TWI674298B - Colored photosensitive resin composition, color filter and image display device using the same - Google Patents

Abstract

The invention relates to a colored photosensitive resin composition, a color filter manufactured using the composition, and an image display device including the color filter. The colored photosensitive resin composition includes a colorant (A) and a binder resin. (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E); wherein the colorant (A) includes CI Pigment Green 59, and one or more selected from pigments and dyes; and The polymerization initiator (D) includes one or more selected from a phenyl-based oxime initiator and a carbazole-based oxime initiator.

Description

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

The present invention relates to a coloring photosensitive resin composition, a coloring pattern formed using the resin composition, a color filter including the coloring pattern, and an image display device having the color 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 application range is rapidly increasing. The color filters used in the imaging device, the liquid crystal display device, and the like are formed with colored patterns of three colors of red, green, and blue, or formed with colored patterns of three colors of yellow, magenta, and cyan.

Each colored pattern of the color filter is generally 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. Processing of a colored pattern using the colored photosensitive resin composition is generally performed by a photolithography method.

Recently, in order to improve workability and product quality, Color filters used in various display devices including solid-state image devices such as digital cameras and liquid crystal display devices (LCD) have high brightness and high colorability.

Meanwhile, 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 colorability are not satisfied at the same time.

[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 foregoing, and an object of the present invention is to provide a coloring photosensitive resin composition having excellent brightness and excellent coloring properties and having high sensitivity.

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 including a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein The colorant (A) includes CI Pigment Green 59, and one or more selected from pigments and dyes; and the photopolymerization initiator (D) includes a phenyl-based oxime initiator and a carbazole-based One or more of the oxime initiators.

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

Another aspect of the present invention provides an image display device including the color filter.

FIG. 1 is a graph showing a transmittance spectrum of each colorant.

Detailed description of the preferred embodiment

The present invention provides a colored photosensitive resin composition including a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the coloring The agent (A) includes a compound represented by the following Chemical Formula 1, and one or more selected from pigments and dyes; and the photopolymerization initiator (D) includes a phenyl-based oxime initiator and a carbazole-based One or more of the oxime initiators.

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

Hereinafter, the colored photosensitive resin group forming the present invention will be described. The components of the composition. However, the present 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 a pigment (a1). The compound represented by the following Chemical Formula 1 has a zinc phthalocyanine (ZnPc) structure. The colorant (A) of the present invention including a compound represented by the following Chemical Formula 1 has an advantage of high color reproduction.

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

Preferred examples of the compound represented by Chemical Formula 1 may include C.I. Pigment Green 59 (hereinafter, also referred to as 'G59').

C.I. Pigment Green 58 (G58) has the advantage of having high brightness, however, In order to achieve high colorability, the pigment content is increased, and when such a large amount of the pigment is included in the composition, problems may occur, such as a decrease in developability, a pattern formed with the composition has a risk of peeling, and a decrease in sensitivity .

However, the present invention can design a resist capable of highly color reproduction even with a small pigment content by using a pigment represented by Chemical Formula 1, particularly G59 as a colorant.

Meanwhile, the inclusion of C.I. Pigment Green 7 (G7) in the resin composition is advantageous because high colorability can be obtained even at a low pigment content, but it has a problem of low brightness. However, the compound of the chemical formula 1, particularly G59, included in the colored photosensitive resin composition of the present invention functions to exhibit excellent brightness when included in the colored photosensitive resin composition, and at the same time to exhibit CI pigment green 7 Similar transmittance spectrum and color coordinates when used as a pigment. As indicated in FIG. 1, the transmittance spectrum of C.I. Pigment Green 59 at a wavelength of 400 nm to 610 nm is similar to that of C.I. Pigment Green 7.

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

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 coloring sensitivity of the compound of the chemical formula 1 with respect to the present invention The total weight of the resin composition preferably accounts for 0.05 to 30% by weight, more preferably 0.05 to 25% by weight and still more preferably 0.05 to 20% by weight. The compound of the chemical formula 1 based on the above-mentioned standards occupying a range of 0.05% to 30% by weight is preferable because a resist having high brightness and excellent coloring properties can be obtained.

The colorant (A) according to the present invention includes, in addition to the compound of Chemical Formula 1, a pigment selected from components generally used in the art as a component capable of exhibiting a color such as red, green, or blue in order to prepare a pattern having a target color. And dyes, and these can be prepared in the form of a paint paste.

In the composition of the present invention, the compound represented by Chemical Formula 1 and the one or more selected from pigments and dyes are preferably in a weight ratio of 1: 0.050 to 1: 18.0, more preferably 1: 0.1 to 1: 9. And more preferably 1: 0.2 to 1: 4 are included. Including the above-mentioned weight ratio, it is preferable because of improved processing margin and excellent sensitivity, and exhibiting high colorability and high brightness.

In this case, the coloring agent including the compound according to Chemical Formula 1 as a pigment in the XYZ chromaticity system may have a color coordinate of x = 0.1 to 0.35 when y = 0.6 or higher.

Meanwhile, when G58 is used as an example, a color coordinate 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 use G58 to have a value close to x = 0.1, it is necessary to include a mixed color with blue, and this is not preferable due to the problem of decreased brightness.

When G7 is used as another example, the area that can show color The domain can be large, but has the problem of low brightness.

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

The organic pigment may be: rosin-treated; surface-treated with a pigment derivative that introduces an acidic group or a basic group; graft-treated with a polymer or the like on the pigment surface; sulfuric acid powdering method, etc. Powdered; or washed with organic solvents or water to remove impurities.

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 a more specific example 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 so on.

Specific examples of the pigment (a1) may more preferably include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists), and more specifically include compounds consisting of Color Index (CI) number exemplified pigments. However, the pigment is not limited thereto, and one or more kinds selected therefrom may be co-dispersed with a binder resin, a dispersant, or the like for use in order to obtain a target chromaticity.

Specific examples of CI Pigment Yellow can 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 .; CI pigment blue Specific examples 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 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 preferable.

Dye (a2)

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

As the dye (a2), an acid dye selected from an acid dye having an acid group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, an acid One or more of sulfonamide and the like of the dye, and derivatives thereof. In addition to these, the dye may be selected from azo-based, xanthene-based, and phthalocyanine-based acid dyes, and derivatives thereof.

The dye (a2) may preferably include a compound classified as a dye in a color index (published by The Society of Dyers and Colourists) or described in a Dye Note (Color and Dye Corporation) Of known dyes.

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 red 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; C.I. Solvent Green 3, C.I. Solvent Green 5 and C.I. Solvent Green 7, and the like, but are not limited thereto.

The colorant (A) may preferably account for 5 to 70% by weight and more preferably 10 to 50% by weight with respect to the solid in the colored photosensitive resin composition of the present invention. When the content of the colorant (A) is less than 5% by weight, the formed pattern may have reduced color separation ability, and when the content is more than 70% by weight, the lithographic efficiency may decrease, resulting in residues or Problems like development.

The solid content in the colored photosensitive resin composition in the present invention refers to 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 colored photosensitive resin composition of the present invention is a component that provides solubility to an alkali developing solution used in the developing process. In the present invention, the binder resin is not particularly limited, but is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.

The monomer having a carboxyl group is not particularly limited, and specific examples thereof may include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and carboxyl groups at both ends Mono (meth) acrylates of polymers with hydroxyl groups such as ω-carboxy polycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are more preferred. One or more of these can be selected and used.

The copolymerizable other monomer is not particularly limited as long as it is a monomer having a carbon-carbon unsaturated bond, and specific examples thereof may include aromatic compounds. Group vinyl compounds such as styrene, α-methylstyrene and vinyl toluene; unsaturated carboxylic acid ester compounds such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, and benzyl methacrylate; unsaturated amino alkyl carboxylic acid ester compounds such as amino ethyl acrylate; not Saturated glycidyl carboxylate compounds such as glycidyl methacrylate; vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; Unsaturated oxetane carboxylate compounds such as 3-methyl-3-propenyloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane Alkane, 3-ethyl-3-propenyloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-propene Ethoxyethyloxetane, 3-methyl-3-methacryl ethoxyethyloxetane, 3-methyl -3- Bing Xixi yloxy ethyloxetane and 3-ethyl-3-methyl oxetane Bing Xixi yloxy, and the like. These monomers may be used alone or as a combination of two or more.

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

The binder resin (B) preferably has an acid value of 30 mgKOH / g to 170 mgKOH / g and more preferably 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 not preferable because it is difficult to ensure a sufficient development rate for the colored photosensitive resin composition. And an acid value greater than 170 mgKOH / g is not preferable because the pattern is prone to short circuit due to reduced adhesion to the substrate, and the problem of colorant precipitation in the colored photosensitive resin composition may occur due to the compatibility with the colorant Or, because the storage stability of the colored photosensitive resin composition is reduced, a problem that viscosity increases may occur.

The binder resin (B) preferably accounts for 5 to 85% by weight and more preferably 10 to 70% by weight with respect to the solid in the colored photosensitive resin composition of the present invention. The content of the binder resin (B) from 5% to 85% by weight based on the above-mentioned standards is preferable because it is difficult to cause development residues on the non-pixel portion of the substrate due to sufficient solubility in 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) included in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by an active group, an acid, or the like, which is generated by light irradiation from a photopolymerization initiator (D) described later, and There is no particular limitation 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 acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate Esters, N-vinylpyrrolidone, etc., and their products 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 are not limited thereto.

Specific examples of the bifunctional monomer may include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate Esters, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, 3-methylpentanediol bis (methyl) Base) acrylate, propylene glycol dimethacrylate, urethane (meth) acrylate, etc., and its products 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 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 not limited thereto.

Among the photopolymerizable compounds exemplified above, the use of a trifunctional or higher polyfunctional monomer is more preferable, and in terms of their excellent polymerizability and ability to improve strength, (meth) acrylates and Urethane (meth) acrylate is more preferred.

The photopolymerizable compound (C) preferably accounts for 5 to 45% by weight and more preferably 10 to 35% by weight with respect to the solid in the colored photosensitive resin composition of the present invention. The photopolymerizable compound (C) which occupies a range of 5% to 45% by weight based on the above criteria is preferable because the strength or flatness of the pixel unit becomes favorable.

(D) Photopolymerization initiator

The photopolymerization initiator (D) included in the colored photosensitive resin composition of the present invention is capable of generating the binder resin (B) and the photopolymerizable compound (C) capable of initiating the above-described description by exposure to visible rays, ultraviolet rays, far ultraviolet rays, and electrons. Beams and radiation are compounds such as X-ray polymerized groups.

The photopolymerization initiator (D) of the present invention includes one or more selected from a phenyl-based oxime initiator and a carbazole-based oxime initiator. The photopolymerization initiator of the present invention including a phenyl-based oxime initiator or a carbazole-based oxime initiator has the advantages of excellent brightness and sensitivity, and because of advantages in terms of polymerizability, initiation efficiency, and absorption wavelength, More preferred.

Specific examples of the phenyl-based oxime initiator may include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, (Z) -2-((benzyloxy Group) imino) -1- (4- (phenylthio) phenyl) oct-1-one (a compound of the following Chemical Formula 2) and the like, but are not limited thereto.

Specific examples of the carbazole-based oxime initiator may include (E) -1-(((1- (9-ethyl-6- (2-methylbenzylidene) -9H-carbazole-3 -Yl) ethinyl) amino) oxy) ethanone (compound of Chemical Formula 3 below), (E) -1-(((1- (6- (4-((2,2-dimethyl- 1,3-dioxolane-4-yl) methoxy-2-methylbenzylidene) -9-ethyl-9H-carbazol-3-yl) ethinyl) amino) oxy ) Ethyl ketone (compound of Chemical Formula 4 below) and the like, but are not limited thereto.

In addition, a typical commercial example includes BASF Corporation's OXE-01, OXE-02 and OXE-03.

[Chemical Formula 4]

The content of one or more selected from the group consisting of a phenyl-based oxime initiator and a carbazole-based oxime initiator according to the present invention is not particularly limited within a range satisfying its function, and is relative to the photopolymerization initiator (C The total weight of) is preferably from 10% to 100% by weight, more preferably from 40% to 100% by weight, and even more preferably from 70% to 100% by weight. Contents in the above range can maximize brightness and sensitivity.

As long as the purpose of the present invention is not impaired, the colored photosensitive resin composition of the present invention may further include a photopolymerization initiator commonly used in the art other than the oxime initiator as a photopolymerization initiator. Typical examples thereof may include triazine-based compounds, acetophenone-based compounds, biimidazole-based compounds, benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. Etc., but is not limited thereto, and one or more kinds may be selected and used.

Specific examples of the triazine-based compound may include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-1,3,5 -Triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2 -Based) ethylene Group] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine, etc. , But not limited to this.

Specific examples of the acetophenone-based compound may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylsulfide Phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) but-1-one, 2-hydroxy- 2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like, but are not limited thereto.

Specific examples of the biimidazole-based compound may include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2 , 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 2,2- Bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, or phenyl at the 4,4', 5,5 'position is Carboxyalkoxy substituted imidazole compounds and the like, and may preferably include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole and the like, but are not limited thereto.

Specific examples of the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like, but are not limited thereto.

Specific examples of the benzophenone-based compound include benzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldione Phenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like, but are not limited thereto.

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxyl Butithioxanthone and the like, but are not limited thereto.

Specific examples of the anthracene-based compound may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl -9,10-diethoxyanthracene and the like, but not limited thereto.

Other specific examples may include 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, Camphorquinone, methylphenylglyoxylate, titanocene compound, etc.

The content of the photopolymerization initiator (D) is not particularly limited, however, the photopolymerization initiator preferably contains 0.1 to 40% by weight based on the solid weight in the binder resin (B) and the photopolymerizable compound (C). % And more preferably 1% to 30% by weight. The content of the photopolymerization initiator 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 by using the colored photosensitive resin composition of the present invention and the flatness of the surface of the pixel unit can become advantageous.

Meanwhile, according to an embodiment of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiation aid (d1) to improve the Sensitivity of the colored photosensitive resin composition. The colored photosensitive resin composition according to the present invention can improve productivity by further increasing sensitivity by containing the photopolymerization initiation aid.

Examples of the photopolymerization initiation aid (d1) may preferably include one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

(E) Solvent

The solvent (E) according to the present invention may be a solvent commonly used in the art, and is not particularly limited as long as it effectively dissolves other components included in the colored photosensitive resin composition. As specific examples of the solvent, one or more selected from the group consisting of ether, acetate, aromatic hydrocarbon, ketone, alcohol, ester, amidine, and the like may be used, however, the solvent is not limited thereto.

Specific examples of the ether-based 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 dioxane; 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 an 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 acetates such as methoxybutyl acetate and methoxypentyl acetate; and the like.

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

Specific examples of the ketone-based solvent may include methyl ethyl Ketones, acetone, methylpentyl ketone, methyl isobutyl ketone, cyclohexanone and the like.

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

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

Specific examples of the amidoamine-based solvent may include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like.

According to coatability and drying property, the solvent (E) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C, and may more preferably include an alkylene glycol alkyl ether acetate; a ketone; an ester such as 3-ethoxy Ethyl propionate 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 Esters, methyl 3-methoxypropionate, and the like. These solvents may be used alone or as a mixture of two or more.

The content of the solvent (E) included in the colored photosensitive resin composition of the present invention is preferably from 60% to 90% by weight and more preferably from 70% to 85% by weight with respect to the total weight of the colored photosensitive resin composition of the present invention. %. When the solvent (E) is included in the above range, when using coating equipment such as a roll coater, spin coater, slit spin coater, slit coater (sometimes referred to as a die coater), and inkjet coating In this case, a favorable coating effect can be provided.

(F) Additives

To the extent that the object of the present invention is not impaired, the colored photosensitive resin composition of the present invention may further include additives (F) other than the above-mentioned components, such as other polymer compounds, curing agents, tables, etc., as required by those skilled in the art. Surfactants, adhesion promoters, antioxidants, deagglomeration agents and pigment dispersants.

Specific examples of the other polymer compounds may include cured resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl groups. Acrylates, polyesters, and polyurethanes are not limited thereto.

The curing agent is used for deep curing and improving mechanical strength, and specific examples thereof may include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like, but are not limited thereto.

Specific examples of the epoxy compound may include bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolac Type epoxy resin, other aromatic hydrocarbon-based epoxy resin, alicyclic hydrocarbon-based epoxy resin, glycidyl ester-based resin, glycidylamine-based resin, or brominated derivative of such an epoxy resin, epoxy resin Aliphatic, cycloaliphatic or aromatic epoxy compounds other than resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene (co) polymer epoxides, (methyl ) Glycidyl acrylate (co) polymer, triglycidyl isocyanurate, and the like, but are not limited thereto.

Specific examples of the oxetane compound may include carbonate dioxetane, xylene dioxetane, adipate dioxetane, terephthalate dioxane Heterobutane, cyclohexanedicarboxylic acid dioxetane, and the like are not limited thereto.

As the curing agent, a curing assistant compound capable of ring-opening polymerization of an epoxy group of the epoxy compound and an oxetane skeleton of the oxetane compound together with the curing agent can be used. The curing aid Examples of the compound include polyvalent carbonic acid, polyvalent carbonic anhydride, an acid generator, and the like. As the carbonic anhydride, a compound commercially available as an epoxy resin curing agent can be used. Specific examples of the epoxy resin curing agent may include a trade name (Adeka primer EH-700) (manufactured by Adeka Corporation), a trade name (Rikacid HH) (manufactured by New Japan Chemical Co., Ltd.), and a trade name (MH- 700) (manufactured by New Japan Chemical Co., Ltd.) and the like.

The curing agents and curing assistants exemplified above may be used alone or as a mixture of two or more.

The surfactant can be used to further improve the film-forming property of the photosensitive resin composition, and as a specific example of the surfactant, a fluorine-based surfactant, a silicone-based surfactant, or the like can be preferably used. .

As a commercial product, examples of the fluorine-based surfactant include Megafac F-470, F-471, F-475, F-482, F-489, and the like manufactured by DIC Corporation.

As a commodity, examples of the silicone-based surfactant include DC3PA, DC7PA, SH11PA, SH21PA, SH-8400, and the like manufactured by Dow Corning Toray Silicone Co., Ltd., and by GE Toshiba Silicone Co., Ltd. Manufactured TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc.

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

As specific examples of the adhesion promoter, one or more selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropene Alkoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

The adhesion promoter may account for 0.01 to 10% by weight and more preferably 0.05 to 2% by weight with respect to the solid in the colored photosensitive resin composition of the present invention.

Specific examples of the antioxidant may include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy -5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphacycloheptene, 3 , 9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanyloxy} -1,1-dimethylethyl] -2,4,8 , 10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 4,4'-butylenebis (6-tert-butyl) Methyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6-tert-butyl-4-methyl) Phenol), 3,3'-thiodipropionate dilauryl, 3,3'-thiodipropionate dimyristyl, 3,3'-thiodipropionate distearyl, pentaerythritol tetra ( 3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5"- Hexa-tert-butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetra [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6 -Di-tert-butyl-4-methylphenol and the like, but is not limited thereto.

Specific examples of the deagglomeration agent may include, but are not limited to, sodium polyacrylate.

The pigment dispersant is a component that can be added in order to deagglomerate the pigment (a1) and maintain stability. An example of a method of uniformly dispersing the pigment (a1) particles includes a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution by adding a pigment dispersant to a dispersion treatment.

As the pigment dispersant, those generally used in the art can be used without limitation. Preferably, an acrylate-based dispersant (hereinafter, also referred to as an 'acrylic dispersant'), including butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate ( DMAEMA). Commercial products of the acrylate-based dispersant may include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, DISPER BYK LPN-6919, and the like. The acrylic dispersant exemplified above may be used alone or as a combination of two or more.

In addition to the above-mentioned acrylate-based dispersant, other resin-based pigment dispersants may be used as the pigment dispersant. Examples of the other resin-based pigment dispersants may include known resin-based pigment dispersants, especially oily dispersants such as polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamines, Polycarboxylic acids, (partial) amine salts of polycarboxylic acids, Ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, hydroxyl-containing polycarboxylic acid esters and modified products thereof, or Ammonium amine or its salt formed by the reaction of polyester with poly (lower alkyleneimine); water-soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- ( (Meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinylpyrrolidone; polyesters; modified polyacrylates; ethylene oxide / propylene oxide adducts; phosphate esters, and many more.

Examples of the commercial product of the resin-based pigment dispersant may include trade names of BYK Chemie: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade names of BASF Corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA- 4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, and EFKA-4800; Trade names of Lubrizol Corporation: SOLSPERS-24000, SOLSPERS-32550, and NBZ- 4204/10; Trade names of Kawaken Fine Chemicals Co., Ltd .: HINOACT T-6000, HINOACT T-7000, and HINOACT T-8000; Trade names of Ajinomoto Fine-Techno Co., Inc .: AJISPER PB-821, AJISPER PB-822 and AJISPER PB-823; trade names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, and FLORENE DOPA-44, etc.

The dispersant is preferably included in an amount of 5 to 60 parts by weight and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the solid of the pigment (a1) used. When the content of the dispersant is less than 5 parts by weight, powdering of the pigment may be difficult or a problem such as gelation after dispersion may occur, and when it is more than 60 parts by weight, viscosity may not be preferable because it may increase.

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

First, the pigment (a1) in the colorant (A) and the solvent (E) are mixed and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. Here, as needed, 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.

To the mixed dispersion liquid, a dye (a2), the remaining binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), an additive (F), and a solvent (E) as necessary So that it has a specific concentration, and a colored photosensitive resin composition according to the present invention can be prepared.

In addition, 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 photo-curing and developing the product. The thickness of the colored pattern is not particularly limited, and may be, for example, from 1 μm to 6 μm.

<Color filter>

In addition, the present invention provides a method comprising using the colored photosensitive resin composition. Prepared color filters of colored patterns. The color filter of the present invention includes a substrate and a coloring pattern prepared on the substrate using the coloring 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 may be used. Preferably, a glass having excellent chemical stability and high strength can be used.

As a method of manufacturing the color filter, a general method 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 a display device 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, a portable terminal such as a mobile A display device for a mobile phone, a display device for a digital camera, a display device for car navigation, and the like, and a color display device is particularly suitable.

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 embodiments are only for illustrative purposes, and the present invention is not limited to the following embodiments, and may be variously modified and changed within the scope of the present invention. The scope of the present invention is determined by the technical idea of the scope of patent application described later.

In addition, the following preparation examples, examples, and comparative examples are shown. The contents of "%" and "parts" are based on weight unless specifically stated otherwise.

Preparation of colored photosensitive resin composition

A colored photosensitive resin composition having the composition and content listed in Table 1 below was prepared.

<Preparation Example 1> Production of color filter

A color filter was manufactured using the colored photosensitive resin composition prepared in Examples 1 to 7 and Comparative Examples 1 to 5.

Each colored photosensitive resin composition was applied on a glass substrate by a spin coating method, and the resultant was placed on a hot plate and held at 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern whose transmittance changes in a stepwise manner from 1% to 100% and a line / space pattern of 1 μm to 50 μm is placed on the film at a distance of 100 μm from the test photomask. Exposure to ultraviolet rays. Here, a 1 KW high-pressure mercury vapor lamp containing all g, h, and i-rays was used as an ultraviolet light source, and light was irradiated at an intensity of 100 mJ / cm ² without using a special filter. The UV-irradiated film was developed by immersing it in a developing solution of an aqueous KOH solution at pH 10.5 for 2 minutes. The film-coated glass plate was washed with distilled water, and then dried by blowing nitrogen, and heated at 200 ° C. for 1 hour in a heating oven to manufacture a color filter. The film thickness of the color filter manufactured as described above was 2.0 μm.

<Test Example> Evaluation of colored photosensitive resin composition

Test example 1. Measurement of brightness

The brightness was measured using a microspectrometer OSP-SP2000, and the results are listed in Table 2 below.

<Brightness Evaluation Standard>

When the color coordinates (Gx, Gy) = (0.262, 0.650);

○: 47.0 or higher is suitable

X: less than 47.0 is inappropriate

When the color coordinates (Gx, Gy) = (0.180, 0.670);

○: 31.0 or higher is suitable

X: less than 31.0 is inappropriate

Test example 2. Measurement of chromaticity (color coordinates)

The color coordinates of the colored layer were measured using a microspectrometer OSP-SP2000, and the results are listed in Table 2 below.

Test example 3. Sensitivity measurement

The test was performed in the same manner as the method for measuring brightness in Test Example 1 except that the pattern mask was used to change the transmittance in a stepwise range from 1% to 100%, and reached (film thickness before development / development After film thickness) x100%) The minimum exposure of 90% is expressed as sensitivity, and the results according to the following evaluation criteria are listed in Table 2.

<Evaluation criteria>

Pattern retention at sensitivity less than 60 (mJ / cm ² ): ○

Pattern retention at sensitivity of 60 (mJ / cm ² ) or higher: X

As can be seen from the results of Table 2, it was identified that the color filters formed using the photosensitive resin compositions of Examples 1 to 7 included in the scope of the present invention showed excellent sensitivity and excellent sensitivity based on the same color coordinates. brightness.

Meanwhile, as can be identified in the results of Comparative Examples 1 to 5, the color filters identified in the Comparative Example showed results that were inappropriate in one or more evaluation results of brightness and sensitivity. Especially in the range of about x = 0.1, Comparative Example 5 has a poor luminance result.

Claims (11)

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) includes CI Pigment Green 59, and one or more selected from pigments and dyes; and the photopolymerization initiator (D) includes one selected from phenyl-based oxime initiator and carbazole-based oxime initiator Or more. The colored photosensitive resin composition according to claim 1, wherein the C.I. pigment green 59 accounts for 0.05 to 30% by weight with respect to the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition as claimed in claim 1, comprising: the colorant (A) in a weight fraction of 5% to 70% by weight relative to the solids in the colored photosensitive resin composition; and relative to the adhesive The photopolymerization initiator (D) has a total solid weight in the resin (B) and the photopolymerizable compound (C) of 0.1 to 40% by weight. The colored photosensitive resin composition as claimed in claim 1, wherein the total weight of the C.I. Pigment Green 59 and one or more selected from the group consisting of pigments and dyes is included in a weight ratio of 1: 0.050 to 1: 18.0. The colored photosensitive resin composition as claimed in claim 1, wherein one or more selected from the group consisting of a phenyl-based oxime initiator and a carbazole-based oxime initiator with respect to the total weight of the photopolymerization initiator (D) accounts for 10 % By weight to 100% by weight. The colored photosensitive resin composition according to claim 1, further comprising one or more additives selected from other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, deagglomeration agents, and pigment dispersants. The colored photosensitive resin composition as claimed in claim 1, wherein the C.I. Pigment Green 59 has a Tmax of 500 nm to 530 nm. The colored photosensitive resin composition as claimed in claim 1, wherein the CI Pigment Green 59 has a T _{50% of} 445 nm to 580 nm. The colored photosensitive resin composition as claimed in 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 including a coloring pattern prepared using the coloring photosensitive resin composition according to any one of claims 1 to 9. An image display device includes a color filter as claimed in claim 10.