KR102299970B1 - Colored photosensitive resin composition - Google Patents

Abstract

The present invention includes a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), wherein the colorant (A) is a compound represented by Formula 1, and containing at least one selected from pigments and dyes; _{T max} of the compound represented by Formula 1 is 500 to 530 nm; The photopolymerization initiator (D) is a colored photosensitive resin composition comprising at least one selected from a phenyl-based oxime initiator and a carbazole-based oxime initiator, a color filter prepared using the same, and an image display comprising the color filter It's about the device.

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

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

A color filter is widely used in various display devices such as an imaging device and a liquid crystal display (LCD), and its application range is rapidly expanding. The color filter used in the imaging device, the liquid crystal display device, etc. is composed of a coloring pattern of three colors of red, green, and blue, or yellow, magenta and cyan ( It consists of a coloring pattern of 3 colors of Cyan).

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

In recent years, color filters for various display devices including solid-state imaging devices such as digital cameras and liquid crystal display devices (LCDs) have been required to have high luminance and high coloration in order to improve fairness and quality.

On the other hand, Korean Patent Application Laid-Open No. 2013-0134494 discloses C.I. Pigment Green 7 and C.I. Although a resin composition using Pigment Yellow 185 has been disclosed, there is a problem that high brightness and high coloring properties are not simultaneously satisfied.

Republic of Korea Patent Publication No. 2013-0134494

The present invention has been devised to solve the problems of the prior art,

It aims at providing the coloring photosensitive resin composition which is excellent in a brightness|luminance and colorability, and has 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 same.

The present invention is

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

The colorant (A) includes a compound represented by the following Chemical Formula 1, and at least one selected from pigments and dyes;

_{T max} of the compound represented by Formula 1 is 500 to 530 nm;

The photopolymerization initiator (D) provides a colored photosensitive resin composition comprising at least one selected from a phenyl-based oxime initiator and a carbazole-based oxime initiator.

[Formula 1]

In 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 are Cl, and 5 to 13 are Br.

Also, the present invention

It provides a color filter including a pattern formed of the colored photosensitive resin composition.

Also, the present invention

It provides an image display device including the color filter.

The coloring photosensitive resin composition of this invention shows the characteristic of the outstanding brightness|luminance and high sensitivity, and can provide the effect excellent in coloring power.

1 is a graph showing the transmission spectrum of each colorant.

The present invention is

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

The colorant (A) includes a compound represented by the following Chemical Formula 1, and at least one selected from pigments and dyes;

_{T max} of the compound represented by Formula 1 is 500 to 530 nm;

The photopolymerization initiator (D) provides a colored photosensitive resin composition comprising at least one selected from a phenyl-based oxime initiator and a carbazole-based oxime initiator.

[Formula 1]

In 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 are Cl, and 5 to 13 are Br.

Hereinafter, each component which comprises the coloring photosensitive resin composition of this invention is demonstrated. However, the present invention is not limited to these components.

(A) Colorant

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

Pigment (a1)

The colorant (A) contained in the colored photosensitive resin composition of the present invention comprises a compound represented by the following formula (1) as the pigment (a1). The compound represented by Formula 1 below has a structure of ZnPc (Zinc Phthalocyanine). When the colorant (A) of the present invention comprises a compound represented by the following formula (1) It has the advantage of high color reproduction.

[Formula 1]

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

more preferably 1 to 6 are H, 0 to 5 are Cl, and 7 to 13 are Br;

More preferably, 2 to 5 may be H, 0 to 3 may be Cl, and 8 to 13 may be Br. In this case, it is preferable in that the effect of the present invention is further maximized.

C.I. Pigment Green 58 (G58) has the advantage of high luminance, but the content of pigment is increased in order to realize high colorability. There may be a problem that the sensitivity is lowered.

However, in the present invention, by using the pigment represented by Formula 1 as a colorant, it is possible to design a resist with high color reproduction even if the content of the pigment is small.

On the other hand, C.I. When Pigment Green 7 (G7) is included in the resin composition, it can exhibit high colorability even with a small amount of pigment, which is advantageous for use, but has a problem of low luminance. However, the compound of Formula 1 included in the colored photosensitive resin composition of the present invention is a pigment in C.I. While showing a transmission spectrum and color coordinates similar to those of Pigment Green 7, it is included in the colored photosensitive resin composition and functions to exhibit excellent luminance. As can be seen in Figure 1, the compound of Formula 1 is C.I. Similar to Pigment Green 7, it has a transmission spectrum at a wavelength of 400 nm to 610 nm.

In the present specification, T _max means the wavelength at the point where the transmittance of the pigment is the maximum, and T _50% means the wavelength at the point where the transmittance of the pigment is 50% or more of the maximum value.

In one embodiment of the present invention, T _max of the compound represented by Formula 1 may be 500 to 530 nm, and in this case, it is preferable in terms of excellent colorability.

In addition, in another embodiment of the present invention, T _50% of the compound represented by Formula 1 may be 445 to 580 nm, and in this case, it is preferable in terms of excellent colorability.

The compound of Formula 1 is preferably contained in an amount of 0.05 to 30% by weight, more preferably in an amount of 0.05 to 25% by weight, and more preferably in an amount of 0.05 to 20% by weight based on the total weight of the colored photosensitive resin composition of the present invention. more preferably. When the compound of Formula 1 is included in the range of 0.05 to 30% by weight based on the above, it is preferable because it is possible to express a high-brightness resist while having excellent colorability.

The colorant (A) according to the present invention is a component capable of expressing colors such as red, green, or blue so as to produce a pattern having a desired color in addition to the compound of Formula 1, and a pigment commonly used in the art and It is characterized in that it contains one or more selected from dyes, and may be prepared in the form of a wheat base.

The compound represented by Formula 1 and at least one selected from pigments and dyes are preferably 1: 0.050 to 1: 18.0, more preferably 1: 0.1 to 1: 9, further preferably 1: 0.2 to It is preferable to be included in a weight ratio of 1: 4. When included in the above weight ratio, there are advantages of high coloration and high brightness, and it is preferable because of the advantages of improved process margin and excellent sensitivity.

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

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

The organic pigment may be treated with rosin, if necessary; surface treatment using a pigment derivative into which an acidic group or a basic group is introduced; graft treatment to the surface of the pigment using a polymer compound or the like; fine-graining treatment by a sulfuric acid fine-graining method or the like; or washing treatment with an organic solvent or water to remove impurities; it may have been

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

As a specific example of the pigment (a1), more preferably, a compound classified as a pigment in the Color Index (Publisher: The Society of Dyers and Colorists) may be mentioned, and more specifically, the following color index ( CI) may include, but are not limited to, the pigments exemplified by the numbers, and at least one selected therefrom may be co-dispersed using a binder resin, a dispersant, etc. to match the desired chromaticity.

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

C.I. As a specific example of the pigment orange, C.I. pigment orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

C.I. As a specific example of pigment red, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264 and 265. there is;

C.I. As a specific example of pigment blue, C.I. Pigment Blue 15:3, 15:4, 15:6, 16, 22, 28, 60 and the like;

C.I. As a specific example of pigment violet, C.I. Pigment Violet 14, 19, 23, 29, 32, 177, etc. are mentioned,

C.I. As a specific example of pigment green, C.I. Pigment Green 7, 36, 58, etc. are mentioned.

Among the pigments exemplified above, preferably, C.I. Pigment Yellow 138, C.I. Pigment Yellow 129, C.I. Pigment Yellow 150, C.I. It may be more preferable to include at least one selected from the group consisting of Pigment Yellow 185.

dye (a2)

The dye (a2) that may be included in the colorant (A) of the present invention may be used without limitation as long as it has solubility in an organic solvent or is dispersible. Preferably, it is preferable to use a dye that has solubility in organic solvents and can secure reliability such as solubility in alkali developer, heat resistance and solvent resistance. In the case of dyes that are not soluble in organic solvents, it is also possible to disperse them and use them.

As the dye (a2), at least one selected from acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof may be used. In addition, it may be selected from azo-based, xanthene-based, phthalocyanine-based acid dyes and derivatives thereof.

Preferred examples of the dye (a2) include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists), and well-known dyes described in the dyeing notes (color dyes).

As a specific example of the dye (a2),

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

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

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

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

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

C.I. Solvent Green No. 3, C.I. Solvent Green No. 5, C.I. Solvent Green No. 7 may be mentioned, but is not limited thereto.

The colorant (A) may be included in an amount of preferably 5 to 70% by weight, more preferably 10 to 50% by weight based on the solid content in the colored photosensitive resin composition of the present invention. If the content of the colorant (A) is less than 5% by weight, the color separation ability of the formed pattern may be reduced, and if it exceeds 70% by weight, the lithography performance is lowered, and problems such as residues or non-development may occur.

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

(B) binder resin

Binder resin (B) contained in the coloring photosensitive resin composition of this invention is a component which provides solubility with respect to the alkali developing solution used in the image development 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 include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; Polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, etc. are mentioned, and acrylic acid and methacrylic acid are more preferable. These can be used by selecting one or more types.

The other copolymerizable monomer is not particularly limited as long as it is a monomer having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate unsaturated carboxylate compounds such as acrylates; unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; unsaturated 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; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane; 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, etc. of unsaturated oxetane carboxylate compounds, and the like. These monomers can be used individually or in combination of 2 or more types, respectively.

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

The acid value of the binder resin (B) is preferably 30 to 170 mgKOH/g based on solid content, and more preferably 50 to 150 mgKOH/g. When the acid value of the binder resin (B) is less than 30 mgKOH/g, it is difficult for the colored photosensitive resin composition to secure a sufficient development speed. This is easy to occur, and compatibility with the colorant is problematic, and the colorant in the colored photosensitive resin composition may precipitate, or the storage stability of the colored photosensitive resin composition may decrease and the viscosity may increase, which is not preferable.

The binder resin (B) is preferably contained in an amount of 5 to 85% by weight, more preferably 10 to 70% by weight based on the solid content in the colored photosensitive resin composition of the present invention. When the content of the binder resin (B) is 5 to 85% by weight based on the above criteria, the solubility in the developer is sufficient, so that the development residue is hardly generated on the substrate of the non-pixel portion, and the film of the pixel portion of the exposed portion during development It is preferable because the decrease is prevented and the omission property of the non-pixel portion tends to be good.

(C) photopolymerizable compound

The photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by active radicals, acids, etc. generated from a photopolymerization initiator (D) to be described later by light irradiation, and is polymerized by the action of the photopolymerization initiator. It will not specifically limit if it is a compound which can do it. Preferably, a monofunctional monomer, a difunctional monomer, or a trifunctional or more polyfunctional monomer may be used, and one or more monomers selected therefrom may be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinylpi Rollidone and the like, and commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), or Biscott 158 (Osaka Yuki Chemical High School). it is not

Specific examples of the bifunctional monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylic rate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, propylene glycol dimethacrylate, urethane (meth)acrylate Examples of commercially available products include Aronix M-210, M-1100, 1200 (Toagosei), KAYARAD HDDA (Nippon Kayaku), Biscott 260 (Osaka Yuki Chemical High School), AH-600, AT- 600 or UA-306H (Kyoeisha Chemical), and the like, but is not limited thereto.

Specific examples of the trifunctional or more multifunctional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate , pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta (meth) acrylate, ethoxyl rated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and commercially available products include Aronix M -309, TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA, or KAYARAD DPHA-40H (Nippon Kayaku), but is not limited thereto.

Among the photopolymerizable compounds exemplified above, it is more preferable to use a trifunctional or more polyfunctional monomer, and (meth)acrylates and urethane (meth)acrylates have excellent polymerizability and can improve strength. desirable.

The photopolymerizable compound (C) is preferably contained in an amount of 5 to 45% by weight, and more preferably in an amount of 10 to 35% by weight, based on the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound (C) is in the range of 5 to 45 wt % based on the above-mentioned basis, it is preferable because the strength and smoothness of the pixel portion are improved.

(D) photoinitiator

The photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention is the binder resin (B) and the photopolymerizable compound (B) described above by exposure to radiation such as visible ray, ultraviolet ray, far ultraviolet ray, electron beam, and X-ray ( It is a compound which generate|occur|produces the radical etc. which can initiate the polymerization of C).

The photopolymerization initiator (D) of the present invention includes at least one selected from a phenyl-based oxime initiator and a carbazole-based oxime initiator. When the photopolymerization initiator of the present invention includes a phenyl-based oxime initiator or a carbazole-based oxime initiator, there are advantages in luminance and sensitivity, and it is advantageous in terms of polymerization characteristics, initiation efficiency, absorption wavelength, and the like, which may be more preferable.

Specific examples of the phenyl oxime initiator include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and (Z)-2-((benzoyloxy)imino)-1-(4 -(phenylthio)phenyl)octan-1-one (a compound of Formula 2 below), but is not limited thereto.

[Formula 2]

Specific examples of the carbazole-based oxime initiator include (E)-1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidine)amino)oxy Ethanone (compound of formula 3 below) and (E)-1-(((1-(6-(4-((2,2-dimethyl-1,3-dioxolan-4-yl)methoxy) -2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl)ethylidin)amino)oxy)ethanone (a compound of Formula 4 below), but is not limited thereto.

Moreover, as an example, OXE-01, OXE-02, and OXE-03 of BASF are representative as a commercial item.

[Formula 3]

[Formula 4]

The content of the at least one selected from the phenyl-based oxime initiator and the carbazole-based oxime initiator according to the present invention is not particularly limited within the range capable of fulfilling its function, and preferably, the photopolymerization initiator (C) is based on the total weight It may contain from 10 to 100% by weight, more preferably from 40 to 100% by weight, more preferably from 70 to 100% by weight. When the content is within the above range, luminance and sensitivity may be maximized.

The colored photosensitive resin composition of the present invention may further include a photopolymerization initiator commonly used in the art within a range that does not impair the object of the present invention in addition to the oxime initiator as a photoinitiator. Representative examples include, but are not limited to, triazine-based, acetophenone-based, biimidazole-based, benzoin-based, benzophenone-based, thioxanthone-based and anthracene-based compounds. Can be used.

Examples of the triazine-based compound 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-piperonyl-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)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like, but are not limited thereto.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-1-[4-(2-) Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- 1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

Examples of the biimidazole-based compound 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)bi Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)- 4,4',5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group; Preferably 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, etc. may be mentioned, but is not limited thereto.

Examples of the benzoin-based compound include, but are not limited to, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like, but are not limited thereto.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. may be mentioned, but is not limited thereto.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. may be mentioned, but is not limited thereto.

As other specific examples, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, phenylclioxyl A methyl acid, a titanocene compound, etc. are mentioned.

The content of the photopolymerization initiator (D) is not particularly limited, but is preferably included in an amount of 0.1 to 40% by weight based on the total weight of the solid content in the binder resin (B) and the photopolymerizable compound (C), and 1 to 30% by weight It is more preferable to be included in %. When the content of the photopolymerization initiator is within the above range, it is preferable because the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Moreover, since the intensity|strength of the pixel part formed using the coloring photosensitive resin composition of this invention and the smoothness in the surface of the said pixel part can become favorable, it is preferable.

Meanwhile, according to an embodiment of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiator auxiliary (d1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation adjuvant, thereby further increasing the sensitivity and improving productivity.

The photopolymerization initiation adjuvant (d1) may be, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler ketone) ), 4,4'-bis(diethylamino)benzophenone, and the like can be used.

The carboxylic acid compound is preferably aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptobutyl rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like. can

(E) solvent

As long as the solvent (E) according to the present invention is effective for dissolving other components included in the colored photosensitive resin composition, a solvent commonly used in the art may be used without particular limitation. The solvent may be used by selecting one or more types from ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, and amides as specific examples, but is not limited thereto.

The ether solvent is specifically, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;

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

The acetate solvent is specifically, alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like. ;

alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; and the like.

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

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

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

Specifically, the ester solvents include cyclic esters such as γ-butyrolactone;

3-ethoxy ethyl propionate, 3-methoxy methyl propionate, ethyl 3-ethoxy propionate, etc. are mentioned.

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

The solvent (E) is preferably an organic solvent having a boiling point of 100° C. to 200° C. in terms of coatability and dryness, more preferably alkylene glycol alkyl ether acetates; ketones; Esters, such as 3-ethoxy ethyl propionate and 3-methoxy methyl propionate; are mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3-ethoxy propionic acid are mentioned. Ethyl, 3-methoxymethyl propionate, etc. are mentioned. These solvents can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent (E) contained in the colored photosensitive resin composition of the present invention is preferably 60 to 90% by weight, more preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. may be included as When the solvent (E) is contained within the above range, the coating property becomes good when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet. effect can be provided.

(F) additives

The colored photosensitive resin composition of the present invention contains, in addition to the above components, other high molecular compounds, curing agents, surfactants, adhesion promoters, antioxidants, aggregation inhibitors, pigment dispersants, etc. (F) may be further included.

Specific examples of the other high molecular compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, etc. may be mentioned, but is not limited thereto.

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

Specific examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolak epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, Glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxide, isoprene (co) ) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like, but is not limited thereto.

Specific examples of the oxetane compound include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like, but limited thereto. it's not going to be

The curing agent may be used together with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Specifically, as the curing aid compound, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, acid generators, and the like may be used. As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. The commercially available epoxy resin curing agent includes, for example, a trade name (Adecahadona EH-700) (manufactured by Adeka Industrial Co., Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin-Nippon Ewha Co., Ltd.), trade name (MH-700) (manufactured by Nippon Ewha Co., Ltd.) and the like.

The curing agent and curing auxiliary compound exemplified above may be used alone or in combination of two or more.

The surfactant may 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 or a silicone-based surfactant may be preferably used.

The fluorine-based surfactants include, for example, Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink Chemical Co., Ltd. as a commercially available product.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc., manufactured by Dow Corning Toray Silicone Co., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF- 4460, TSF-4452, and the like.

Each of the surfactants exemplified above may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl At least one selected from trimethoxysilane, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane can be used.

The adhesion promoter may be included in an amount of 0.01 to 10% by weight, more preferably 0.05 to 2% by weight based on the solid content in the colored photosensitive resin composition of the present invention.

Specific examples of the antioxidant 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)prop Foxy]- 2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine, 3,9-bis[2-{3-(3-tert) -Butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis( 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5- methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityltetrakis(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, pentaerythritoltetrakis[3-(3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and 2,2'-thiobis (4-methyl-6-t-butylphenol), 2 ,6-di-t-butyl-4-methylphenol, and the like, but are not limited thereto.

Specific examples of the aggregation inhibitor include, but are not limited to, sodium polyacrylate.

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

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

As the pigment dispersant, a pigment dispersant of a resin type other than the acrylate-based dispersant may be used. The pigment dispersants of the other resin types include known resin type pigment dispersants, in particular polyurethane, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free oily pigment dispersants such as amides or salts thereof formed by the reaction of polyester having a carboxyl group and poly(lower alkyleneimine); water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylates; adducts of ethylene oxide/propylene oxide and phosphate esters; and the like.

Commercial products of the above-mentioned resin-type pigment dispersant include, for example, BYK-Chemie's trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK- 166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF trade names: 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, EFKA-4800; Trade names from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Corporation: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, etc. are mentioned.

The pigment dispersant is preferably included in an amount of 5 to 60 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1) used. When the content of the pigment dispersant is included in less than 5 parts by weight based on the above, it is difficult to atomize the pigment, or it may cause problems such as gelation after dispersion, and if it exceeds 60 parts by weight, the viscosity may increase, so it is not preferable .

A method for producing the colored photosensitive resin composition of the present invention will be described by way of example.

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

In the mixed dispersion, the dye (a2), the remainder of the binder resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D) and, if necessary, the additive (F) and the solvent (E) are added to a predetermined concentration. It can be added to prepare a colored photosensitive resin composition according to the present invention.

In addition, the present invention includes a colored pattern prepared from the colored photosensitive resin composition. The colored pattern may be prepared by coating the colored photosensitive resin composition of the present invention on a substrate, photocuring and developing. The thickness of the coloring pattern is not particularly limited, and may be, for example, 1 to 6 μm.

The coloring pattern may be formed, for example, by the following method.

First, the colored photosensitive resin composition is applied on a substrate or a layer made of the solid content of the previously formed photosensitive resin composition, and volatile components such as a solvent are removed by prebaking from the applied photosensitive resin composition layer to obtain a smooth coating film.

As said coating method, the spin coating method, the casting|flow_spread coating method, the roll coating method, the slit-and-spin coating method, or the slit coating method etc. can be implemented, for example.

After the said application|coating, a coloring photosensitive resin composition layer is formed by heating after prebaking (heat drying) or reduced pressure drying to volatilize volatile components, such as a solvent. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C.

An ultraviolet-ray is irradiated to the coating film obtained in this way through the mask for forming the target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel rays are uniformly irradiated to the entire exposed portion and the mask and the substrate are precisely aligned.

In addition, the desired pattern shape can be obtained by contacting the cured coating film with an alkali developer to dissolve the unexposed portion and then developing the cured coating film. As the developing method, a liquid addition method, a dipping method, a spraying method, etc. may be performed, and the substrate may be tilted at an arbitrary angle during development.

The said developing solution used for image development after patterning exposure is an aqueous solution containing an alkaline compound and surfactant normally. Any of inorganic and/or organic alkaline compounds may be sufficient as the said alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, carbonate Potassium, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. You may use these inorganic and organic alkaline compounds individually or in combination of 2 or more types, respectively.

The concentration of the alkaline compound in the alkaline developer is, for example, 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

Any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant may be sufficient as surfactant in the said alkaline developing solution.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid Ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylarylsulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate; and the like.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride; quaternary ammonium salts; and the like.

These surfactants can be used individually or in mixture of 2 or more types.

The concentration of the surfactant in the alkaline developer is, for example, 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight.

After the development, it may be washed with water and, if necessary, may be post-baked at 150 to 230°C for 10 to 60 minutes.

<Color filter>

The present invention also provides a color filter comprising a colored pattern prepared from the colored photosensitive resin composition. The color filter of the present invention includes a substrate and a colored pattern made of the colored photosensitive resin composition of the present invention on the substrate. The substrate is a transparent material, and a material having sufficient strength and support for the stability of the color filter may be used. Preferably, a glass having excellent chemical stability and high strength may be used.

A method of manufacturing the color filter may use a conventional method well known in the art.

<Image display device>

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

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

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples, and may be variously modified and changed within the scope of the present invention. The scope of the present invention will be determined by the spirit of the claims to be described later.

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

Preparation of colored photosensitive resin composition

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

(parts by weight) division Example
One Example
2 Example
3 Example
4 comparative example
One comparative example
2 comparative example
3 comparative example
4 Colorant (A) A-1 3.0618 3.0618 3.0618 3.0618 3.0618 - - - A-2 - - - - - 3.0618 3.0618 3.0618 A-3 2.6082 2.6082 2.6082 - - - - 2.6082 A-4 2.6082 2.6082 2.6082 2.6082 - binder
Resin (B) B-1 4.1 4.1 4.1 4.1 4.1 2.95 2.95 4.64 Photopolymerizable compound (C) C-1 2.8 2.8 2.8 2.8 2.8 2.44 2.44 2.98 light curing
Initiator (D) D-1 1.2 - 0.6 1.2 - - - - D-2 - 1.2 0.6 - - - - - D-3 - - - - - 0.8 - 0.8 D-4 - - - - - 0.4 - 0.4 D-5 - - - - 12 - 1.2 - Solvent (E) E-1 70 70 70 70 70 70 70 70 E-2 15 15 15 15 15 15 15 15 Additive (F) F-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 F-2 1.17 1.17 1.17 1.17 1.17 1.17 1.17 1.17 F-3 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 A-1: in the structure of Formula 1, Cl: 2, Br: 9, H: 5 (T _max : 515 nm, T _50% : 450 to 575 nm) (Manufacturer: DIC)
A-2: G7 (in the structure of Formula 1, a central atom is Cu, A ¹ to A ¹⁶ are Cl: 14 to 16, H: 0 to 2 mixtures)
A-3: Y138 (Manufacturer: BASF)
A-4: Y129 (Manufacturer: DIC)

B-1: methacrylic acid: benzyl methacrylate = 31: 69 (molar ratio), weight average molecular weight = 30,000, acid value = 105 copolymer of methacrylic acid and benzyl methacrylate

C-1: dipentaerythritol hexaacrylate (KAYARAD DPHA; Manufacturer: Nippon Kayaku Co., Ltd.)

D-1: OXE-01 (Manufacturer: Ciba)
D-2: OXE-02 (Manufacturer: Ciba)
D-3: D-1 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (I-369, manufactured by Ciba)
D-4: 4,4'-bis(diethylamino)benzophenone (manufactured by Ciba)
D-5: piperonyl-1,1-trichloromethyl 3,5S triazine (TAZ-pp)

E-1: propylene glycol monomethyl ether acetate
E-2: ethyl 3-ethoxypropionate

F-1: Silicone-based surfactant (SH-8400)
F-2: Acrylic pigment dispersant (DISPER BYK-2001, manufactured by BYK)
F-3: adhesion promoter (3-methacryloxypropyltrimethoxysilane)

<Production Example> Preparation of color filter

Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4.

Each of the colored photosensitive resin compositions was applied on a glass substrate by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Then, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% and a line/space pattern of 1 µm to 50 µm is placed on the thin film, and the interval from the test photomask is set to 100 µm was investigated. ^{At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm 2} using a 1KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of a KOH aqueous solution having a pH of 10.5 for 2 minutes. The glass plate coated with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220° C. for 1 hour to prepare a color filter. The film thickness of the color filter prepared above was 2.0 μm.

<Experimental example> Evaluation of colored photosensitive resin composition

Experimental Example 1. Luminance Measurement

The luminance was measured using a microscopic spectrometer OSP-SP2000, and the results are shown in Table 2 below.

<Luminance evaluation criteria>

○: Suitable for 47.0 or higher

X: less than 47.0 not suitable

Experimental Example 2. Measurement of chromaticity (color coordinates)

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

Experimental Example 3. Sensitivity Measurement

Except for using a pattern mask that changes the transmittance in a stepwise manner in the range of 1 to 100%, the same procedure as in the luminance measurement method of Experimental Example 1 was carried out, (film thickness after development / film thickness before development) x 100 ) ) ≥ 90% of the minimum exposure amount was expressed as the sensitivity, and the results according to the following evaluation criteria are shown in Table 2.

<Evaluation criteria>

When the pattern remains at a sensitivity of less than 60 (mJ/cm ^{2 ): ○}

When remaining in the pattern at a sensitivity of 60 (mJ/cm ^{2 ) or higher: X}

Sensitivity Color coordinates (Gx, Gy) luminance Example 1 O (0.262, 0.650) O Example 2 O O Example 3 O O Example 4 O O Comparative Example 1 O X Comparative Example 2 X X Comparative Example 3 X X Comparative Example 4 X O

As can be seen from the results of Table 2, based on the same color coordinates, it can be confirmed that the color filters formed of the colored photosensitive resin compositions of Examples 1 to 4 within the scope of the present invention exhibit excellent sensitivity and luminance. , As can be seen from the results of Comparative Examples 1 to 4, it can be confirmed that the comparative example has an unsuitable level in the evaluation results of at least one of luminance and sensitivity.

Claims (12)

a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E);
The colorant (A) includes a compound represented by the following Chemical Formula 1, and at least one selected from pigments and dyes;
_{T max} of the compound represented by Formula 1 is 500 to 530 nm;
_{T 50%} of the compound represented by Formula 1 is 445 to 580 nm;
The photopolymerization initiator (D) is a colored photosensitive resin composition comprising at least one selected from a phenyl-based oxime initiator and a carbazole-based oxime initiator.

[Formula 1]

In 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 are Cl, and 5 to 13 are Br.
The method according to claim 1,
The compound represented by Formula 1 is a colored photosensitive resin composition, characterized in that it is included in an amount of 0.05 to 30% by weight based on the total weight of the colored photosensitive resin composition.
The method according to claim 1,
In a weight fraction with respect to the solid content in a coloring photosensitive resin composition,
5 to 70% by weight of a colorant (A); and
With respect to the total weight of solid content in the binder resin (B) and the photopolymerizable compound (C),
A colored photosensitive resin composition comprising 0.1 to 40 wt% of a photopolymerization initiator (D).
The method according to claim 1,
The color photosensitive resin composition, characterized in that the compound represented by Formula 1, and at least one selected from a pigment and a dye are included in a weight ratio of 1: 0.050 to 1: 18.0.
The method according to claim 1,
In Chemical Formula 1, ^{1 to 6 of A 1} to A ¹⁶ are H, 0 to 5 are Cl, and 7 to 13 are Br.
The method according to claim 1,
In Chemical Formula 1, ^{2 to 5 of A 1} to A ¹⁶ are H, 0 to 3 are Cl, and 8 to 13 are Br.
The method according to claim 1,
Based on the total weight of the photopolymerization initiator (D), at least one selected from the phenyl-based oxime initiator and the carbazole-based oxime initiator is included in an amount of 10 to 100% by weight of the colored photosensitive resin composition.
The method according to claim 1,
A colored photosensitive resin composition further comprising one or more additives selected from other high molecular compounds, curing agents, surfactants, adhesion promoters, antioxidants, aggregation inhibitors, and pigment dispersants.
delete The method according to claim 1,
Colored photosensitive resin composition, characterized in that it has a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more in the XYZ color system.
A color filter comprising a colored pattern made of the colored photosensitive resin composition of any one of claims 1 to 8 and 10.
An image display device comprising the color filter of claim 11 .

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