Photosensitive resin composition, photosensitive resin film utilizing the same, color filter, and display

Abstract

To provide a photosensitive resin composition having high dispersibility and dispersion stability while realizing a color filter excellent in the coloring power and contrast ratio.SOLUTION: In one embodiment, a photosensitive resin composition comprises (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a binder resin, and (E) a solvent. The colorant comprises a pigment, a dispersant, and a dispersing aid represented by a specific chemical formula.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a photosensitive resin composition, a photosensitive resin film utilizing the same, and a color filter. [Background technology]

[0002] Liquid crystal displays (LCDs), a type of display, have advantages such as being lightweight, thin, inexpensive, low power consumption, and having excellent compatibility with integrated circuits, and their range of use is expanding to laptops, monitors, and TV displays.

[0003] Such a liquid crystal display comprises a lower substrate on which a black matrix, color filters, and ITO pixel electrodes are formed, and an upper substrate on which an active circuit section consisting of a liquid crystal layer, thin-film transistors, and an energy storage capacitor layer, and ITO pixel electrodes are formed.

[0004] A color filter consists of a structure in which a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundaries between pixels, and pixel sections arranged in a predetermined order to form each pixel, with multiple colors (usually the three primary colors of red (R), green (G), and blue (B)) arranged in a predetermined order.

[0005] One method for realizing color filters is the pigment dispersion method, which involves coating a transparent substrate provided with a black matrix with a photopolymerizable composition containing a colorant, exposing the pattern of the desired shape to the light, removing the unexposed areas with a solvent, and then repeating the process to form a colored thin film (photosensitive resin film).

[0006] Photosensitive resin compositions (pigment-type photosensitive resin compositions) used in the manufacture of color filters by pigment dispersion generally consist of alkali-soluble resins, photopolymerization monomers, photopolymerization initiators, epoxy resins, solvents, and other additives. Pigment dispersion methods with the above characteristics are actively applied to the manufacture of LCDs for mobile phones, laptops, monitors, TVs, and other devices.

[0007] However, even in photosensitive resin compositions for color filters using pigment dispersion methods, which have various advantages, there is a growing demand for improved performance in addition to excellent pattern characteristics. In particular, there is an urgent need for high color reproduction rates along with improved light-to-dark ratio characteristics. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Korean Patent Publication No. 10-2020-0137750 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] One embodiment aims to provide a photosensitive resin composition that exhibits high dispersibility and dispersion stability while also having excellent coloring power and light-dark ratio when used in color filters.

[0010] Another object of this embodiment is to provide a photosensitive resin film manufactured using a photosensitive resin composition.

[0011] Another object of this embodiment is to provide a color filter that includes a photosensitive resin film. [Means for solving the problem]

[0012] One embodiment provides a photosensitive resin composition comprising (A) a colorant, (B) a photopolymerizable compound, (C) a photoinitiator, (D) a binder resin, and (E) a solvent, wherein the colorant comprises a pigment, a dispersant, and a dispersion aid represented by the following Chemical Formula 1. [Chemical Formula 1] [Chemical Structure] In Chemical Formula 1, M is Cu or Zn, and R 11 ~R 14 , R 21 ~R 24 , and R 31 ~R 34 are each independently a hydrogen atom, a halogen atom, a hydroxy group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R 41 ~R 44 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and at least one of R 41 ~R 44 is an alkoxy group having 1 to 20 carbon atoms substituted with a sulfonate group.

[0013] R 11 ~R 14 may all be hydrogen atoms or may all be halogen atoms.

[0014] One or two of R 21 ~R 24 may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and the rest may all be hydrogen atoms.

[0015] R 31 ~R 34 may all be hydrogen atoms.

[0016] Any one of R 41 ~R 44 is *-O-L 1 -L 2The substituent is represented by -A, and the remaining atoms may all be hydrogen atoms or all be halogen atoms.

[0017] L 1 L is a single bond, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. 2 A is a single bond, or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and A is SO3 - A single anion, or SO3 - and Na + A combination of salts is also acceptable.

[0018] L 1 This may be a single bond or a phenylene group.

[0019] L 2 This may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

[0020] A is SO3 - and Na + A combination of salts is also acceptable.

[0021] *-OL 1 -L 2 -The substituent represented by A is represented by chemical formula 2 or 3 below: [Chemical formula 2] [ka] [Chemical formula 3] [ka] In chemical formula 3, R 51 ~R 55 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted C1-C20 alkyl group, or *-L 2 -A and R 51 ~R 55 At least one of them is *-L 2 -A, and in chemical formulas 2 and 3, L 2A is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and A is SO3 - A single anion, or SO3 - and Na + This is a combination of salts.

[0022] A dispersion aid represented by chemical formula 1 is represented by one of the following chemical formulas 1-1 to 1-4: [Chemical formula 1-1] [ka] [Chemical formula 1-2] [ka] [Chemical formula 1-3] [ka] [Chemical formula 1-4] [ka]

[0023] In chemical formulas 1-1 to 1-4, M is either Cu or Zn, and R 11 ~R 14 , R 21 ~R 24 , R 31 ~R 34 , and R 41 ~R 44 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R 51 ~R 55 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted C1-C20 alkyl group, or *-L 2 -A and R 51 ~R 55 At least one of them is *-L 2 -A and L 2A is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and A is SO3 - A single anion, or SO3 - and Na + This is a combination of salts.

[0024] The dispersion aid represented by chemical formula 1 is selected from the following group: [Chemical formula 1-1-1] [ka] [Chemical formula 1-1-2] [ka] [Chemical formula 1-1-3] [ka] [Chemical formula 1-1-4] [ka] [Chemical formula 1-1-5] [ka] [Chemical formula 1-1-6] [ka] [Chemical formula 1-1-7] [ka] [Chemical formula 1-1-8] [ka] [Chemical formula 1-1-9] [ka] [Chemical Formula 1-1-10]

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[0025] The dispersion aid represented by chemical formula 1 may have a maximum absorption wavelength of 450 nm to 495 nm.

[0026] The dispersion aid represented by chemical formula 1 may be included in an amount of 0.5% to 6% by weight relative to the total amount of the photosensitive resin composition.

[0027] The weight ratio of the dispersion aid represented by chemical formula 1 to the pigment may be 1:20 to 1:70.

[0028] The pigment may include green pigment, yellow pigment, or a combination thereof.

[0029] The photosensitive resin composition may contain, based on the total amount of the photosensitive resin composition, (A) 0.5% to 15% by weight of a colorant, (B) 0.1% to 10% by weight of a photopolymerizable compound, (C) 0.1% to 10% by weight of a photopolymerization initiator, (D) 0.5% to 15% by weight of a binder resin, and (E) the amount of solvent residue.

[0030] Another embodiment provides a photosensitive resin film manufactured using a photosensitive resin composition.

[0031] The photosensitive resin film may be a color negative photoresist.

[0032] Another embodiment provides a color filter including a photosensitive resin film.

[0033] Another embodiment provides a display including a color filter.

[0034] Other specific aspects of the present invention are included in the detailed description below. [Effects of the Invention]

[0035] The photosensitive resin composition according to one embodiment possesses high dispersibility and dispersion stability, while also exhibiting excellent coloring power and brightness-to-dark ratio when used in the realization of a color filter. Therefore, by utilizing the photosensitive resin composition according to one embodiment, excellent color filters and displays can be realized. [Modes for carrying out the invention]

[0036] Embodiments of the present invention will be described in detail below. However, these are presented as examples only, and the present invention is not limited thereto, and is defined solely within the scope of the claims described later.

[0037] Unless otherwise specified herein, “substitution” means that at least one hydrogen atom in a compound is substituted with a substituent of a halogen atom (F, Cl, Br, I), a hydroxyl group, a carbon-1 to carbon-20 alkoxy group, a nitro group, a cyano group, an amino group, an imino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, an ether group, a carboxyl group or its salt, a sulfonic acid group or its salt, a phosphoric acid or its salt, a carbon-1 to carbon-20 alkyl group, a carbon-2 to carbon-20 alkenyl group, a carbon-2 to carbon-20 alkynyl group, a carbon-6 to carbon-30 aryl group, a carbon-3 to carbon-20 cycloalkyl group, a carbon-3 to carbon-20 cycloalkenyl group, a carbon-3 to carbon-20 cycloalkynyl group, a carbon-2 to carbon-20 heterocycloalkyl group, a carbon-2 to carbon-20 heterocycloalkenyl group, a carbon-2 to carbon-20 heterocycloalkynyl group, or a combination thereof.

[0038] Unless otherwise specified herein, “heterocycloalkyl group,” “heterocycloalkenyl group,” “heterocycloalkynyl group,” and “heterocycloalkylene group” mean the presence of at least one N, O, S, or P heteroatom within the cyclic compound of a cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkylene, respectively.

[0039] Unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible.

[0040] Unless otherwise defined herein, “combination” means mixing or copolymerization. “Copolymer” means block copolymerization or random copolymerization, and “copolymer” means block copolymer or random copolymer.

[0041] Unless otherwise defined in the chemical formulas herein, the absence of a chemical bond at a position where one should be depicted means that a hydrogen atom is bonded to that position.

[0042] Unless otherwise defined herein, "*" means a portion that bonds with the same or different atoms or chemical formulas.

[0043] Unless otherwise defined herein, “particle size” means the diameter of a particle, which may be the Z-mean value of the particle diameter measured by dynamic light scattering.

[0044] (Photosensitive resin composition) One embodiment provides a photosensitive resin composition comprising (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a binder resin, and (E) a solvent, wherein the colorant comprises a pigment, a dispersant, and a dispersion aid represented by the following chemical formula 1: [Chemical formula 1] [ka] In chemical formula 1, M is Cu or Zn, and R 11 ~R 14 , R 21 ~R 24 , and R 31 ~R 34 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R 41 ~R 44 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C1-C20 alkoxy group, R41 ~R 44 At least one of these is an alkoxy group having 1 to 20 carbon atoms that is substituted with a sulfonic acid base.

[0045] (A) Coloring agent One embodiment of the photosensitive resin composition is a pigment-type photosensitive resin composition, and the colorant contains a pigment. In color filters manufactured with a pigment-type photosensitive resin composition, there are limitations in brightness and light-dark ratio due to the particle size of the pigment.

[0046] Furthermore, for applications in image sensors, resin compositions consisting of smaller particles are required to form fine patterns. To achieve this, it is necessary to develop compounds that help disperse pigments and prevent re-aggregation, as well as compositions utilizing these compounds.

[0047] The dispersing agent represented by chemical formula 1 has a phthalocyanine core and a sulfonate group asymmetrically substituted on the phthalocyanine core.

[0048] The phthalocyanine core interacts with the pigment, and the sulfonate groups asymmetrically substituted on the phthalocyanine core interact with the dispersant or dispersion resin. Therefore, the dispersion aid represented by chemical formula 1 has the function of assisting the dispersant in the photosensitive resin composition to enhance the dispersibility and dispersion stability of the pigment.

[0049] Furthermore, the phthalocyanine-based nucleus exhibits blue coloration. Therefore, the dispersion aid represented by chemical formula 1 has the function of assisting the colorant in the photosensitive resin composition to enhance its coloring ability.

[0050] Overall, the dispersion aid represented by chemical formula 1 is a dispersion aid that assists the dispersant to improve the dispersibility and dispersion stability of the pigment, and also assists the colorant to enhance its coloring power. Therefore, if a photosensitive resin composition containing the dispersion aid represented by chemical formula 1 is implemented in color filters and displays, it is possible to achieve improved coloring power (color reproduction rate) and brightness-to-dark ratio.

[0051] R 11 ~R 14 Each of these may independently be a hydrogen atom, a halogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0052] For example, R 11 ~R 14 These atoms may all be hydrogen atoms, or they may all be halogen atoms. Here, the halogen atoms may also be chlorine atoms.

[0053] R 21 ~R 24 Each of these may independently be a hydrogen atom, a halogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0054] Specifically, R 21 ~R 24 All of them may be hydrogen atoms. In contrast, R 21 ~R 24 One of them may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and the rest may all be hydrogen atoms. For example, R 21 ~R 24 One or two of these may be branched C4 alkyl groups (tert-butyl groups), and the rest may all be hydrogen atoms.

[0055] R 21 ~R 24 Compared to the case where all are hydrogen atoms, R 21 ~R 24When one or two of them are branched C4 alkyl groups (tert-butyl groups), the solubility of the dispersion aid represented by Chemical Formula 1 in a solvent is improved.

[0056] However, since the dispersion aid represented by Chemical Formula 1 has sufficient solubility in a solvent due to the presence of A(SO3 - a single anion, or a salt of a combination of SO3 - and Na + ), R 21 ~R 24 may all be hydrogen atoms.

[0057] R 31 ~R 34 may each independently be a hydrogen atom, a halogen atom, a hydroxy group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0058] For example, R 31 ~R 34 may all be hydrogen atoms.

[0059] The sulfonate group asymmetrically substituted with respect to the phthalocyanine-based mother nucleus is a substituent represented by *-O-L 1 -L 2 -A, where A is SO3 - a single anion, or a salt of a combination of SO3 - and Na + . Also, there is one or more sulfonate groups asymmetrically substituted with respect to the phthalocyanine-based mother nucleus. This will be described in detail.

[0060] R 41 ~R 44 may each independently be a hydrogen atom, a halogen atom, a hydroxy group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituent represented by *-O-L 1 -L 2 -A, and at least one of R 41 ~R 44 is *-O-L 1 -L2 The substituent may be represented by -A.

[0061] Specifically, R 41 ~R 44 One of the following is *-OL 1 -L 2 -A is a substituent, and the rest may all be hydrogen atoms or all halogen atoms. Here, L 1 L is a single bond, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. 2 A is a single bond, or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and A is SO3 - A single anion, or SO3 - and Na + A combination of salts is also acceptable.

[0062] More specifically, L 1 L may be a phenylene group. 2 A may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. - and Na + A combination of salts is also acceptable.

[0063] More specifically, *-OL 1 -L 2 -The substituent represented by A is represented by chemical formula 2 or 3 below: [Chemical formula 2] [ka] [Chemical formula 3] [ka] In chemical formula 2, R 51 ~R 55 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted C1-C20 alkyl group, or *-L 2 -A and R 51 ~R 55At least one of them is *-L 2 -A, and in chemical formulas 2 and 3, L 2 A is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and A is SO3 - A single anion, or SO3 - and Na + This is a combination of salts.

[0064] A dispersion aid represented by chemical formula 1 is represented by one of the following chemical formulas 1-1 to 1-4: [Chemical formula 1-1] [ka] [Chemical formula 1-2] [ka] [Chemical formula 1-3] [ka] [Chemical formula 1-4] [ka]

[0065] In chemical formulas 1-1 to 1-4, M is either Cu or Zn, and R 11 ~R 14 , R 21 ~R 24 , R 31 ~R 34 , and R 41 ~R 44 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R 51 ~R 55 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted C1-C20 alkyl group, or *-L 2 -A and R 51 ~R 55 At least one of them is *-L2 -A and L 2 A is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and A is SO3 - A single anion, or SO3 - and Na + This is a combination of salts.

[0066] The specific explanations for each substituent in chemical formulas 1-1 to 1-4 are as described above.

[0067] Typical examples of dispersion aids represented by chemical formula 1 are as follows: [Chemical formula 1-1-1] [ka] [Chemical formula 1-1-2] [ka] [Chemical formula 1-1-3] [ka] [Chemical formula 1-1-4] [ka] [Chemical formula 1-1-5] [ka] [Chemical formula 1-1-6] [ka] [Chemical formula 1-1-7] [ka] [Chemical formula 1-1-8] [ka] [Chemical Formula 1-1-9]

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[0068] As described above, the dispersion aid represented by chemical formula 1 has a phthalocyanine-based core that exhibits blue color, and can further improve the coloring power and light-dark ratio of the photosensitive resin composition.

[0069] Specifically, the dispersion aid represented by chemical formula 1 has a maximum absorption wavelength (λ max ) may be 450nm to 495nm.

[0070] The dispersion aid represented by chemical formula 1 is included in the photosensitive resin composition in an amount of 0.5% to 6% by weight, specifically 1% to 5% by weight, for example, 2% to 3% by weight, relative to the total amount of the photosensitive resin composition.

[0071] Furthermore, the weight ratio of the dispersion aid and pigment represented by chemical formula 1 is 1:20 to 1:70, specifically 1:30 to 1:60, and may also be, for example, 1:40 to 1:50.

[0072] Within each of the above-mentioned ranges, the dispersibility and dispersion stability of the photosensitive resin composition according to one embodiment can be improved, and the coloring power and light-dark ratio can be enhanced.

[0073] The coloring agent may contain pigments, and examples of pigments that can be used include green pigment, blue pigment, red pigment, purple pigment, yellow pigment, and black pigment.

[0074] Red pigments can be used within the Color Index, including CI Red Pigment 254, CI Red Pigment 255, CI Red Pigment 264, CI Red Pigment 270, CI Red Pigment 272, CI Red Pigment 177, CI Red Pigment 89, etc. These can be used individually or in combination of two or more, but are not necessarily limited to these.

[0075] The purple pigment can use C.I. Violet Pigment 23 (V.23), C.I. Violet Pigment 29, dioxazine violet, Fast Violet B, methyl violet lake, indanthrene brilliant violet, etc. within the Color Index, and these can be used alone or in combination of two or more, but are not necessarily limited thereto.

[0076] The green pigment can use C.I. Green Pigment 7, C.I. Green Pigment 36, C.I. Green Pigment 58, C.I. Green Pigment 59, etc. within the Color Index, and these can be used alone or in combination of two or more, but are not necessarily limited thereto.

[0077] The blue pigment can use copper phthalocyanine pigments such as C.I. Blue Pigment 15:6, C.I. Blue Pigment 15, C.I. Blue Pigment 15:1, C.I. Blue Pigment 15:2, C.I. Blue Pigment 15:3, C.I. Blue Pigment 15:4, C.I. Blue Pigment 15:5, C.I. Blue Pigment 15:6, C.I. Blue Pigment 16, etc. within the Color Index, and these can be used alone or in combination of two or more, but are not necessarily limited thereto.

[0078] The yellow pigment can use isoindoline pigments such as C.I. Yellow Pigment 185, C.I. Yellow Pigment 139, etc., quinophthalone pigments such as C.I. Yellow Pigment 138, nickel complex pigments such as C.I. Yellow Pigment 150, etc. within the Color Index, and these can be used alone or in combination of two or more, but are not necessarily limited thereto.

[0079] Black pigments can include aniline black, perylene black, titanium black, and carbon black within the Color Index, and these can be used individually or in combination of two or more, but are not necessarily limited to these.

[0080] Pigments can be used individually or in mixtures of two or more. For example, green pigment, yellow pigment, or mixtures thereof can be used as pigments.

[0081] The dispersant plays a role in uniformly dispersing the pigment in the dispersion, and nonionic, anionic, or cationic dispersants can be used. Specifically, polyalkylene glycol or its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts, alkylamines, etc., can be used individually or in combination of two or more.

[0082] The pigment is included in the photosensitive resin composition for color filters in the form of a dispersion. Such a pigment dispersion may further contain a dispersion solvent, a dispersion resin, and the like, in addition to the pigment, dispersant, and dispersion aid. The solid pigment, excluding the solvent, is included in an amount of 5% to 20% by weight, for example, 8% to 15% by weight, relative to the total amount of the pigment dispersion.

[0083] As the solvent for the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc., can be used, and of these, propylene glycol methyl ether acetate can be used.

[0084] As the dispersion resin, an acrylic resin containing carboxyl groups can be used, which not only improves the stability of the pigment dispersion but also improves the patternability of the pixels.

[0085] The colorant may include a pigment and may further include a dye, in which case the resin composition of one embodiment may be a hybrid composition. Furthermore, the dye is not particularly limited and may include metal complex dyes.

[0086] Metal complex dyes can use compounds that have maximum absorbance in the wavelength range of 200 nm to 650 nm. To match the color coordinates of the dye combination, any metal complex dye of any color that is soluble in organic solvents and has absorbance within the above range can be used.

[0087] Specifically, the metal complex dyes that can be used are green dyes having maximum absorbance in the wavelength range of 530 nm to 680 nm, yellow dyes having maximum absorbance in the wavelength range of 200 nm to 400 nm, orange dyes having maximum absorbance in the wavelength range of 300 nm to 500 nm, red dyes having maximum absorbance in the wavelength range of 500 nm to 650 nm, or combinations thereof.

[0088] Metal complex dyes that can be used include direct dyes, acid dyes, basic dyes, acid mordant dyes, sulfur dyes, reductive dyes, azoic dyes, disperse dyes, reactive dyes, oxidation dyes, oil-soluble dyes, azo dyes, anthraquinone dyes, indigoid dyes, carbonium ion dyes, phthalocyanine dyes, nitro dyes, quinoline dyes, cyanine dyes, polymethine dyes, or combinations thereof.

[0089] Metal complex dyes may contain at least one metal ion selected from the group consisting of Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd, and Fe.

[0090] Metal complex dyes include CI oil-soluble dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and CI acid dyes such as CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109. CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes, CI Basic Green 1 and other CI basic dyes, CI Modant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and others. A complex of a metal ion with at least one selected from the group consisting of any CI acidic mordant dye, phthalocyanine pigments such as CI pigment greens 7, 36, and 58, solvent yellow 19, solvent yellow 21, solvent yellow 25, solvent yellow 79, solvent yellow 82, solvent yellow 88, solvent orange 45, solvent orange 54, solvent orange 62, solvent orange 99, solvent red 8, solvent red 32, solvent red 109, solvent red 112, solvent red 119, solvent red 124, solvent red 160, solvent red 132, and solvent red 218 can be used.

[0091] The dye containing the metal complex has a solubility of 5 or higher in the solvent used in the photosensitive resin composition according to one embodiment, that is, in the solvent described later, and specifically may be 5 to 10. Solubility can be obtained as the amount (g) of dye that dissolves in 100g of solvent. When the solubility of the dye containing the metal complex is within the above range, compatibility with other components of the photosensitive resin composition according to one embodiment and coloring ability can be ensured, and precipitation of the dye can be prevented.

[0092] As solvents, for example, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone, 3-methoxy-1-butanol, or combinations thereof can be used.

[0093] Having the above-mentioned specific range, it can be usefully used in color filters for LCDs, LEDs, etc., that exhibit high brightness and high contrast ratio at desired color coordinates.

[0094] The dye containing the metal complex is included in the photosensitive resin composition in an amount of 0.01% to 1% by weight, for example, 0.01% to 0.5% by weight, relative to the total amount. When the dye containing the metal complex is used within the above range, high brightness and light-to-dark ratio can be achieved in the desired color coordinates.

[0095] When mixing dyes and pigments, they can be used in a weight ratio of 0.1:99.9 to 99.9:0.1, specifically 1:9 to 9:1. Mixing within this weight ratio range allows for appropriate control of chemical resistance and maximum absorption wavelength, resulting in high brightness and contrast ratios at the desired color coordinates.

[0096] The coloring agent is included in an amount of 5% to 50% by weight, specifically 6% to 40% by weight, or for example, 7% to 30% by weight, based on the solid content of the photosensitive resin composition. When the coloring agent is included within the above range, excellent coloring effect and developability can be achieved.

[0097] (B) Photopolymerizable compound As the photopolymerizable compound, monofunctional or polyfunctional esters of (meth)acrylic acid having at least one ethylenically unsaturated double bond can be used.

[0098] Photopolymerizable compounds, by possessing ethylenically unsaturated double bonds, can undergo sufficient polymerization during exposure in the pattern formation process, thereby forming patterns with excellent heat resistance, light resistance, and chemical resistance.

[0099] Specific examples of photopolymerizable compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Examples include acrylates, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, and novolac epoxy(meth)acrylate.

[0100] Examples of commercially available photopolymerizable compounds include the following: Examples of monofunctional esters of (meth)acrylic acid include Arronix® M-101, M-111, and M-114 from Toagosei Chemical Industry Co., Ltd., KAYARAD® TC-110S and TC-120S from Nippon Kayaku Co., Ltd., and V-158 and V-2311 from Osaka Organic Chemical Industry Co., Ltd. Examples of difunctional esters of (meth)acrylic acid include Arronix® M-210, M-240, and M-6200 from Toagosei Chemical Industry Co., Ltd., KAYARAD® HDDA, HX-220, and R-604 from Nippon Kayaku Co., Ltd., and V-260, V-312, and V-335HP from Osaka Organic Chemical Industry Co., Ltd. Examples of trifunctional esters of (meth)acrylic acid include Aronix® M-309, M-400, M-405, M-450, M-710, M-8030, and M-8060 from Toagosei Chemical Industry Co., Ltd., KAYARAD® TMPTA, DPCA-20, -30, -60, and -120 from Nippon Kayaku Co., Ltd., and V-295, -300, -360, -GPT, -3PA, and -400 from Osaka Organic Chemical Industry Co., Ltd. The products can be used individually or in combination of two or more.

[0101] Photopolymerizable compounds can also be treated with acid anhydrides before use to impart better developability.

[0102] The photopolymerizable compound is included in the photosensitive resin composition at an amount of 0.1% to 20% by weight, specifically 1% to 15% by weight, for example, 2% to 13% by weight, relative to the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, sufficient curing occurs during exposure in the pattern formation process, resulting in excellent reliability and excellent developability in alkaline developers.

[0103] (C) Photopolymerization initiator Photopolymerization initiators are commonly used initiators in photosensitive resin compositions, and for example, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, or combinations thereof can be used.

[0104] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one.

[0105] Examples of benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0106] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0107] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0108] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine. Examples include din, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, and 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

[0109] Examples of oxime compounds include O-acyl oxime compounds, 2-(o-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropane-1-one. Specific examples of O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butan-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0110] In addition to the compound, other photopolymerization initiators that can be used include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, and fluorene compounds.

[0111] Photopolymerization initiators can also be used in conjunction with photosensitizers, which absorb light, become excited, and then transfer that energy to initiate a chemical reaction.

[0112] Examples of photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol tetrakis-3-mercaptopropionate.

[0113] The photopolymerization initiator is included in an amount of 0.1% to 5% by weight, for example, 1% to 3% by weight, relative to the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, sufficient curing occurs during exposure in the pattern formation process, resulting in excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, as well as excellent resolution and adhesion, and preventing a decrease in transmittance due to unreacted initiators.

[0114] (D) Binder resin The binder resin may include acrylic resins.

[0115] Acrylic resins are copolymers of a primary ethylenically unsaturated monomer and a secondary ethylenically unsaturated monomer copolymerizable therewith, and are resins containing one or more acrylic repeating units.

[0116] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

[0117] The primary ethylenically unsaturated monomer is included in an amount of 5% to 50% by weight, for example, 10% to 40% by weight, relative to the total amount of the acrylic binder resin.

[0118] Examples of secondary ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzyl methyl ether; unsaturated carboxylic acid ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and phenyl (meth)acrylate; unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; vinyl carboxylic acid ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; and unsaturated amide compounds such as (meth)acrylamide. These can be used individually or in combination of two or more.

[0119] Specific examples of acrylic resins include (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, and (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited to these, and can be used individually or in combination of two or more.

[0120] The binder resin may include epoxy-based binder resins.

[0121] The heat resistance of the binder resin can be improved by further including an epoxy binder resin. Examples of epoxy binder resins include, but are not limited to, phenol novolac epoxy resins, tetramethylbiphenyl epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, alicyclic epoxy resins, or combinations thereof.

[0122] Furthermore, binder resins containing epoxy-based binder resins ensure the dispersion stability of colorants such as pigments, as described later, while simultaneously helping to form pixels of the desired resolution during the development process.

[0123] The epoxy binder resin is included in an amount of 1% to 10% by weight, for example, 5% to 10% by weight, relative to the total amount of binder resin. When the epoxy binder resin is included within the above range, the residual film rate and chemical resistance are significantly improved.

[0124] The epoxy equivalent weight of the epoxy binder resin may be between 150 g / eq and 200 g / eq. When an epoxy binder resin having an epoxy equivalent weight within the above range is included in the binder resin, it has a favorable effect on improving the degree of curing of the formed pattern and on the adhesion of the colorant within the structure in which the pattern is formed.

[0125] The binder resin can be dissolved in a solvent described later in solid form to form a photosensitive resin composition. In this case, the amount of binder resin in solid form may be about 0.1% to 30% by weight, for example, 20% to 30% by weight, relative to the total amount of the binder resin solution dissolved in the solvent.

[0126] The binder resin is included in an amount of 0.1% to 20% by weight, specifically 0.5% to 15% by weight, or for example, 1% to 10% by weight, relative to the total amount of the photosensitive resin composition, based on the solid content. When the binder resin is included within the above range, excellent developability, improved crosslinking properties, and superior surface smoothness can be obtained during the manufacture of color filters.

[0127] (E) Solvent As a solvent, a substance that is compatible with but does not react with colorants, binder resins, photopolymerizable compounds, and photopolymerization initiators can be used.

[0128] Examples of solvents include alcohols such as methanol and ethanol, ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate, carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl-n-propyl ketone. Ketones such as methyl-n-butyl ketone, methyl-n-amyl ketone, 2-heptanone, saturated aliphatic monocarboxylate alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, lactic acid esters such as methyl lactate, ethyl lactate, alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, alkyl alkoxyacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-hydroxypropionate, 3- 3-hydroxypropionate alkyl esters such as ethyl oxypropionate, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate ethyl, 3-ethoxypropionate methyl and other 3-alkoxypropionate alkyl esters, 2-hydroxypropionate methyl, 2-oxypropionate ethyl, 2-oxypropionate propyl and other 2-hydroxypropionate alkyl esters, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-ethoxypropionate ethyl,Alkyl 2-alkoxypropionates such as methyl 2-ethoxypropionate, 2-oxy-2-methylpropionates such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, alkyl monooxymonocarboxylates of alkyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate, esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate, Examples include ketonic acid esters such as ethyl pyruvate, as well as high-boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0129] Of these, considering compatibility and reactivity, the solvent can be propylene glycol monomethyl ether acetate (PGMEA), n-butyl acetate (n-BA), ethylene glycol dimethyl ether, or a combination thereof.

[0130] The solvent is included in the remainder of the total amount of the photosensitive resin composition, for example, 70% to 90% by weight, or for example, 80% to 90% by weight. When the solvent is included within the above range, a coating film with excellent coatability and flatness can be obtained from the photosensitive resin composition.

[0131] (F) Other additives The photosensitive resin composition may further contain at least one additive selected from malonic acid; 3-amino-1,2-propanediol; coupling agents containing vinyl groups or (meth)acrylooxy groups, leveling agents, surfactants, and radical polymerization initiators in order to prevent stains and spots during application, improve leveling performance, and prevent the formation of residues due to undeveloped material.

[0132] The additives can be easily adjusted according to the desired physical properties.

[0133] The coupling agent is a silane-based coupling agent. Examples of silane-based coupling agents include trimethoxysilylbenzoic acid, γ-methacrylateoxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-epoxycyclohexyl)ethyltrimethoxysilane. These can be used individually or in combination of two or more.

[0134] Specifically, the silane coupling agent can be used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the photosensitive resin composition.

[0135] Furthermore, the photosensitive resin composition for color filters may further contain a surfactant, such as a fluorinated surfactant, as needed.

[0136] Examples of fluorinated surfactants include, but are not limited to, DIC's F-482, F-484, and F-478.

[0137] The surfactant is preferably present in an amount of 0.01% to 5% by weight, and more preferably in an amount of 0.01% to 2% by weight, relative to the total amount of the photosensitive resin composition. If it falls outside this range, it may cause problems such as the formation of foreign matter after development, and is therefore undesirable.

[0138] Furthermore, the photosensitive resin composition may also contain a certain amount of other additives, such as antioxidants and stabilizers, as long as they do not impair its physical properties.

[0139] (Photosensitive resin film, color filter, and display) According to another embodiment, a photosensitive resin film is provided that is manufactured using the photosensitive resin composition according to one embodiment.

[0140] One embodiment of the photosensitive resin film can be broadly classified into a color-positive photoresist composition and a color-negative photoresist composition.

[0141] The photosensitive resin film in one embodiment may be a color-negative photoresist. This has the advantage that no coloring occurs due to the photoresist and that it is relatively more photosensitive than a positive photoresist.

[0142] In yet another embodiment, a color filter manufactured using the above-described photosensitive resin composition is provided.

[0143] A method for manufacturing a color filter according to one embodiment is as follows:

[0144] A photosensitive resin composition layer is formed on a glass substrate by applying the above-mentioned photosensitive resin composition to a thickness of, for example, 0.5 μm to 10 μm using an appropriate method such as spin coating, roller coating, or spray coating.

[0145] Next, the substrate on which the photosensitive resin composition layer is formed is irradiated with light to form the pattern required for the color filter. UV, electron beams, or X-rays can be used as the light source for irradiation, and for example, UV in the 190nm to 450nm range, specifically in the 200nm to 400nm range, can be irradiated. The above irradiation step can also be carried out using a photoresist mask. After performing this irradiation step, the photosensitive resin composition layer that has been irradiated with the light source is treated with a developer solution. At this time, the unexposed parts of the photosensitive resin composition layer dissolve, forming the pattern required for the color filter. By repeating this process according to the required number of colors, a color filter with the desired pattern can be obtained. Furthermore, if the image pattern obtained by development in the above step is heated again or cured by active ray irradiation, crack resistance, solvent resistance, etc., can be improved.

[0146] Another embodiment provides a display including the color filter described above.

[0147] The display may be an LCD display, a CMOS image sensor, or the like. [Examples]

[0148] The present invention will be described in more detail below with reference to examples, but the following examples are merely preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0149] Synthesis Example 1 (1) Production of intermediate 1-1 [ka]

[0150] 10 g of 2-(4-Hydroxyphenyl)ethanol and 100 g of bromate were placed in a 250 ml flask, and a condenser was connected to create a nitrogen atmosphere. The mixture was heated at 80°C while stirring. After the reaction was complete, the mixture was extracted with MC (Dichloromethane). The extracted organic layer was dewatered with MgSO4, concentrated, and vacuum-dried to obtain intermediate 1-1.

[0151] (2) Production of intermediates 1-2 [ka]

[0152] In a 100 ml flask, intermediate 1-1 (5 g) from Synthesis Example 1, 4-Nitrophthalonitrile (4.31 g), K2CO3 (6.19 g), and N,N-dimethylformamide (DMF) (25 ml) were added and heated at 70°C while stirring. After the reaction was complete, the mixture was extracted with EA (ethyl acetate). After extraction, the mixture was concentrated and purified by column chromatography. After purification, the mixture was vacuum-dried to obtain intermediate 1-2.

[0153] (3) Production of intermediates 1-3 [ka]

[0154] In a 100 mL flask, intermediate 1-9 (3 g), phthalonitrile (3.52 g), 1,8-Diazabicycloundec-7-ene (1.98 g), and 1-pentanol (30 g) were placed and heated at 90°C to dissolve the solid. Then, zinc acetate (1.68 g) was added and the mixture was stirred while heating at 140°C. After the reaction was complete, precipitation was confirmed with methanol, and the mixture was filtered and vacuum-dried. The dried solid was purified by column chromatography. After purification, MC was added to the obtained solid to dissolve it, and then methanol was added to crystallize it. The crystallized solid was filtered and vacuum-dried to obtain the compound represented by intermediate 1-3.

[0155] (4) Preparation of the compound represented by chemical formula 1-1-1 Intermediate 1-3 (1.0 g), sodium sulfite (0.32 g), and DMF (10 ml) were placed in a 100 mL flask, and a condenser was connected to create a nitrogen atmosphere. The mixture was heated at 120 °C while stirring. After the reaction was complete, the mixture was extracted with MC. The extracted organic layer was concentrated by removing water with MgSO4. After dissolving the obtained solid with an appropriate amount of MC, methanol was added and crystallization was carried out. The crystallized solid was filtered and vacuum-dried to obtain the compound represented by the following chemical formula 1-1-1. [Chemical formula 1-1-1] [ka] Maldi-TOF MS: 777 m / z

[0156] Synthesis Example 2 (1) Synthesis of intermediates 1-4 [ka]

[0157] In a 100 mL flask, intermediates 1-2 (4 g), phthalonitrile (2.75 g), 4-tert-Butylphthalonitrile (1.98 g), 1,8-Diazabicycloundec-7-ene (2.08 g), and 1-pentanol (30 g) were placed and heated at 90°C to dissolve the solid. Then, zinc acetate (1.97 g) was added and the mixture was stirred while heating at 140°C. After the reaction was complete, precipitation was confirmed with methanol, and the mixture was filtered and vacuum-dried. The dried solid was purified by column chromatography. After purification, MC was added to the obtained solid to dissolve it, and then methanol was added to crystallize it. The crystallized solid was filtered and vacuum-dried to obtain intermediates 1-4.

[0158] (2) Preparation of the compound represented by chemical formula 1-1-2 Intermediate 1-4 (1.0 g), sodium sulfite (0.33 g), and DMF (10 ml) were placed in a 100 mL flask, and a condenser was connected to create a nitrogen atmosphere. The mixture was heated at 120 °C while stirring. After the reaction was complete, the mixture was extracted with MC. The extracted organic layer was concentrated by removing water with MgSO4. After dissolving the obtained solid with an appropriate amount of MC, methanol was added and crystallization was carried out. The crystallized solid was filtered and vacuum-dried to obtain the compound represented by the following chemical formula 1-1-2. [Chemical formula 1-1-2] [ka] Maldi-TOF MS: 834 m / z

[0159] Synthesis Example 3 (1) Production of intermediates 1-5 [ka]

[0160] Intermediate 1-1 (5g), 3,4,5,6-tetrachlorophthalonitrile (6.61g), K2CO3 (6.19g), and N,N-dimethylformamide (DMF) (25ml) were placed in a 100ml flask and stirred while heating at 70°C. After the reaction was complete, the mixture was extracted with EA (ethyl acetate). After extraction, the solution was concentrated and purified by column chromatography. After purification, the solution was vacuum-dried to obtain intermediate 1-5.

[0161] (2) Production of intermediates 1-6 [ka]

[0162] In a 100 mL flask, intermediates 1-5 (2 g), phthalonitrile (1.19 g), 4-tert-Butylphthalonitrile (0.86 g), 1,8-Diazabicycloundec-7-ene (2.08 g), and 1-pentanol (15 g) were added and heated at 90°C to dissolve the solid. Then, zinc acetate (0.85 g) was added and the mixture was stirred while heating at 140°C. After the reaction was complete, precipitation was confirmed with methanol, and the mixture was filtered and vacuum-dried. The dried solid was purified by column chromatography. After purification, MC was added to the obtained solid to dissolve it, and then methanol was added to crystallize it. The crystallized solid was filtered and vacuum-dried to obtain intermediate 1-6.

[0163] (3) Preparation of the compound represented by chemical formula 1-1-4 Intermediate 1-6 (1.0 g), Na2SO3 (0.54 g), and DMF (10 ml) were placed in a 100 mL flask, and a condenser was connected to create a nitrogen atmosphere. The mixture was heated at 60°C while stirring. After the reaction was complete, the mixture was extracted with MC. The extracted organic layer was concentrated by removing water with MgSO4. MC was added to the resulting solid to dissolve it, and then methanol was added to crystallize it. The crystallized solid was filtered and vacuum-dried to obtain the compound represented by the following chemical formula 1-1-4.

[0164] [Chemical formula 1-1-4] [ka] Maldi-TOF MS: 937 m / z

[0165] Synthesis Example 4 (1) Production of intermediates 1-7 [ka]

[0166] 10 g of 2-Hydroxyphenethyl alcohol and 100 g of bromate were placed in a 250 ml flask, a condenser was connected, and a nitrogen atmosphere was created. The mixture was heated at 80°C while stirring. After the reaction was complete, the mixture was extracted with MC (Dichloromethane). The extracted organic layer was dewatered with MgSO4, concentrated, and vacuum-dried to obtain intermediates 1-7.

[0167] (2) Production of intermediates 1-8 [ka]

[0168] In a 100 ml flask, intermediates 1-7 (5 g), 3,4,5,6-tetrachlorophthalonitrile (6.61 g), K2CO3 (6.19 g), and N,N-dimethylformamide (DMF) (25 ml) were added and heated at 70°C while stirring. After the reaction was complete, the mixture was extracted with EA (ethyl acetate). After extraction, the solution was concentrated and purified by column chromatography. After purification, the solution was vacuum-dried to obtain intermediates 1-8.

[0169] (3) Production of intermediates 1-9 [ka]

[0170] In a 100 mL flask, intermediate 1-8 (2 g), phthalonitrile (1.19 g), 4-tert-Butylphthalonitrile (0.86 g), 1,8-Diazabicycloundec-7-ene (2.08 g), and 1-pentanol (15 g) were placed and heated at 90°C to dissolve the solid. Then, zinc acetate (0.85 g) was added and the mixture was stirred while heating at 140°C. After the reaction was complete, precipitation was confirmed with methanol, and the mixture was filtered and vacuum-dried. The dried solid was purified by column chromatography. After purification, MC was added to the obtained solid to dissolve it, and then methanol was added to crystallize it. The crystallized solid was filtered and vacuum-dried to obtain intermediate 1-9.

[0171] (4) Preparation of the compound represented by chemical formula 1-1-14 Intermediate 1-9 (1.0 g), Na2SO3 (0.54 g), and DMF (10 ml) were placed in a 100 mL flask, and a condenser was connected to create a nitrogen atmosphere. The mixture was heated at 60°C while stirring. After the reaction was complete, the mixture was extracted with MC. The extracted organic layer was concentrated by removing water with MgSO4. After dissolving the obtained solid with an appropriate amount of MC, methanol was added and crystallization was carried out. The crystallized solid was filtered and vacuum-dried to obtain the compound represented by the following chemical formula 1-1-14. [Chemical formula 1-1-14] [ka] Maldi-TOF MS: 937 m / z

[0172] Synthesis Example 5 (1) Production of intermediates 1-10 [ka]

[0173] 10 g of 2-(3-Hydroxyphenyl)ethanol and 100 g of bromate were placed in a 250 ml flask, and a condenser was connected to create a nitrogen atmosphere. The mixture was heated at 80°C while stirring. After the reaction was complete, the mixture was extracted with MC (Dichloromethane). The extracted organic layer was dewatered with MgSO4, concentrated, and vacuum-dried to obtain intermediates 1-10.

[0174] (2) Production of intermediates 1-11 [ka]

[0175] In a 100 ml flask, intermediates 1-10 (5 g), 3,4,5,6-tetrachlorophthalonitrile (6.61 g), K2CO3 (6.19 g), and N,N-dimethylformamide (DMF) (25 ml) were added and heated at 70°C while stirring. After the reaction was complete, the mixture was extracted with EA (ethyl acetate). After extraction, the mixture was concentrated and purified by column chromatography. After purification, the mixture was vacuum-dried to obtain intermediates 1-11.

[0176] (3) Production of intermediates 1-12 [ka]

[0177] In a 100 mL flask, intermediates 1-11 (2 g), phthalonitrile (1.19 g), 4-tert-Butylphthalonitrile (0.86 g), 1,8-Diazabicycloundec-7-ene (2.08 g), and 1-pentanol (15 g) were added and heated at 90°C to dissolve the solid. Then, zinc acetate (0.85 g) was added and the mixture was stirred while heating at 140°C. After the reaction was complete, precipitation was confirmed with methanol, and the mixture was filtered and vacuum-dried. The dried solid was purified by column chromatography. After purification, MC was added to the obtained solid to dissolve it, and then methanol was added to crystallize it. The crystallized solid was filtered and vacuum-dried to obtain intermediates 1-9.

[0178] (4) Preparation of the compound represented by chemical formula 1-1-14 Intermediate 1-12 (1.0 g), Na2SO3 (0.54 g), and DMF (10 ml) were placed in a 100 mL flask, and a condenser was connected to create a nitrogen atmosphere. The mixture was heated at 60°C while stirring. After the reaction was complete, the mixture was extracted with MC. The extracted organic layer was concentrated by removing water with MgSO4. After dissolving the obtained solid with an appropriate amount of MC, methanol was added and crystallization was carried out. The crystallized solid was filtered and vacuum-dried to obtain the compound represented by the following chemical formula 1-1-24. [Chemical formula 1-1-24] [ka] Maldi-TOF MS: 937 m / z

[0179] Synthesis Example 6 (1) Production of intermediates 1-13 [ka]

[0180] 3-(4-Hydroxyphenyl)-1-propanol (10 g) and bromate (100 g) were placed in a 250 ml flask, and a condenser was connected to create a nitrogen atmosphere. The mixture was heated at 80°C while stirring. After the reaction was complete, the mixture was extracted with MC (Dichloromethane). The extracted organic layer was dewatered with MgSO4, concentrated, and vacuum-dried to obtain intermediates 1-13.

[0181] (2) Production of intermediates 1-14 [ka]

[0182] Intermediate 1-13 (5g), 3,4,5,6-tetrachlorophthalonitrile (6.18g), K2CO3 (6.08g), and N,N-dimethylformamide (DMF) (25ml) were placed in a 100ml flask and heated with stirring at 70°C. After the reaction was complete, the mixture was extracted with EA (ethyl acetate). After extraction, the solution was concentrated and purified by column chromatography. After purification, the solution was vacuum-dried to obtain intermediate 1-14.

[0183] (3) Production of intermediates 1-15 [ka]

[0184] In a 100 mL flask, intermediate 1-14 (2 g), phthalonitrile (1.15 g), 4-tert-Butylphthalonitrile (0.83 g), 1,8-Diazabicycloundec-7-ene (2.08 g), and 1-pentanol (15 g) were placed and heated at 90°C to dissolve the solid. Then, zinc acetate (0.83 g) was added and the mixture was stirred while heating at 140°C. After the reaction was complete, precipitation was confirmed with methanol, and the mixture was filtered and vacuum-dried. The dried solid was purified by column chromatography. After purification, MC was added to the obtained solid to dissolve it, and then methanol was added to crystallize it. The crystallized solid was filtered and vacuum-dried to obtain intermediate 1-15.

[0185] (5) Preparation of the compound represented by chemical formula 1-1-34 Intermediate 1-15 (1.0 g), Na2SO3 (0.27 g), and DMF (10 ml) were placed in a 100 mL flask, and a condenser was connected to create a nitrogen atmosphere. The mixture was heated at 60°C while stirring. After the reaction was complete, the mixture was extracted with MC. The extracted organic layer was concentrated by removing water with MgSO4. After dissolving the obtained solid with an appropriate amount of MC, methanol was added and crystallization was carried out. The crystallized solid was filtered and vacuum-dried to obtain the compound represented by the following chemical formula 1-1-34. [Chemical formula 1-1-34] [ka] Maldi-TOF MS: 951 m / z

[0186] Comparative Synthesis Example 1 (1) Production of intermediates 1-9 [ka]

[0187] 4-Propylphenol (5g), 4-Nitrophthalonitrile (6.35g), K2CO3 (6.08g), and N,N-dimethylformamide (DMF) (25ml) were placed in a 100ml flask and heated and stirred at 70°C. After the reaction was complete, the mixture was extracted with EA (ethyl acetate). After extraction, the mixture was concentrated and purified by column chromatography. After purification, the mixture was vacuum-dried to obtain intermediates 1-9.

[0188] (2) Preparation of the compound represented by chemical formula A [ka]

[0189] In a 100 mL flask, intermediate 1-9 (3 g), phthalonitrile (4.40 g), 1,8-Diazabicycloundec-7-ene (2.08 g), and 1-pentanol (30 g) were placed and heated at 90°C to dissolve the solid. Then, zinc acetate (2.10 g) was added and the mixture was stirred while heating at 140°C. After the reaction was complete, precipitation was confirmed with methanol, and the mixture was filtered and vacuum-dried. The dried solid was purified by column chromatography. After purification, MC was added to the obtained solid to dissolve it, and then methanol was added to crystallize it. The crystallized solid was filtered and vacuum-dried to obtain the compound represented by chemical formula A. [Chemical formula A] [ka] Maldi-Tof MS: 712.11 m / z

[0190] Production of green pigment dispersion The green pigment dispersions of Production Examples 1-11 and Production Comparative Examples 1 and 2 were prepared by mixing the pigments according to the compositions shown in Tables 1-3 below.

[0191] Specifically, a green pigment, a dispersant, a dispersion aid, and a solvent were mixed. 300 parts of zirconia beads (diameter: 0.4 μm) were added to 100 parts by weight of this mixture, and the mixture was shaken for 3 hours using a paint shaker to disperse the beads. The zirconia beads were then removed by filtration to obtain a green pigment dispersion. [Table 1]

[0192] [Table 2]

[0193] [Table 3]

[0194] The substances used in Tables 1-3 above are as follows: Green pigment: CIPIGMENT Green 58 (G58) Dispersant: BYK-LPN6919 (Manufacturer: BYK) Dispersion aids: Compounds from Synthesis Examples 1-6 and Comparative Synthesis Example 1 Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

[0195] Production of yellow pigment dispersion A yellow pigment dispersion was obtained by mixing 12.0 parts by weight of yellow pigment (CIPIGMENT Yellow 138), 3.0 parts by weight of dispersant (BYK-LPN6919, manufacturer: BYK), and 85.0 parts by weight of solvent (propylene glycol monomethyl ether acetate, PGMEA). 300 parts of zirconia beads (diameter: 0.4 μm) were added to 100 parts by weight of this mixture, and the mixture was shaken for 3 hours using a paint shaker to disperse the particles. The zirconia beads were then removed by filtration.

[0196] Manufacturing of photosensitive resin compositions The photosensitive resin compositions of Examples 1-11 and Comparative Examples 1 and 2 were prepared by mixing the materials according to the compositions shown in Tables 4-6 below.

[0197] Specifically, a photosensitive colored resin composition was produced by mixing a green pigment dispersion, a yellow pigment dispersion, a photopolymerizable monomer, a photopolymerization initiator, a binder resin, and a solvent. [Table 4]

[0198] [Table 5]

[0199] [Table 6]

[0200] The substances used in Tables 4-6 above are as follows:

[0201] (A) Coloring agent Green pigment dispersions: Green pigment dispersions from Production Examples 1-11 and Production Comparative Examples 1 and 2 Yellow pigment dispersion

[0202] (B) Photopolymerizable monomers Dipentaerythritol hexaacrylate (DPHA, Manufacturer: Nippon Kayaku Co., Ltd.)

[0203] (C) Photopolymerization initiator C-1:1,2-Octanedione C-2:2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one

[0204] (D) Binder resin A resin copolymerized with benzyl methacrylate and methacrylic acid in an 85:15 ratio (Mw=22,000)

[0205] (E) Solvent Propylene glycol monomethyl ether acetate (PGMEA)

[0206] Evaluation Example 1: Dispersion and Dispersion Stability The particle size of solids contained in each photosensitive resin composition in Examples 1 to 11 and Comparative Examples 1 and 2 was measured using a dynamic light scattering analyzer, and the results are shown in Table 7 below.

[0207] Furthermore, the viscosity of each photosensitive resin composition from Examples 1 to 11 and Comparative Examples 1 and 2 was evaluated using a Brookfield DV-II Pro viscometer and a CPE-52 Spindle at 5 rpm (selected at rpm that resulted in a Torque value of 50-100%) and 25°C, before and after storage at 23°C for one week. The results are shown in Table 7 below. [Table 7]

[0208] According to Table 7 above, the photosensitive resin compositions of Examples 1 to 11 show less difference in viscosity as well as less difference in solid particle size before and after one week of storage compared to the photosensitive resin compositions of Comparative Examples 1 and 2.

[0209] Evaluation Example 2: Coloring Power and Light-to-Dark Ratio Each of the photosensitive resin compositions from Examples 1-10 and Comparative Examples 1 and 2 was applied to a degreased and cleaned 1 mm thick glass substrate to a thickness of 1-3 μm, and dried on a hot plate at 90°C for 2 minutes to obtain a coating film. Next, the coating film was exposed using a high-pressure mercury lamp with a dominant wavelength of 365 nm, and then dried in a hot air circulating drying oven at 200°C for 5 minutes to obtain a color filter test piece.

[0210] The pixel layer was analyzed using a spectrophotometer (MCPD3000, Otsuka Electronic Co., Ltd.) to measure the color coordinates (x, y), luminance (Y), and brightness-to-dark ratio of a color filter test piece. The results are shown in Tables 8-10 below. [Table 8]

[0211] [Table 9]

[0212] [Table 10]

[0213] According to Tables 8-10 above, the color filter test specimens of Examples 1-11 showed improved coloring power and light-to-dark ratio compared to the color filter test specimens of Comparative Examples 1 and 2.

[0214] Overall, by using the dispersion aid represented by chemical formula 1, we were able to realize a photosensitive resin composition with high pigment dispersibility and dispersion stability, as well as excellent coloring power and light-to-dark ratio when used in color filters.

[0215] Examples 1 to 11 are presented here as representative examples, but it would be possible to adjust within the scope of one embodiment to control dispersibility, dispersion stability, coloring power, light-dark ratio, etc., to the desired level.

[0216] Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and can be implemented in various ways within the scope of the claims, the detailed description of the invention, and the attached drawings, and these also naturally fall within the scope of the present invention.

Claims

1. (A) Coloring agent, (B) photopolymerizable compound, (C) Photopolymerization initiator, (D) Binder resin, and (E) containing a solvent, The colorant is a photosensitive resin composition comprising a pigment, a dispersant, and a dispersion aid represented by the following chemical formula 1: [Chemical formula 1] 【Chemistry 1】 In the aforementioned chemical formula 1, M is either Cu or Zn. R １１ ~R １４ , R ２１ ~R ２４ , and R ３１ ~R ３４ Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ４１ ~R ４４ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or *-O-L １ -L ２ -A, and The aforementioned R ４１ ~R ４４ At least one of them is *-O-L １ -L ２ -A is, Said L １ This is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Said L ２ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, A is SO ３ － A single anion, or SO ３ － and Na ＋ It is a combination of salts, The dispersion aid represented by the chemical formula 1 is selected from the group consisting of the following: [Chemical formula 1-1-1] 【Transformation 8】 [Chemical formula 1-1-2] 【Chemistry 9】 [Chemical formula 1-1-3] 【Chemistry 10】 [Chemical formula 1-1-4] 【Chemistry 11】 [Chemical formula 1-1-5] 【Chemistry 12】 [Chemical formula 1-1-6] 【Chemistry 13】 [Chemical formula 1-1-7] 【Chemistry 14】 [Chemical formula 1-1-8] 【Chemistry 15】 [Chemical formula 1-1-9] 【Chemistry 16】 [Chemical formula 1-1-10] 【Chemistry 17】 [Chemical formula 1-1-11] [Chemistry 18] [Chemical formula 1-1-12] 【Chemistry 19】 [Chemical formula 1-1-13] 【Chemistry 20】 [Chemical formula 1-1-14] 【Chemistry 21】 [Chemical formula 1-1-15] 【Chemistry 22】 [Chemical formula 1-1-16] 【Chemistry 23】 [Chemical formula 1-1-17] 【Chemistry 24】 [Chemical formula 1-1-18] 【Chemistry 25】 [Chemical formula 1-1-19] 【Chemistry 26】 [Chemical formula 1-1-20] 【Chemistry 27】 [Chemical formula 1-1-21] 【Chemistry 28】 [Chemical formula 1-1-22] 【Chemistry 29】 [Chemical formula 1-1-23] 【Transformation 30】 [Chemical formula 1-1-24] 【Chemistry 31】 [Chemical formula 1-1-25] 【Chemistry 32】 [Chemical formula 1-1-26] 【Transformation 33】 [Chemical formula 1-1-27] 【Transformation 34】 [Chemical formula 1-1-28] 【Chemistry 35】 [Chemical formula 1-1-29] 【Transformation 36】 [Chemical formula 1-1-30] 【Chemistry 37】 [Chemical formula 1-1-31] 【Transformation 38】 [Chemical formula 1-1-32] 【Chemistry 39】 [Chemical formula 1-1-33] 【Chemistry 40】 [Chemical formula 1-1-34] 【Chemistry 41】 [Chemical formula 1-1-35] 【Chemistry 42】 [Chemical formula 1-1-36] 【Chemistry 43】 [Chemical formula 1-1-37] 【Chemistry 44】 [Chemical formula 1-1-38] 【Chemistry 45】 [Chemical formula 1-1-39] 【Chemistry 46】 [Chemical formula 1-1-40] 【Chemistry 47】 。

2. The photosensitive resin composition according to claim 1, wherein the dispersion aid represented by the chemical formula 1 has a maximum absorption wavelength of 450 nm to 495 nm.

3. The photosensitive resin composition according to claim 1, wherein the dispersion aid represented by the chemical formula 1 is contained in an amount of 0.5% to 6% by weight relative to the total amount of the photosensitive resin composition.

4. The photosensitive resin composition according to claim 1, wherein the weight ratio of the dispersion aid represented by the chemical formula 1 to the pigment is 1:20 to 1:

70.

5. The photosensitive resin composition according to claim 1, wherein the pigment comprises a green pigment, a yellow pigment, or a combination thereof.

6. The photosensitive resin composition is, in relation to the total amount of the photosensitive resin composition, The aforementioned (A) coloring agent, 0.5% to 15% by weight, The above (B) photopolymerizable compound 0.1% to 10% by weight, The above (C) photopolymerization initiator in an amount of 0.1% to 10% by weight, The above (D) binder resin 0.5% to 15% by weight, and The photosensitive resin composition according to claim 1, comprising the solvent (E) mentioned above.

7. A photosensitive resin film manufactured using the photosensitive resin composition described in any one of claims 1 to 6.

8. The photosensitive resin film according to claim 7, wherein the photosensitive resin film is a color negative photoresist.

9. A color filter comprising the photosensitive resin film described in claim 7.

10. A display including the color filter described in claim 9.

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