maleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polystyrene macromolecular copolymer, (meth) acrylic acid / N-phenylmaleimide/styrene/phenyl (meth)acrylate/2-hydroxyethyl (meth)acrylate/polymethyl methacrylate macromolecular copolymer, (meth)acrylic acid /N-phenylmaleimide/styrene/benzyl (meth)acrylate/n-butyl (meth)acrylate/2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid /N-phenylmaleimide/styrene/benzyl (meth)acrylate/n-butyl (meth)acrylate/glycerol mono(meth)acrylate, (meth)acrylic acid/N- Phenylmaleimide/styrene/benzyl (meth)acrylate/2-ethylhexyl (meth)acrylate/2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid/ N-phenylmaleimide/styrene/benzyl (meth)acrylate/2-ethylhexyl (meth)acrylate/glycerol mono(meth)acrylate, (meth)acrylic acid/ Mono[2-(methyl)acryloxyethyl)succinate/N-phenylmaleimide/styrene/benzyl (meth)acrylate copolymer, (meth)acrylic acid/single [ 2-(Methyl)propenyloxyethyl]succinate/N-p-hydroxyphenylmaleimide/styrene/benzyl (meth)acrylate copolymer, (meth)acrylic acid/single [ 2-(Methyl)propenyloxyethyl]succinate/N-phenylmaleimide/styrene/allyl (meth)acrylate copolymer, (meth)acrylic acid/single [2] -(Methyl)acryloxyethyl)succinate/N-cyclohexylmaleimide/styrene/allyl (meth)acrylate copolymer, (meth)propene Acrylic acid/mono[2-(methyl)acryloxyethyl]succinate/N-cyclohexylmaleimide/styrene/benzyl (meth)acrylate copolymer, (meth)acrylic acid /mono[2-(methyl)acryloxyethyl]succinate/N-phenylmaleimide/styrene/n-butyl (meth)acrylate/2-hydroxy(meth)acrylate Ethyl ester copolymer, (meth)acrylic acid / mono [2-(methyl) propylene methoxyethyl] succinate / N-phenyl maleimide / styrene / (meth) acrylate Ester/mono(meth)acrylate copolymer, (meth)acrylic acid/mono[2-(methyl)acryloxyethyl]succinate/N-phenylmaleimide/styrene /2-ethylhexyl (meth)acrylate / 2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid / mono [2-(methyl) propylene methoxyethyl] succinate /N-phenylmaleimide/styrene/2-ethylhexyl (meth)acrylate/single (meth)acrylic acid glyceride copolymer, (meth)acrylic acid/ω-carboxypolycaprolactone mono(meth)acrylate/N-m-hydroxyphenylmaleimide/styrene/(methyl) Benzyl acrylate copolymer, (meth)acrylic acid / ω-carboxy polycaprolactone mono (meth) acrylate / N-p-hydroxyphenyl maleimide / styrene / benzyl (meth) acrylate copolymerization , (meth)acrylic acid / ω-carboxy polycaprolactone mono (meth) acrylate / N-phenyl maleimide / styrene / benzyl (meth) acrylate / mono (meth) acrylate Glyceride copolymer, (meth)acrylic acid / ω-carboxy polycaprolactone mono (meth) acrylate / N-p-hydroxyphenyl maleimide / styrene / benzyl (meth) acrylate / single (meth)acrylic acid glyceride copolymer, (meth)acrylic acid/ω-carboxypolycaprolactone mono(meth)acrylate/N-phenylmaleimide/styrene/(meth)acrylic acid Butyl ester / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylate / ω-carboxy polycaprolactone mono (meth) acrylate / N-phenyl maleimide / styrene / N-butyl (meth)acrylate/glycerol mono(meth)acrylate, (meth) propylene /ω-carboxypolycaprolactone mono(meth)acrylate/N-phenylmaleimide/styrene/2-ethylhexyl (meth)acrylate/2-hydroxyethyl (meth)acrylate Ester copolymer, (meth)acrylic acid / ω-carboxy polycaprolactone mono (meth) acrylate / N-phenyl maleimide / styrene / 2-ethylhexyl (meth) acrylate / A mono(meth)acrylate copolymer or the like is not limited thereto.

In other words, the copolymer included in the binder resin (B) can be produced by copolymerizing (meth)acrylic acid (b1), N-substituted maleimide (b2), and unsaturated compound (b3). In addition, other unsaturated monomers (b4) may also be included and copolymerized.

Here, the components derived from (b1), (b2), (b3), and (b4) The ratio is preferably in the range below with respect to the total weight of the copolymer component.

The component derived from (b1): 5 wt% to 40 wt% and more preferably 10 wt% to 30 wt%; the component derived from (b2): 5 wt% to 40 wt% and more preferably 10 wt% to 30 wt% %; component derived from (b3): 30% by weight to 80% by weight and more preferably 30% by weight to 75% by weight; and component derived from (b4): 0% by weight to 30% by weight and more preferably 0% by weight Up to 20% by weight.

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

The polymer (B2) is one or more types of repeating units selected from the following Chemical Formula 2 and Chemical Formula 3.

In Chemical Formula 2, R ₁ , R ₂ , R ₃ and R ₄ are each independently an organic residue having 1 to 20 carbon atoms and capable of containing a hydrogen atom, a halogen atom or an oxygen atom.

[Chemical Formula 3]

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

In the description of Chemical Formula 2 and Chemical Formula 3, the organic residue may include an aromatic organic residue, an aliphatic organic residue, an alicyclic organic residue, a heterocyclic organic residue, or an aromatic ring in the chain. An aliphatic organic residue, an alicyclic organic residue or a heterocyclic organic residue.

The polymer (B2) preferably accounts for 1% by weight to 99% by weight, more preferably 1% by weight to 50% by weight and still more preferably 1% by weight to 30% by weight based on the total weight of the binder resin (B). The above range is preferable because the degree of curing is improved, and therefore, the pattern is accurately formed when development is performed even in the case where the composition is high in the pigment content.

Further, in addition to the repeating unit of Chemical Formula 2 or Chemical Formula 3, the present invention may additionally include a carboxyl group-containing monomer and a copolymer having another monomer copolymerizable with the monomer.

Examples of the carboxyl group-containing monomer may include an unsaturated carboxylic acid such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated polyvalent carboxylic acid having one or more carboxyl groups in the molecule such as an unsaturated tricarboxylic acid. acid.

Specific examples of the unsaturated monocarboxylic acid may include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like.

Specific examples of the unsaturated dicarboxylic acid may include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like.

The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples thereof may include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester thereof, and specific examples thereof may include mono(2-propenyloxyethyl) succinate, single ( 2-methylpropenyloxyethyl) succinate, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl)phthalic acid Acid esters, etc. The both ends of the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer, and specific examples thereof may include ω-carboxy polycaprolactone monoacrylate, ω-carboxy polycaprolactone Methacrylate and the like.

The carboxyl group-containing monomer may be used singly or as a mixture of two or more types.

The copolymer (B3) is obtained by copolymerizing an aromatic vinyl compound (B'1), a compound having an unsaturated bond and an epoxy group in one molecule (B'2), and a compound of the following Chemical Formula 4 (B' 3) and get it.

More specifically, the copolymer (B3) includes a copolymer containing an unsaturated group by reacting the compound (B'3) represented by the following Chemical Formula 4 to pass through the aromatic vinyl compound (B'1) and It is obtained by copolymerizing a copolymer obtained by copolymerizing a compound (B'2) having an unsaturated bond and an epoxy group in one molecule.

[Chemical Formula 4]

In Chemical Formula 4, R ₁ and R ₂ are each independently a C1 to C6 alkyl group which is unsubstituted or substituted with one or more types selected from a halogen, a ketone group, an ester group, and a thiol group, and A is unsubstituted or An aliphatic polycyclic group substituted with one or more types selected from the group consisting of halogen, methoxy, and ethoxy; and unsubstituted or selected from the group consisting of allyl, halogen, methoxy, ethoxy, and C1 to One or more types of substituted aromatic polycyclic groups in the C8 alkoxy group; and N and m are each 0 or 1.

Specific examples of the aromatic vinyl compound (B'1, hereinafter also simply referred to as 'B'1') may include vinyl toluene, styrene, α-methylstyrene, α-chlorostyrene, vinyl Pyrrolidone, divinylbenzene, and the like, but are not limited thereto, and these may be used singly or in combination of two or more types. When considering the availability, reliability, and the like, it is more preferable to use vinyl toluene as the aromatic vinyl compound (B'1). In particular, the colored photosensitive resin composition containing the binder resin (B) prepared by including vinyl toluene as an aromatic vinyl compound has an advantage of effectively reducing the generation of outgas.

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 may include glycidyl (meth)acrylate, (methyl) 3,4-ethoxycyclohexyl acrylate, 3,4-ethoxycyclohexylmethyl (meth)acrylate, methyl glycidyl (meth)acrylate Oil esters and the like, but are not limited thereto, and these may be used singly or in combination of two or more types. In particular, glycidyl (meth)acrylate is excellent in preparation availability and reliability, and can be more preferably used.

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

Further, the compound of Chemical Formula 4 (B'3, hereinafter also simply referred to as 'B'3') is not particularly limited, however, one or more types selected from the compounds represented by the following Chemical Formula 5 to Chemical Formula 9 are used. Preferred.

[Chemical Formula 8]

According to the present invention, the binder resin (B) is preferably measured by gel permeation chromatography (GPC using tetrahydrofuran as an elution solvent) to have a polystyrene-equivalent weight average molecular weight (hereinafter also referred to simply as 'weight average molecular weight'). ') is a resin of 2,000 to 100,000, and more preferably a resin having a polystyrene-equivalent weight average molecular weight of 3,000 to 50,000. The weight average molecular weight is preferably in the above range because the film hardness is improved, the film retention rate is high, the storage stability is excellent, the solubility of the non-exposed unit in the developing solution is excellent, and the resolution is improved.

Further, the molecular weight distribution of the binder resin (B), that is, the weight average molecular weight is preferably compared with the number average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) in terms of developability and storage stability. It is from 1.5 to 6.0 and more preferably from 1.8 to 4.0.

The binder resin (B) preferably has an acid value of from 30 mgKOH/g to 170 mgKOH/g and more preferably from 50 mgKOH/g to 150 mgKOH/g based on the solid. The binder resin (B) having an acid value of less than 30 mgKOH/g is difficult to ensure a sufficient development rate because the colored photosensitive resin composition is not preferable, and the acid value is large. It is not preferable at 170 mgKOH/g because the pattern is liable to be short-circuited due to a decrease in adhesion to the substrate, and a problem of precipitation of the coloring agent in the colored photosensitive resin composition may occur due to the problem of compatibility with the coloring agent, or due to coloring The storage stability of the photosensitive resin composition is lowered, and the problem of an increase in viscosity may occur.

The binder resin (B) preferably accounts for 1% by weight to 85% by weight and more preferably 10% by weight to 70% by weight based on the solids in the colored photosensitive resin composition of the present invention. The content of the binder resin (B) from 1% by weight to 85% by weight based on the above criteria is preferable because development solubility is not easily exhibited on the non-pixel portion of the substrate due to sufficient solubility to the developing solution, and by preventing The film of the pixel portion of the exposure unit is reduced during development, and the loss of the non-pixel portion tends to be good.

(C) Photopolymerizable compound

The photopolymerizable compound (C) to be included in the coloring photosensitive resin composition of the present invention is a polymerizable compound of a reactive group, an acid or the like which is produced by light irradiation from a photopolymerization initiator (D) described below. And it is not particularly limited as long as it is a compound polymerizable by the action of the photopolymerization initiator. Preferably, a monofunctional monomer, a difunctional monomer or a trifunctional or higher polyfunctional monomer may be used, and one or more types of monomers selected therefrom may be used.

Specific examples of the monofunctional monomer may include nonylphenyl carbitol acetate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate An ester, N-vinylpyrrolidone or the like, and the commercial product thereof may include Aronix M-101 (Toagosei Co., Ltd.), KAYARAD TC-110S (Nippon Kayaku Co., Ltd.), Biscoat 158 (Osaka Yuki Kagaku Kogyo Co., Ltd.), and the like, but is not limited thereto.

Specific examples of the difunctional monomer may include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylic acid. Ester, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di Methyl) acrylate, propylene glycol dimethacrylate, urethane (meth) acrylate, etc., and the products thereof may include Aronix M-210, M-1100 or 1200 (Toagosei Co., Ltd.), KAYARAD HDDA (Nippon Kayaku Co., Ltd.), Biscoat 260 (Osaka Yuki Kagaku Kogyo Co., Ltd.), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.), etc., but not Limited to this.

Specific examples of the trifunctional or higher polyfunctional monomer may include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxy group Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta (methyl Acrylate, ethoxylated dipentaerythritol hexa(meth) acrylate, propoxylated dipentaerythritol hexa(meth) acrylate, dipentaerythritol hexa(meth) acrylate, etc., and its products may include Aronix M -309, TO-1382 (Toagosei Co., Ltd.), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku Co., Ltd.), etc., but is not limited thereto.

Among the photopolymerizable compounds exemplified above, the use of the three senses Energy- or higher polyfunctional monomers are more preferred, and (meth) acrylates and urethane (meth) acrylates are more in terms of their excellent polymerizability and ability to increase strength. Preferred.

The photopolymerizable compound (C) preferably accounts for 1% by weight to 50% by weight and more preferably 10% by weight to 35% by weight based on the solids in the colored photosensitive resin composition of the present invention. The photopolymerizable compound (C) in the range of 1% by weight to 50% by weight based on the above criteria is preferable because the strength or flatness of the pixel unit becomes advantageous.

(D) Photopolymerization initiator

The photopolymerization initiator (D) included in the coloring photosensitive resin composition of the present invention is produced by exposure to visible rays, ultraviolet rays, far ultraviolet rays, electron beams, and radiation such as X-rays, and is capable of eliciting the photopolymerizability described above. A compound such as a group polymerized with the compound (C).

The type of the photopolymerization initiator (D) is not particularly limited as long as it is a compound commonly used in the art within the range not impairing the object of the present invention and is capable of polymerizing the binder resin and the photopolymerizable compound. Typical examples thereof include an anthraquinone compound, an acetophenone compound, a benzoin compound, a benzophenone compound, a biimidazole compound, a triazine compound, a thioxanthone compound, an anthraquinone compound, etc., but Not limited to this, and one or more types can be selected and used. Among these, when a polymerization property, an initiation efficiency, an absorption wavelength, or the like is considered, it is more preferable to use a quinone compound.

Examples of the hydrazine compound may include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, (Z)-2-((benzylideneoxy)imido)- 1-(4-(benzene sulfur) (phenyl) oct-1-one (referred to as the following Chemical Formula 10), (E)-1-(((1-(9-ethyl-6-(2-methylbenzylidene)-9H-fluorene) Zyrid-3-yl)ethylidene)amino)oxy)ethanone (referred to as the following Chemical Formula 11), (E)-1-(((1-(6-(4-((2,2-) -1,3-dioxolan-4-yl)methoxy)-2-methylbenzhydryl)-9-ethyl-9H-carbazol-3-yl)ethylidene) Oxy) ethyl ketone (refer to the following Chemical Formula 12) and the like, and its commercial products may include OXE-01 and OXE-02 of BASF Corporation and the like, but are not limited thereto.

[Chemical Formula 12]

The content of the photopolymerization initiator (D) is not particularly limited, however, the photopolymerization initiator preferably accounts for 0.1% by weight to 40% by weight and more preferably 1% by weight with respect to the total solid weight in the colored photosensitive resin composition. Up to 30% by weight. The photopolymerization initiator content within the above range is preferable because the colored photosensitive resin composition becomes highly sensitive, shortens the exposure time, and therefore, improves productivity and maintains high resolution. In addition, the strength of the pixel unit formed using the colored photosensitive resin composition of the present invention and the flatness of the surface of the pixel unit can be advantageous.

Meanwhile, according to an embodiment of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiating auxiliary (d1) to enhance the sensitivity of the coloring photosensitive resin composition of the present invention. When the colored photosensitive resin composition of the present invention contains the photopolymerization initiation aid, productivity can be improved by further increasing sensitivity.

The example of the photopolymerization initiation aid (d1) may preferably include one or more types of compounds selected from the group consisting of an amine compound, a carboxylic acid compound, an organic sulfur compound having a thiol group, and an alkoxy fluorene compound. But it is not limited to this.

(E) solvent

The solvent (E) according to the present invention may use a solvent which is conventionally used in the art, and is not particularly limited as long as it is effective for dissolving other components included in the colored photosensitive resin composition. As a specific example of the solvent, one or more types selected from the group consisting of ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, guanamines, and the like can be used, however, the solvent is not limited thereto. .

Specific examples of the ether solvent may 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 II Alkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; and the like.

Specific examples of the acetate-based solvent may include alkylene glycol alkyl ether acetate 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 acetate such as methoxybutyl acetate and methoxypentyl acetate;

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

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

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

Specific examples of the ester solvent may include a cyclic ester such as γ-butyrolactone; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

Specific examples of the guanamine-based solvent may include N,N-dimethylformamidine Amine, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

The solvent (E) is preferably an organic solvent having a boiling point of from 100 ° C to 200 ° C, and more preferably includes an alkylene glycol alkyl ether acetate; a ketone; an ester such as 3- depending on coating properties and drying properties. Ethyl ethoxypropionate and methyl 3-methoxypropionate, and may more preferably include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionic acid 3 - Ethyl ester, methyl 3-methoxypropionate, and the like. These solvents may be used singly or as a mixture of two or more types.

The content of the solvent (E) included in the coloring photosensitive resin composition of the present invention is preferably from 30% by weight to 95% by weight and more preferably from 70% by weight to 85% by weight based on the total weight of the colored photosensitive resin composition of the present invention. . When the solvent (E) accounts for the above range, it is coated with a coating device such as a roll coater, a spin coater, a slit coater, a slit coater (sometimes referred to as a die coater), and an inkjet machine. When it is possible, an effect of favorable coating properties can be provided.

(F) additive

The coloring photosensitive resin composition of the present invention may further include an additive (F) other than the above components, such as a filler, other polymer compound, curing agent, according to the needs of those skilled in the art, without damaging the object of the present invention. , surfactants, adhesion promoters, antioxidants, deagglomerating agents, pigment dispersants and UV absorbers.

The surfactant may be used to further improve the film-forming property of the photosensitive resin composition, and specific examples of the surfactant may preferably include a fluorine-based surfactant, an organic quinone-based surfactant, and the like.

As a commodity, examples of the fluorine-based surfactant include, by DIC Megafac F-470, F-471, F-475, F-482, F-489, etc. manufactured by Corporation.

As a commercial product, examples of the organic terpene surfactant include DC3PA, DC7PA, SH11PA, SH21PA, SH-8400, and the like manufactured by Dow Corning Toray Silicone Co., Ltd., and manufactured by GE Toshiba Silicone Co., Ltd. TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, and the like.

The surfactants exemplified above may be used singly or as a mixture of two or more types.

The pigment dispersant is a component which can be added for depolymerization of the pigment (a1) and maintaining stability. One example of the method of uniformly dispersing the particles of the pigment (a1) includes dispersion treatment by adding a pigment dispersant, and a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.

As the pigment dispersant, those generally used in the art can be used without limitation.

An example of a method of preparing the colored photosensitive resin composition of the present invention can be described as follows.

First, the pigment (a1) in the colorant (A) is mixed and dispersed with a solvent (E) by a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. Here, the pigment dispersant, a part or all of the binder resin (B), or the dye (a2) may be mixed with the solvent (E) and dissolved or dispersed, as needed.

Further, the dye (a2), the remaining binder resin (B), the photopolymerizable compound (C), and the photopolymerization initiator (D) are further added to the mixed dispersion. The additive (F) and the solvent (E) are required to have a specific concentration, and a colored photosensitive resin composition according to the present invention can be prepared.

Further, the present invention includes a colored pattern prepared using the colored photosensitive resin composition. The colored pattern can be prepared by applying the colored photosensitive resin composition of the present invention on a substrate, and photocuring and developing the resultant. The thickness of the colored pattern is not particularly limited, and may be, for example, from 1 μm to 6 μm.

<Color Filter>

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

As a method of manufacturing the color filter, a general method well known in the art can be used.

<Image display device>

The present invention also provides an image display device including the color filter. Specific examples of the image display device may include display devices such as a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device of a game machine, and a portable terminal such as a mobile device Display device of a telephone, display device of a digital camera, display device of a car navigation, etc., and a color display device is particularly suitable of.

In addition to providing the color filter, the image display device includes a configuration known to those skilled in the art, in other words, the present invention includes an image display device capable of using the color filter of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples are for illustrative purposes only, and the present invention is not limited to the following examples, and may be variously modified and changed within the scope of the invention. The scope of the invention is determined by the technical idea of the scope of the patent application described later.

Further, "%" and "parts" indicating the contents in the following Preparation Examples, Examples and Comparative Examples are based on the weight unless otherwise specifically stated.

<Synthesis Example>

<Synthesis Examples 1 to 6>

150 parts by weight of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermostat, a reflux cooling tube, a dropping lot, and a nitrogen introduction tube, and after the atmosphere in the flask was converted from air to nitrogen , raise the temperature to 100 °C. Thereafter, the binder resin was synthesized according to each of Synthesis Examples 1 to 6.

Synthesis Example 1. Adhesive Resin B-1

15 parts by weight of methacrylic acid, 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 And after 2.5 parts by weight of α-methylstyrene dimer (chain transfer agent), 1 part by weight of 2,2'-azobis (2,4) was dropped from the dropping funnel to the flask over 2 hours. - dimethyl valeronitrile) added to 50 weights The solution in propylene glycol monomethyl ether acetate was weighed and the resultant was further stirred at 100 ° C for 5 hours.

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

Synthesis Example 2. Adhesive Resin B-2

15 parts by weight of methacrylic acid, 25 parts by weight of N-benzyl maleimide, 35 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 15 parts by weight of styrene And after 2.5 parts by weight of α-methylstyrene dimer (chain transfer agent), 1 part by weight of 2,2'-azobis (2,4) was dropped from the dropping funnel to the flask over 2 hours. - dimethyl valeronitrile) was added to 50 parts by weight of a solution of propylene glycol monomethyl ether acetate, and the resultant was further stirred at 100 ° C for 5 hours.

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

Synthesis Example 3. Adhesive Resin B-3

15 parts by weight of methacrylic acid, 10 parts by weight of ω-carboxydicaprolactone monoacrylate, 25 parts by weight of N-phenylmaleimide, 35 parts by weight of benzyl methacrylate, 10 parts by weight a portion of glycerol monomethacrylate, 15 parts by weight of styrene and 2.5 parts by weight of α-methylstyrene dimer (chain transfer agent), then drip from the dropping funnel to the flask over 2 hours. 1 part by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added to 50 parts by weight of a solution of propylene glycol monomethyl ether acetate, and the resultant was further stirred at 100 ° C. hour.

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

Synthesis Example 4. Adhesive Resin B-4

15 parts by weight of methacrylic acid, 10 parts by weight of mono((2-methylpropoxy oxyethyl) succinate, 25 parts by weight of N-phenylmaleimide, 25 parts by weight of methyl group After benzyl acrylate, 25 parts by weight of styrene, and 2.5 parts by weight of α-methylstyrene dimer (chain transfer agent), 1 part by weight of 2 was dropped from the dropping funnel into the flask over 2 hours. A solution of 2'-azobis(2,4-dimethylvaleronitrile) was added to 50 parts by weight of propylene glycol monomethyl ether acetate, and the resultant was further stirred at 100 ° C for 3 hours.

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

Synthesis Example 5. Adhesive 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 After 15 parts by weight of 2-hydroxyethyl methacrylate and 2.5 parts by weight of α-methylstyrene dimer (chain transfer agent), 1 weight was dropped from the dropping funnel to the flask over 2 hours. A solution of 2,2'-azobis(2,4-dimethylvaleronitrile) was added to 50 parts by weight of propylene glycol monomethyl ether acetate, and the resultant was further stirred at 100 ° C for 3 hours.

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

Synthesis Example 6. Adhesive Resin B-6

15 parts by weight of methacrylic acid, 10 parts by weight of ω-carboxydicaprolactone monoacrylate, 15 parts by weight of N-phenylmaleimide, 33 parts by weight of 2-ethylhexyl methacrylate After ester, 12 parts by weight of styrene, 15 parts by weight of glycerol monomethacrylate, and 2.5 parts by weight of α-methylstyrene dimer (chain transfer agent), the dropping funnel was used for 2 hours. The flask was dropped with a solution of adding 1 part by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate, and the resultant was at 100 ° C. Stirring was continued for another 3 hours.

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

Synthesis Example 7. Adhesive Resin B-7

To a 4-necked flask equipped with a dropping funnel, a thermostat, a cooling tube, and a stirrer, 23.3 g of methyl-2-(bromomethyl)acrylate (product of Sigma-Aldrich Co. LLC), 15.8 g was added. Triethylamine (product of Sigma-Aldrich Co. LLC.) and 115.0 g of propylene glycol monomethyl ether (product of TCI Co., Ltd.), and the inside of the 4-necked flask was replaced with nitrogen. Next, the flask was heated to 90 ° C, and 15.1 g of methyl-2-(hydroxymethyl)-acrylate (product of Sigma-Aldrich Co. LLC.), 3.2 g was added dropwise thereto over 1 hour. 2,2'-azobisisobutyronitrile (product of Wako Pure Chemical Industries, Ltd.) and 110.0 g of propylene glycol monomethyl ether (product of TCI Co., Ltd.) The solution was subjected to a polymerization reaction for 30 minutes to produce a pyran-containing polymer. Then, 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 225.0 g of propylene glycol monomethyl ether, and 3.2 g of 2,2'-azobisisobutyronitrile were slowly added dropwise thereto over 1 hour. A mixed solution of (a product of Wako Pure Chemical Industries, Ltd.) was subjected to polymerization for 8 hours, and then the resultant was allowed to cool to room temperature.

After replacing the inside of the 4-necked flask with nitrogen, 61.5 g of glycidyl methacrylate (product of Mitsubishi Rayon) and 3.6 g of tetra-n-butylammonium bromide (TCI Co., Ltd.) were added to the flask. Product) and 0.15 g of methoquinone (product of Junsei Chemical Co., Ltd.), and the product was reacted at 80 ° C for 12 hours to add glycidyl methacrylate to the carboxyl group of the copolymer. The ester (GMA), thus, the binder resin B-7 was obtained.

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

Synthesis Example 8. Adhesive Resin B-8

To a 4-necked flask equipped with a dropping funnel, a thermostat, a cooling tube, and a stirrer, 37.5 g of methacrylic acid (product of Kyoeisha Chemical Co., Ltd.) and 19.0 g of methyl methacrylate (Kyoeisha Chemical Co) were added. .product of Ltd.), 9.1 g of 2,5-dihydrofuran (product of TCI Co., Ltd.) and 225.0 g of propylene glycol monomethyl ether (product of TCI Co., Ltd.), and replaced with nitrogen The inside of the 4-necked flask. Next, the flask was heated to 70 ° C, and 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 9.1 g of 2,5-dihydrofuran, 225.0 g were slowly added dropwise thereto over 1 hour. Propylene glycol monomethyl ether and 3.2 g of 2,2'-azobisisobutyronitrile (Wako Pure Chemical A mixed solution of the product of Industries, Ltd.). After 8 hours of polymerization, the resultant was left to cool to room temperature, and the inside of the 4-necked flask was replaced with nitrogen, and then 61.5 g of glycidyl methacrylate (product of Mitsubishi Rayon), 3.6 g was added to the flask. Tetra-n-butylammonium bromide (product of TCI Co., Ltd.) and 0.15 g of formazan (product of Junsei Chemical Co., Ltd.), and the resultant was reacted at 80 ° C for 12 hours to The carboxyl group of the copolymer was added with glycidyl methacrylate (GMA), and thus, a binder resin B-8 was obtained.

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

Synthesis Example 9. Adhesive Resin B-9

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermostat, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, and after the atmosphere in the flask was converted from air to nitrogen, the temperature was raised to 80 ° C. 3.6 g of azobisisobutyronitrile was added to a mixture comprising 85.2 g (0.6 mol) of glycidyl methacrylate, 23.6 g (0.2 mol) of vinyl toluene and 136 g of propylene glycol monomethyl ether acetate. The solution was dropped from the dropping funnel into the flask over 2 hours, and the resultant was further stirred at 80 ° C for further 5 hours. Then, the atmosphere in the flask was switched from nitrogen to air, and 29.6 g [0.6 mol (relative to the epoxy group of glycidyl methacrylate used in the reaction was 33.33 mol%)] The compound, 0.9 g of trimethylaminomethylphenol and 0.145 g of hydroquinone were introduced into the flask, and the resultant was further reacted at 110 ° C for 4 hours to obtain a binder resin B-9. The polystyrene-equivalent weight average molecular weight measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Synthesis Examples 10 to 13. Adhesive Resins B-10 to B-13

The binder resin was prepared in the same manner as in Synthesis Example 9, except that the respective components and contents were changed as shown in Table 1 below.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder polymer was carried out by the GPC method under the following conditions: Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL+TSK-GELG2000HXL (series)

Column temperature: 40 ° C

Moving solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Injection volume: 50μl

Detector: RI

Measuring 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 and the number average molecular weight obtained above is used in a molecular weight distribution (Mw/Mn).

Preparation of coloring 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.

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

Example 1.

Preparation of liquid composition (G1)

40 parts by weight of a 60/40 (by weight) mixture of CI Pigment Green 59 (manufacturer: DIC Corporation) and CI Pigment Yellow 185 as a pigment, and 24 parts by weight (about 10.8 parts by weight in terms of solids) as a dispersing agent BYK A mixed liquid of 2001 (DISPER BYK: manufactured by BYK Chemie, solid concentration: 45.1% by weight) and 136 parts by weight of propylene glycol monomethyl ether acetate as a solvent was mixed/dispersed by a bead mill for 12 hours to prepare a pigment dispersion liquid.

Subsequently, 400 parts by weight of the obtained pigment dispersion liquid, 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, and 40 parts by weight were used as light. 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone as a polymerization initiator -1, and 1000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (G1).

Examples 2 to 6.

Preparation of liquid compositions (G2 to G6)

200 parts by weight of the resin solution (B-2) (Example 2), 200 parts by weight of the resin solution (B-3) (Example 3), 200 parts by weight of the resin solution (B-4) (Example 4), 200 parts by weight of the resin solution (B-6) (Example 5) or 200 parts by weight of the resin solution (B-5) (Example 6) instead of 200 parts by weight of the resin solution (B-1) as a binder resin, liquid The compositions (G2 to G6) were prepared in the same manner as in Example 1.

Example 7.

Preparation of liquid composition (G7)

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

Example 8.

Preparation of liquid composition (G8)

The 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) as the binder resin.

Example 9.

Preparation of liquid composition (G9)

The 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) as the binder resin.

Comparative Example 1.

Preparation of liquid composition (g1)

In place of 40 parts by weight of a mixture of CI Pigment Green 7 and CI Pigment Yellow 185 (weight ratio of 56:44) instead of 40 parts by weight of the CI Pigment Green 59 (manufacturer: DIC Corporation) and CI Pigment Yellow 185 60/ The liquid composition (g1) was prepared in the same manner as in Example 1 except that a 40 (by weight) mixture was used as the pigment.

Comparative Example 2.

Preparation of liquid composition (g2)

In place of 40 parts by weight of a mixture of CI Pigment Green 7 and CI Pigment Yellow 150 (weight ratio 55:45) instead of 40 parts by weight of a 60/40 (by weight) mixture of the CI Pigment Green 59 and CI Pigment Yellow 150 as In addition to the pigment, the liquid composition (g2) was prepared in the same manner as in Example 7.

<Examples 10 to 18 and Comparative Examples 3 to 5>

<Test Example> Evaluation of Colored Photosensitive Resin Composition

<Test Examples 1 to 3>

Pixel pattern formation

A 2 square inch glass substrate (manufactured by Corning Incorporated, #1737) was successively washed with a neutral detergent, water and alcohol, and then dried. Each of the compositions of Examples 1 to 9 and Comparative Examples 1 and 2 was spin-coated on the glass substrate such that when exposed with an exposure amount of 100 mJ/cm ² (365 nm) and the color development process was skipped, after post-baking The film thickness became 2.0 μm, and then the resultant was preliminarily dried at 100 ° C for 3 minutes in a clean oven. After cooling, the colored photosensitive resin composition was coated between a substrate and a photomask made of quartz glass (a pattern having a transmittance changed from 1 to 100% in a stepwise manner and a line/void pattern of 1 μm to 50 μm) The distance was kept at 100 μm, and an ultrahigh pressure mercury lamp (product name USH-250D) manufactured by USHIO Inc. was irradiated with light of an exposure amount (365 nm) of 100 mJ/cm ² under an atmospheric atmosphere.

Thereafter, the film was developed by immersion in a developing aqueous solution containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C for a fixed period of time, and then the resultant was washed, followed by drying at 220 ° C for 30 minutes.

Test Example 1. Brightness measurement

The brightness was measured using a microspectrometer OSP-SP2000, and the brightness values at the same color coordinates are listed in Table 3 below.

Test Example 2. Evaluation of color coordinates

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

Test Example 3. Contrast evaluation

The substrate obtained above was placed between two polarizing plates, and the maximum value of the light intensity was measured while irradiating the fluorescent light (wavelength range 380 nm to 780 nm) from the rear side using a BM-5A type contrast measuring device manufactured by Topcon Korea Corporation. The minimum value, the contrast is evaluated by dividing the maximum value by the value of the minimum value. The measurement standard is based on a comparison of 1/30000 of the glass substrate (before the formation of the colored layer).

Further, after storing at 23 ° C for one month, the contrast was evaluated in the same manner using various liquid compositions (G1 to G9, g1 and g2), and the results are shown in Table 3 below.

<Test Examples 4 to 7>

Each of the photocurable resin compositions prepared in Examples 10 to 13 and Comparative Examples 3 and 4 was coated on a 50 mm × 50 mm glass substrate while controlling the number of revolutions by a spin coater so that the film thickness after drying became 2.5 μm. The resultant was dried in an oven at 100 ° C for 3 minutes.

The dried substrate was exposed such that the integrated exposure amount of the fusion lamp became 40 mJ at a distance of 300 μm from the photomask, and a color filter was fabricated.

Thereafter, the tests were carried out by the respective methods described in Test Examples 4 to 7.

Test Example 4. Sensitivity evaluation

Thereafter, the color filter was developed with a spray developing device with a pH 10.5 KOH aqueous solution for 1 minute, rinsed and air-dried. Thereafter, the resultant was cured in an oven at 230 ° C for 20 minutes, and the pattern line width and the degree of pattern peeling in the color filter were measured.

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

<Linewidth Evaluation Criteria>

+5 or higher: suitable

Greater than or equal to -5 and less than +5; good

Less than -5: not suitable

<Pattern peeling evaluation standard>

○: no pattern peeling

△: 1 to 3 pattern peeling

X: 4 or more pattern peeling

Test Example 5. Evaluation of solvent resistance

Thereafter, the color filter was developed with a spray developing device with a pH 10.5 KOH aqueous solution for 1 minute, rinsed and air-dried. Thereafter, the resultant was cured in an oven at 230 ° C for 20 minutes. The color filter was immersed in an NMP solution at room temperature for 30 minutes, washed with ultrapure water, and dried on a hot plate heated to 120 ° C for 2 minutes, and the color before and after the immersion was measured. The equation used here is calculated by the following Mathematical Formula 1, which indicates discoloration in a 3-dimensional colorimeter defined by L*, a*, and b*, and can be manufactured high because of small coloration Reliability color filter. The results are shown in Table 4 below.

[Math 1] △Eab*=[(△L*)2+(△a*)2+(△b*)2]^0.5

<Solvent resistance evaluation standard>

△Eab* is 3 or smaller: suitable

△Eab* is greater than 3: not suitable

Test Example 6. Evaluation of the degree of reverse taper

Thereafter, the color filter was developed with a spray developing device with a pH 10.5 KOH aqueous solution for 1 minute, rinsed and air-dried. Thereafter, the end of the produced pattern was measured by a scanning electron microscopy (HITACHI S4300) to measure the degree of the reverse taper. As the measurement, the length of the portion where the groove was formed from the end toward the inside of the pattern was measured and compared. The results are shown in Table 4 below.

Test Example 7. Brightness evaluation

Thereafter, the color filter was developed with a spray developing device with a pH 10.5 KOH aqueous solution for 1 minute, rinsed and air-dried. Thereafter, the resultant was cured in an oven at 230 ° C for 20 minutes. Brightness using microspectrometer OSP-SP2000 The measurement lists the brightness values at the same color coordinates (x = 0.260, y = 0.640). The results are shown in Table 4 below.

<Test Examples 8 to 11>

The colored photosensitive resin compositions each prepared in Examples 14 to 18 and Comparative Example 5 were coated on a glass substrate (#1737, manufactured by Corning Incorporated) by spin coating, and the resultant was placed on a hot plate at 100 The temperature was maintained at °C for 3 minutes to form a film.

Subsequently, a 1 KW high-pressure mercury vapor lamp containing all of g, h, and i rays was used as an ultraviolet light source, and light was irradiated onto the film at an intensity of 100 mJ/cm ² . Here, no special filters are used. The ultraviolet-irradiated film was immersed in a developing solution of a KOH aqueous solution of pH 10.5 for 2 minutes for development.

The film-coated glass substrate was washed with distilled water, then dried with nitrogen gas, and heated in a heating furnace at 220 ° C for 30 minutes to produce a colored layer. The coloring layer produced above has a thickness of from 1 μm to 5 μm.

Test Example 8. Evaluation of heat resistance

After the pattern was finally formed, the discoloration (heat resistance) before and after 230 ° C / 2 hr was compared and evaluated. Here, the change in the calculated Eab to 1 or less is determined to be excellent, 3 or less is good, and more than 3 is bad.

The equation used here is calculated by the following <Formula 1>, which represents the discoloration in the 3-dimensional colorimeter defined by L*, a*, and b*, and because of the small discoloration, Create high-reliability color filters. The results are shown in Table 5 below.

<Math 1>△Eab*=[(ΔL*)2+(Δa*)2+(△b*)2]1/2

Test Example 9. Developmentability evaluation

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

<developability evaluation standard>

○: 2 minutes or less

△: longer than 2 minutes and shorter than or equal to 4 minutes

X: longer than 4 minutes and stripped

Test Example 10. Evaluation of development residue

No development residue on the substrate is listed as '○', and development occurs on the substrate. The column of the residue is '×'. The results are shown in Table 5 below.

Test Example 11. Brightness measurement

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

As shown in Table 3, it can be seen that based on the same color coordinates, when G59 is used, the index of transmittance, the brightness Y, is increased by 7.0% to 8.0% as compared with the case of using CI Pigment Green 7 (G7). .

In addition, when compared with the comparative example having the same color coordinates, the contrast is also improved by 300 to 3000, and even after storage for one month at 23 ° C, the rate of decrease in contrast is small, indicating that high contrast is maintained, therefore, It was confirmed that it has stability over time.

From the results of Table 4, it was confirmed that the colored photosensitive resin compositions of Examples 10 to 13 included in the scope of the present invention had excellent evaluation results in sensitivity, solvent resistance and brightness, and also exhibited inverted cones. Less than the shape Excellent results of 1.5μm. Meanwhile, the colored photosensitive resin compositions of Comparative Examples 3 and 4 had poor results in sensitivity, solvent resistance, reverse taper, and brightness evaluation.

In Table 5, it was confirmed that the color filter formed using the colored photosensitive resin compositions of Examples 14 to 18 included in the scope of the present invention had excellent heat resistance and developability, and no development residue appeared. At the same time, it was confirmed that the evaluation results of the brightness and the development residue in particular were not excellent in Comparative Example 5.

In other words, the colored photosensitive resin composition of the present invention is a composition having high luminance properties, high coloring properties, and high sensitivity while having a target color coordinate value and having excellent heat resistance and solvent resistance.

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

In addition, it is possible to provide a picture element having excellent light transmittance and excellent contrast, an effect of improving reliability by improving the degree of curing, and an effect of reducing the reverse taper.

Further, a color filter and an image display device prepared using the colored photosensitive resin composition can be provided.

Claims (12)

A colored photosensitive resin composition comprising: 5% by weight to 85% by weight of a coloring agent (A) with respect to a solid in the colored photosensitive resin composition; and 1% by weight to 85% by weight of a binder resin (B) 1% by weight to 50% by weight of the photopolymerizable compound (C); 0.1% by weight to 40% by weight of the photopolymerization initiator (D); and 30% by weight based on the total weight of the colored photosensitive resin composition To 95% by weight of the solvent (E), wherein the colorant (A) comprises CI Pigment Green 59, and one or more types selected from the group consisting of pigments and dyes, wherein the binder resin (B) comprises a copolymer selected from the group consisting of One or more types of B1), polymer (B2) and copolymer (B3), the copolymer (B1) comprises a copolymer of (meth)acrylic acid (b1); N-substituted maleimide (b2) And one or more types of unsaturated compounds (b3) selected from the group consisting of styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, methyl (meth)acrylate, (methyl) ) n-butyl acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, mono (methyl) ) glyceryl acrylate, mono [2-(methyl) propylene methoxyethyl] succinate, ω-carboxy polycaprolactone mono (meth) acrylate, polystyrene macromonomer and polymethyl a methyl acrylate macromonomer; the polymer (B2) is one or more types of repeating units selected from the following Chemical Formula 2 and Chemical Formula 3; the copolymer (B3) is a copolymerized aromatic vinyl compound (B'1) a copolymer obtained by a compound (B'2) having an unsaturated bond and an epoxy group in one molecule, and a compound (B'3) of the following chemical formula 4, wherein the binder resin (B) comprises copolymerization And (B3), and the ratio of the constituent units derived from the (B'1) is 20 mol% to 60 mol% with respect to the total mol number of the constituent units of the copolymer (B3); and derived from the (B'2) The ratio of constituent units is 20 mol% to 60 mol%: Wherein, in Chemical Formula 2, R ₁ , R ₂ , R ₃ and R ₄ are each independently an organic residue having 1 to 20 carbon atoms and capable of containing a hydrogen atom, a halogen atom or an oxygen atom, In Chemical Formula 3, R ₅ , R ₆ , R ₇ and R ₈ are each independently an organic residue having 1 to 20 carbon atoms and capable of containing a hydrogen atom, a halogen atom or an oxygen atom. In Chemical Formula 4, R ₁ and R ₂ are each independently a C1 to C6 alkyl group which is unsubstituted or substituted with one or more types selected from a halogen, a ketone group, an ester group, and a thiol group, and A is unsubstituted or An aliphatic polycyclic group substituted with one or more types selected from the group consisting of halogen, methoxy, and ethoxy; and unsubstituted or selected from the group consisting of allyl, halogen, methoxy, ethoxy, and C1 to One or more types of substituted polycyclic groups in the C8 alkoxy group; and n and m are each 0 or 1. The colored photosensitive resin composition of claim 1, wherein the binder resin (B) comprises the copolymer (B1), and comprises: from 5% by weight to 40% by weight based on the total weight of the copolymer (B1) The component of (b1); from 5% by weight to 40% by weight of the component derived from the component (b2); and from 30% by weight to 80% by weight of the component derived from the component (b3). The colored photosensitive resin composition of claim 1, wherein the binder resin (B) comprises a polymer (B2), and the polymer (B2) is relative to The total weight of the binder resin is from 1% by weight to 99% by weight. The colored photosensitive resin composition of claim 1, wherein the ratio of the constituent units derived from the (B'3) is from 20 mol to 120 mol with respect to 100 mol of the epoxy group of the (B'2). The colored photosensitive resin composition of claim 1, wherein the binder resin (B) has a weight average molecular weight of from 2,000 to 100,000. The colored photosensitive resin composition of claim 1, wherein the C.I. Pigment Green 59 accounts for 0.05% by weight to 50% by weight based on the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition of claim 1, wherein the C.I. Pigment Green 59 and the one or more selected from the group consisting of pigments and dyes are included in a weight ratio of 1:0.050 to 1:18.0. The colored photosensitive resin composition of claim 1, wherein the C.I. Pigment Green 59 has a Tmax of from 500 nm to 530 nm. The colored photosensitive resin composition of claim 1, wherein the CI Pigment Green 59 has a T _{50% of} 445 nm to 580 nm. The colored photosensitive resin composition of claim 1, which has a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more in the XYZ chromaticity system. A color filter comprising a colored pattern prepared by the colored photosensitive resin composition according to any one of claims 1 to 10. An image display device comprising a color filter as in claim 11.