Photosensitive resin composition, photosensitive resin film and color filter manufactured using the composition

Abstract

The present invention provides a photosensitive resin composition exhibiting excellent spectral characteristics and sensor sensitivity, enabling the realization of thin films, a photosensitive resin film manufactured using the same, and a color filter. [Solution] A photosensitive resin composition according to one embodiment comprises (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a binder resin, and (E) a solvent, wherein the colorant comprises a green dye and a yellow pigment, the green dye comprises a first green dye and a second green dye, the first green dye comprises a core-shell compound consisting of a core represented by chemical formula 1 and a shell surrounding the core represented by chemical formula 2, the second green dye comprises a core-shell compound consisting of a core represented by chemical formula 1 and a shell surrounding the core represented by chemical formula 3, the first green dye is present in a greater weight than the second green dye on a solids basis, and the first green dye is present in a weight of less than nine times the weight of the second green dye on a solids basis.

Description

[Technical Field]

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

[0002] An image sensor is a semiconductor that converts photons into electrons, which can then be displayed on a screen or stored in a storage device. Depending on the manufacturing process and application method, image sensors are classified into charge-coupled device (CCD) image sensors and complementary metal oxide semiconductor (CMOS) image sensors. On the other hand, the image sensor is equipped with a color filter that includes filter segments of additive mixed primary colors: red, green, and blue.

[0003] 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 desired pattern shape to the light, removing the unexposed areas with a solvent, and then thermally curing the mixture. This process is repeated to form a colored thin film. The colored photosensitive resin composition used in the production of color filters by the pigment dispersion method generally consists of a pigment dispersion (a colorant), an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives. The pigment dispersion method, with its aforementioned characteristics, is actively applied to the production of LCDs in mobile phones, laptops, monitors, TVs, and other devices. However, recently, even photosensitive resin compositions for color filters using the pigment dispersion method, which has various advantages, are required to have not only excellent pattern characteristics but also further improved performance. In particular, there is an urgent need for high absorption efficiency along with high brightness and a high light-dark ratio.

[0004] Color filters manufactured from pigment-type photosensitive resin compositions have limitations in brightness and light-to-dark ratio, starting with the size of the pigment particles. Furthermore, in the case of color image sensors for image sensors, even smaller dispersion particle size and higher coloring power are required to form fine patterns. To meet these demands, attempts have been made to manufacture photosensitive resin compositions using dyes that do not form particles instead of pigments, thereby realizing color filters with improved spectral characteristics such as absorbance efficiency (coloring power) and brightness. Diverse research has also been conducted to improve the heat resistance, chemical resistance, and light resistance, which are inferior compared to pigments. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] U.S. Patent Application Publication No. 2019 / 0048196 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] One embodiment provides a photosensitive resin composition that exhibits excellent spectral characteristics and sensor sensitivity and can be realized as a thin film.

[0007] Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

[0008] Another embodiment provides a color filter including the photosensitive resin film. [Means for solving the problem]

[0009] One embodiment includes (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a binder resin, and (E) a solvent. The colorant includes a green dye and a yellow pigment. The green dye includes a first green dye and a second green dye. The first green dye includes a core-shell compound composed of a core represented by the following chemical formula 1 and a shell represented by the following chemical formula 2 surrounding the core. The second green dye includes a core-shell compound composed of a core represented by the following chemical formula 1 and a shell represented by the following chemical formula 3 surrounding the core. Based on the solid content, the first green dye is included in a weight greater than that of the second green dye, and based on the solid content, the first green dye is included in a weight less than 9 times the weight of the second green dye. A photosensitive resin composition is provided.

[0010]

Chemical formula

[0011]

Chemical formula

[0012]

Chemical formula

[0013] In the above Chemical formula 1 to Chemical formula 3, L 1 and L 2 are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R 1 and R[[ID=?]] 2 are each independently an epoxy group, R 3 and R 4 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, L a and L b It seems there is a small error in the original text where "R 2 " is repeated as "R<000000?>" in the translated content. Please check and correct if necessary.is each independently a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R a is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or *-C(=O)OR 0 (R 0 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), m and n2 are each independently an integer of 1 to 10, n1 is an integer of 1 to 4.

[0014] In the above Chemical Formula 1, R 3 is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and R 4 may be a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms.

[0015] The above Chemical Formula 2 can be represented by the following Chemical Formula 2-1.

[0016]

Chemical Formula

[0017] The above Chemical Formula 3 can be represented by the following Chemical Formula 3-1.

[0018]

Chemical Formula

[0019] In the above Chemical Formula 3-1, R b ~R e are each independently a halogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0020] The above first green dye and second green dye may be contained in a weight ratio of 3:1 to 7:1.

[0021] The first green dye has a maximum absorption wavelength (λ) at 640 nm to 650 nm. max ) can have.

[0022] The second green dye has a maximum absorption wavelength (λ) at 660nm to 670nm. max ) can have.

[0023] The first green dye can be represented by the following chemical formula 4-1 or chemical formula 4-2.

[0024] [ka] [Chemical formula 4-1]

[0025] [ka] [Chemical formula 4-2]

[0026] The second green dye can be represented by any one of the following chemical formulas 5-1 to 5-3.

[0027] [ka] [Chemical formula 5-1]

[0028] [ka] [Chemical formula 5-2]

[0029] [ka] [Chemical formula 5-3]

[0030] The green dye and yellow pigment may be present in an amount of 40% to 55% by weight, based on the total amount of solids constituting the photosensitive resin composition.

[0031] The photosensitive resin composition may contain, with respect to the total amount of solids constituting the photosensitive resin composition, 40% to 60% by weight of (A) the colorant, 5% to 30% by weight of (B) the photopolymerizable compound, 0.1% to 20% by weight of (C) the photopolymerization initiator, and 0.5% to 25% by weight of (D) the binder resin.

[0032] The photosensitive resin composition may further contain additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, an antioxidant, or a combination thereof.

[0033] Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

[0034] The photosensitive resin film may be a negative photoresist.

[0035] The photosensitive resin film may have a thickness of 500 nm, a transmittance of 9% or less at 450 nm, a transmittance of 90% or more at 550 nm, a transmittance of 15% or less at 630 nm, a transmittance of 4% or less at 650 nm, and a transmittance of 60% or less at 700 nm.

[0036] Another embodiment provides a color filter including the photosensitive resin film.

[0037] Another embodiment provides an image sensor including the color filter.

[0038] Another embodiment provides a display device including the image sensor.

[0039] Other specific aspects of the present invention are included in the detailed description below. [Effects of the Invention]

[0040] A photosensitive resin composition according to one embodiment has excellent spectral properties, and when a color filter is realized, it does not reduce coloring power, light resistance, and chemical resistance, and has excellent sensor sensitivity, making it possible to realize a thin film color filter for an image sensor, such as a green color filter for an image sensor, an image sensor, and a display device. [Modes for carrying out the invention]

[0041] Embodiments of the present invention will be described in detail below. However, these are presented as examples only and do not limit the present invention, which is defined only within the scope of the claims described below.

[0042] Unless otherwise specified herein, “substitution” means that at least one hydrogen atom in a compound is 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 amine group, an imino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or its salt, a sulfonic acid group or its salt, phosphoric acid or its salt, or a carbon-1 group. This means that the substituents are substituted with alkyl groups with up to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, alkynyl groups with 2 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, cycloalkenyl groups with 3 to 20 carbon atoms, cycloalkynyl groups with 3 to 20 carbon atoms, heterocycloalkyl groups with 2 to 20 carbon atoms, heterocycloalkenyl groups with 2 to 20 carbon atoms, heterocycloalkynyl groups with 2 to 20 carbon atoms, or combinations thereof.

[0043] 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.

[0044] Unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible.

[0045] Unless otherwise defined herein, “combination” means mixing or copolymerization. “Copolymer” means block copolymerization or random copolymerization, and “copolymer” means block copolymerization or random copolymerization.

[0046] 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.

[0047] Unless otherwise defined herein, "*" means a portion that is bonded to the same or different atoms or chemical formulas.

[0048] Unless otherwise defined herein, “particle size” may mean the diameter of a particle, and such particle size may be the Z-mean value of the particle diameter measured by dynamic light scattering.

[0049] For green color filters for image sensors, in order to increase sensor sensitivity, the transmittance must be low in the wavelength ranges of 380nm to 480nm and 630nm to 700nm, and high in the 480nm to 630nm range. Furthermore, in order to realize an ultrathin film of 0.5μm (500nm) or less, the absorbance intensity of the color material must be excellent, and even a small amount of color material must exhibit low transmittance in the required range. In this invention, in order to realize a green color filter that has excellent sensor sensitivity and can be realized as a thin film, the filter has both an enclosure structure and a thermosetting functional group, and the maximum absorption wavelength (λ maxTwo types of squalein-based green dyes, with wavelengths of 640nm-650nm and 660nm-670nm respectively, were mixed with a yellow pigment. The aforementioned coloring composition for green color filters has significantly superior spectral properties (green absorption wavelength and transmission wavelength) compared to pigment-type coloring compositions, and can exhibit similar chemical resistance to pigment-type coloring compositions due to its thermosetting functional groups. Furthermore, the aforementioned coloring composition for green color filters may have superior light resistance under vapor deposition conditions compared to general green coloring compositions containing phthalocyanine-based green pigments. In addition, a photosensitive resin composition to which this is applied can exhibit superior coloring power even at ultrathin film thicknesses of 0.5 μm or less compared to photosensitive resin compositions for color filters to which existing pigment dispersions are applied, and can also exhibit heat resistance and chemical resistance at a level equivalent to or higher than that of general pigment dispersions.

[0050] (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 green dye and a yellow pigment.

[0051] In this case, the green dye comprises a first green dye and a second green dye, the first green dye comprises a core-shell compound consisting of a core represented by the following chemical formula 1 and a shell surrounding the core represented by the following chemical formula 2, and the second green dye comprises a core represented by the following chemical formula 1 and a shell surrounding the core represented by the following chemical formula 3, the first green dye is present in a greater weight than the second green dye on a solids basis, and the first green dye is present in a weight of less than nine times the weight of the second green dye on a solids basis.

[0052] [ka] [Chemical formula 1]

[0053] [ka] [Chemical formula 2]

[0054] [ka] [Chemical formula 3]

[0055] Of the above chemical formulas 1 to 3, L 1 and L 2 Each of these is independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. R 1 and R 2 Each of these is an epoxy group independently, R 3 and R 4 Each of these is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. L a and L b Each of these is independently a single-bonded, substituted, or unsubstituted alkylene group having 1 to 20 carbon atoms. R a This is a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, or *-C(=O)OR 0 (R 0 (where is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms) m and n² are each independent integers between 1 and 10. n1 is an integer between 1 and 4.

[0056] (A) Coloring agent One embodiment of the photosensitive resin composition is a hybrid photosensitive resin composition in which both pigments and dyes are applied as colorants. Generally, hybrid photosensitive resin compositions have excellent spectral properties such as brightness and coloring power, but lack durability such as heat resistance, chemical resistance, and light resistance. Attempts have been made to improve this by changing the structure of the dye or by introducing a crosslinking reactor to combine the cationic structure of the dye with the anionic structure of the compound. However, under ultrathin film conditions of 0.5 μm or less, the absorbance intensity of the colorant is low, and it was difficult to achieve low transmittance in the required region with only a small amount of colorant.

[0057] In one embodiment, the coloring agent contained in the photosensitive resin composition uses a mixture of two different green dyes with a yellow dye. By controlling the structures of the two green dyes and the weight ratio of the two green dyes, the absorbance intensity of the coloring agent is excellent under ultrathin film conditions of 0.5 μm or less, and low transmittance in the required area can be easily achieved even with a small amount.

[0058] In other words, a hybrid colorant having the above-described composition can be used together with a dispersant and a dispersion binder to enhance the solubility of the dye, the dispersibility and dispersion stability of the pigment, and simultaneously enhance the coloring power. Therefore, when a photosensitive resin composition containing a colorant of the above composition is implemented in a color filter, image sensor, and display device, it is possible to achieve even better coloring power (color reproduction rate) and brightness-to-dark ratio.

[0059] In the above chemical formula 1, R 1 and R 2 Each of these functions independently as a thermosetting functional group, and may be, for example, an epoxy group. 1 and R 2 When each of these is an epoxy group, it is easier to control the maximum absorbance wavelength compared to when other types of thermosetting functional groups, such as (meth)acrylate groups, which can be advantageous in maintaining low transmittance in the required region even with small amounts.

[0060] For example, in the above chemical formula 1, R 3R is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms. 4 R may be a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms. For example, in the above chemical formula 1, 3 R is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. 4 The alkyl group may be substituted or unsubstituted, having 5 to 20 carbon atoms. If the chemical formula 1 is a squale-based compound and the number of carbon atoms constituting the alkyl group directly bonded to the nitrogen atom is 6 or more, the solubility in the solvent can be improved.

[0061] For example, chemical formulas 2 and 3 can surround the squalein compound represented by chemical formula 1, so that the green dye has an enclosure structure. This can significantly improve lightfastness.

[0062] On the one hand, the first green dye has a shell containing an unsubstituted benzene ring and an unsubstituted pyridine ring, while the second green dye has a shell containing a substituted benzene ring and an unsubstituted pyridine ring. By controlling the structure of the shells constituting the first and second green dyes as described above, durability can be improved and the coloring power can be greatly enhanced.

[0063] For example, the aforementioned chemical formula 2 can be represented by the following chemical formula 2-1.

[0064] [ka] [Chemical formula 2-1]

[0065] The aforementioned chemical formula 3 can be represented by the following chemical formula 3-1.

[0066] [ka] [Chemical formula 3-1]

[0067] In the above chemical formula 3-1, R b ~R e Each of these is independently a halogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0068] For example, in the above chemical formula 3-1, R b ~R e Each of these may independently be a halogen atom, such as a fluorine atom or a chlorine atom.

[0069] For example, the first green dye and the second green dye may be present in a weight ratio of 3:1 to 7:1. In this case, not only is it possible to produce a photosensitive resin film having a desired transmittance at a desired wavelength even under ultrathin film conditions, but chemical resistance can also be greatly improved without a decrease in light resistance.

[0070] For example, the first green dye has a maximum absorption wavelength (λ) at 640nm to 650nm. max The second green dye may have a maximum absorption wavelength (λ) at 660nm to 670nm. max ) can be achieved. When the maximum absorbance wavelengths of the two types of green dyes are controlled as described above, the solubility of the hybrid colorant in the solvent can be improved.

[0071] For example, the first green dye can be represented by the following chemical formula 4-1 or chemical formula 4-2.

[0072] [ka] [Chemical formula 4-1]

[0073] [ka] [Chemical formula 4-2]

[0074] For example, the second green dye can be represented by any one of the following chemical formulas 5-1 to 5-3.

[0075] [ka] [Chemical formula 5-1]

[0076] [ka] [Chemical formula 5-2]

[0077] [ka] [Chemical formula 5-3]

[0078] Based on the total amount of solids constituting the photosensitive resin composition, the green dye and yellow pigment may be included in amounts of 40% to 55% by weight, for example, 40% to 50% by weight, for example, 40% to less than 47% by weight, for example, 40% to 46% by weight, for example, 42% to 46% by weight. In this case, even with a small amount of the colorant, the coloring power and light-dark ratio can be improved while enhancing the dispersibility and dispersion stability of the colorant.

[0079] For example, the yellow pigment can be an isoindoline pigment such as CI yellow pigment 185 or CI yellow pigment 139 within the Color Index, a quinophthalone pigment such as CI yellow pigment 138, or a nickel complex pigment such as CI yellow pigment 150. These can be used individually or in combination of two or more.

[0080] The coloring agent may further include, in addition to the yellow pigment, a blue pigment, a red pigment, a purple pigment, a black pigment, and the like.

[0081] The aforementioned red pigments may include 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., within the Color Index, and these may be used individually or in combination of two or more, but are not necessarily limited to these.

[0082] The aforementioned purple pigments may include CI violet pigment 23 (V.23), CI violet pigment 29, dioxazine violet, first violet B, methyl violet lake, indantrene brilliant violet, etc., within the Color Index, and may be used individually or in mixtures of two or more, but are not necessarily limited to these.

[0083] The aforementioned blue pigments may include copper phthalocyanine pigments such as CI blue pigment 15:6, CI blue pigment 15, CI blue pigment 15:1, CI blue pigment 15:2, CI blue pigment 15:3, CI blue pigment 15:4, CI blue pigment 15:5, CI blue pigment 15:6, and CI blue pigment 16 within the Color Index, and these may be used individually or in mixtures of two or more, but are not necessarily limited to these.

[0084] The aforementioned black pigments may include aniline black, parylene black, titanium black, carbon black, etc., within the Color Index, and may be used individually or in combination of two or more, but are not necessarily limited to these.

[0085] The coloring agent may further include a dispersant and a dispersion binder.

[0086] The dispersant helps to uniformly disperse 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.

[0087] The pigment may be included in the photosensitive resin composition for color filters in the form of a dispersion. Such a pigment dispersion may further comprise the pigment, the dispersant, the dispersion solvent, and the dispersion binder.

[0088] As the dispersion solvent used in the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, gamma-butyrolactone, propylene glycol methyl ether, etc., can be used, and among these, gamma-butyrolactone, propylene glycol methyl ether acetate, or a mixture thereof can be used.

[0089] The dispersion binder can be an acrylic resin, such as an acrylic resin containing a carboxyl group, which can not only improve the stability of the pigment dispersion but also improve the patternability of the pixels.

[0090] The coloring agent may further contain a metal complex dye in addition to the two types of green dyes.

[0091] The aforementioned metal complex dyes can be compounds that have maximum absorbance in the wavelength range of 200 nm to 650 nm. Any metal complex dye of any color that is soluble in an organic solvent and has absorbance within the aforementioned range can be used to match the color coordinates of the dye combination.

[0092] Specifically, the metal complex dye can be a green dye having maximum absorbance in the 530nm to 680nm wavelength range, a yellow dye having maximum absorbance in the 200nm to 400nm wavelength range, an orange dye having maximum absorbance in the 300nm to 500nm wavelength range, a red dye having maximum absorbance in the 500nm to 650nm wavelength range, or a combination thereof.

[0093] The metal complex dyes may 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.

[0094] The metal complex dye may contain at least one metal ion selected from the group consisting of Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd, and Fe.

[0095] The aforementioned metal complex dyes include CI solvent dyes such as CI solvent greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and CI acid greens such as CI acid greens 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 Dyes, CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. CI Basic Dyes, CI Basic Green 1, etc. CI Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41 A complex of the metal ion with at least one selected from the group consisting of CI mordant dyes such as 43 and 53, green 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.

[0096] The dye containing the metal complex may have a solubility of 5 or higher in the solvent used in the photosensitive resin composition according to one embodiment, i.e., the solvent described later, and specifically may be 5 to 10. The solubility can be obtained by the amount (g) of the dye that dissolves in 100g of the solvent. When the solubility of the dye containing the metal complex is within the above range, compatibility with other components constituting the photosensitive resin composition according to one embodiment and coloring ability can be ensured, and precipitation of the dye can be prevented.

[0097] The solvent may be, for example, gamma-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone, 3-methoxy-1-butanol, or a combination thereof.

[0098] Having the aforementioned specific range, it can be usefully used in color filters for LCDs, LEDs, and the like to produce high brightness and a high contrast ratio at desired color coordinates.

[0099] The coloring agent may be included in an amount of 40% to 60% by weight, for example, 30% to 50% by weight, for example, 35% to 50% by weight, or for example, 40% to 50% by weight, relative to the total amount of solids constituting the photosensitive resin composition. When the coloring agent is included within the above range, it is possible to control the chemical resistance and maximum absorption wavelength within an appropriate range, and to achieve high brightness and light-dark ratio in the desired color coordinate, resulting in excellent coloring effect and developability.

[0100] (B) Photopolymerizable compound The photopolymerizable compound can be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

[0101] The photopolymerizable compound, by having the aforementioned ethylenically unsaturated double bond, can undergo sufficient polymerization during exposure in the pattern formation process, thereby forming a pattern with excellent heat resistance, light resistance, and chemical resistance.

[0102] 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.

[0103] Examples of commercially available photopolymerizable compounds include the following: Examples of monofunctional esters of (meth)acrylic acid include Aronix M-101 (registered trademark), M-111 (registered trademark), and M-114 (registered trademark) from Toagosei Chemical Industry Co., Ltd., KAYARAD TC-110S (registered trademark) and TC-120S (registered trademark) from Nippon Kayaku Co., Ltd., and V-158 (registered trademark) and V-2311 (registered trademark) from Osaka Organic Chemical Industry Co., Ltd. Examples of the aforementioned difunctional esters of (meth)acrylic acid include Aronix M-210 (registered trademark), M-240 (registered trademark), and M-6200 (registered trademark) from Toagosei Chemical Industry Co., Ltd., KAYARAD HDDA (registered trademark), HX-220 (registered trademark), and R-604 (registered trademark) from Nippon Kayaku Co., Ltd., and V-260 (registered trademark), V-312 (registered trademark), and V-335 HP (registered trademark) from Osaka Organic Chemical Industry Co., Ltd. Examples of the aforementioned trifunctional esters of (meth)acrylic acid include Aronix M-309 (registered trademark), M-400 (registered trademark), M-405 (registered trademark), M-450 (registered trademark), M-710 (registered trademark), M-8030 (registered trademark), and M-8060 (registered trademark) from Toagosei Chemical Industry Co., Ltd., KAYARAD TMPTA (registered trademark), DPCA-20 (registered trademark), DPCA-30 (registered trademark), DPCA-60 (registered trademark), and DPCA-120 (registered trademark) from Nippon Kayaku Co., Ltd., and V-295 (registered trademark), DPCA-300 (registered trademark), DPCA-360 (registered trademark), DPCA-GPT (registered trademark), DPCA-3PA (registered trademark), and DPCA-400 (registered trademark) from Osaka Organic Chemical Industry Co., Ltd. The above products can be used individually or in combination of two or more.

[0104] The aforementioned photopolymerizable compound can also be treated with an acid anhydride before use to impart better developability.

[0105] The photopolymerizable compound may be present in an amount of 5% to 30% by weight, specifically 10% to 25% by weight, for example 15% to 20% by weight, relative to the total amount of solids constituting the photosensitive resin composition. When the photopolymerizable compound is present within the above range, sufficient curing occurs during exposure in the pattern formation process, resulting in excellent reliability and excellent developability in alkaline developers.

[0106] (C) Photopolymerization initiator The photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, and may include, for example, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, or combinations thereof.

[0107] Examples of the aforementioned 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.

[0108] Examples of the aforementioned 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.

[0109] Examples of the thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0110] Examples of the aforementioned benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0111] Examples of the aforementioned 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-tri Examples include azine, 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.

[0112] Examples of the aforementioned oxime compounds include O-acyloxime compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one. Specific examples of the 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)-octan-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0113] In addition to the aforementioned compounds, the photopolymerization initiator can also be carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, and the like.

[0114] The aforementioned photopolymerization initiator can also be used together with a photosensitizer that absorbs light, becomes excited, and then transmits that energy to initiate a chemical reaction.

[0115] Examples of the aforementioned photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol tetrakis-3-mercaptopropionate.

[0116] The photopolymerization initiator may be present in an amount of 0.1% to 20% by weight, for example, 1% to 10% by weight, relative to the total amount of solids constituting the photosensitive resin composition. When the photopolymerization initiator is present within this range, sufficient curing occurs during exposure in the pattern formation process, resulting in excellent reliability. The pattern exhibits excellent heat resistance, light resistance, and chemical resistance, as well as excellent resolution and adhesion. Furthermore, a decrease in transmittance due to unreacted initiators can be prevented.

[0117] (D) Binder resin The binder resin may include an acrylic resin.

[0118] The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing one or more acrylic repeating units.

[0119] 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.

[0120] The first ethylenically unsaturated monomer may be present 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.

[0121] The second 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.

[0122] Specific examples of the aforementioned 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.

[0123] The binder resin may include epoxy resins.

[0124] The heat resistance can be improved by further including an epoxy resin in the binder resin. Examples of the epoxy resin include, but are not limited to, phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, or combinations thereof.

[0125] Furthermore, the binder resin containing the epoxy resin ensures the dispersion stability of colorants such as pigments described later, while simultaneously helping to form pixels of the desired resolution during the development process.

[0126] The epoxy resin may be included in an amount of 1% to 10% by weight, for example, 5% to 10% by weight, relative to the total amount of the binder resin. When the epoxy resin is included within this range, the residual film rate and chemical resistance can be greatly improved.

[0127] The epoxy equivalent weight of the epoxy resin may be between 150 g / eq and 200 g / eq. When an epoxy resin having an epoxy equivalent weight within this range is included in the binder resin, it has a beneficial 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.

[0128] The binder resin can be dissolved in a solvent described later in solid form to constitute a photosensitive resin composition. In this case, the amount of the 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.

[0129] Furthermore, the binder resin may be included in an amount of 0.5% to 25% by weight, specifically 1% to 20% by weight, for example, 1% to 10% by weight, relative to the total amount of solids constituting the photosensitive resin composition. When the binder resin is included within the above range, the developability during the manufacture of color filters is excellent, the crosslinking properties are improved, and excellent surface smoothness can be obtained.

[0130] (E) Solvent The solvent can be a substance that is compatible with but does not react with the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator.

[0131] Examples of the aforementioned 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, lactate 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-oxypropionate, 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-oxypropionate methyl, 2-oxypropionate ethyl, 2-oxypropionate propyl and other 2-oxypropionate 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.

[0132] 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.

[0133] The solvent may be included in the remainder of the total amount of the photosensitive resin composition, for example, 40% to 90% by weight, or for example, 45% to 70% by weight. The solvent may be included in an amount of 3 to 7 times the total amount of solids constituting the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition exhibits excellent coatability, and a coating film with excellent flatness can be obtained.

[0134] (F) Other additives The photosensitive resin composition may further contain additives such as malonic acid, 3-amino-1,2-propanediol, coupling agents, leveling agents, surfactants, antioxidants, or combinations thereof, in order to prevent unevenness and spots during application, improve leveling performance, and prevent the formation of residue due to undeveloped material.

[0135] The aforementioned additive can be easily adjusted according to the desired physical properties.

[0136] The coupling agent may be 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.

[0137] 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.

[0138] Furthermore, the photosensitive resin composition for the color filter may further contain a surfactant, such as a fluorinated surfactant, as needed.

[0139] Examples of the aforementioned fluorinated surfactants include, but are not limited to, DIC's F-482, F-484, and F-478.

[0140] 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 the amount deviates from the above range, it may lead to problems such as the formation of foreign matter after development, which is undesirable.

[0141] Furthermore, the photosensitive resin composition may contain a certain amount of other additives, such as antioxidants and stabilizers, as long as they do not impair its physical properties.

[0142] The antioxidant may include, but is not limited to, a hydroquinone compound, a catechol compound, or a combination thereof. By further including the hydroquinone compound, catechol compound, or a combination thereof in the photosensitive resin composition according to one embodiment, room-temperature crosslinking can be prevented between printing (coating) and exposure of the photosensitive resin composition.

[0143] For example, the hydroquinone compounds, catechol compounds, or combinations thereof may include, but are not limited to, hydroquinone, methylhydroquinone, methoxyhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis(1,1-dimethylbutyl)hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, catechol, t-butylcatechol, 4-methoxyphenol, pyrogallol, 2,6-di-t-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminium, or combinations thereof.

[0144] The hydroquinone-based compound, catechol-based compound, or combination thereof can be used in the form of a dispersion, and the antioxidant in dispersion form may be present in an amount of 0.001% to 3% by weight, for example, 0.1% to 2% by weight, relative to the total amount of solids constituting the photosensitive resin composition. When the antioxidant is present within the above range, the problem of aging at room temperature can be solved at the same time as preventing a decrease in sensitivity and surface peeling phenomena.

[0145] (Photosensitive resin film, color filter, and display device) According to another embodiment, a photosensitive resin film manufactured using the photosensitive resin composition according to one embodiment is provided.

[0146] The photosensitive resin film of one embodiment can be broadly classified into a positive photoresist composition and a negative photoresist composition.

[0147] The photosensitive resin film in one embodiment may be a negative photoresist. This has the advantage of not causing discoloration due to the photoresist and having relatively higher light sensitivity than a positive photoresist.

[0148] For example, the photosensitive resin film may have a thickness of 500 nm, a transmittance of 9% or less at 450 nm, a transmittance of 90% or more at 550 nm, a transmittance of 15% or less at 630 nm, a transmittance of 4% or less at 650 nm, and a transmittance of 60% or less at 700 nm. When the photosensitive resin film has the above-mentioned transmittances for each wavelength band at the aforementioned thickness, it may be easy to realize an ultrathin film with excellent sensor sensitivity.

[0149] Another embodiment provides a color filter manufactured using the aforementioned photosensitive resin composition.

[0150] A method for manufacturing a color filter according to one embodiment is as follows:

[0151] A photosensitive resin composition layer is formed on a glass substrate by applying the aforementioned photosensitive resin composition to a thickness of, for example, 0.3 μm to 0.5 μm using an appropriate method such as spin coating, roller coating, or spray coating.

[0152] 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 region, specifically in the 200nm to 400nm region, can be irradiated. The irradiation step can also be carried out using a photoresist mask. After performing the irradiation step in this manner, 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 are dissolved, thereby forming the pattern required for the color filter. By repeating this process for the required number of colors, a color filter having the desired pattern can be obtained. Furthermore, if the image pattern obtained by development in the above step is heated again or cured by chemical beam irradiation, crack resistance, solvent resistance, etc., can be improved.

[0153] Another embodiment provides an image sensor including the aforementioned color filter.

[0154] Another embodiment provides a display device including the aforementioned image sensor.

[0155] The aforementioned display device may be a liquid crystal display device or the like.

[0156] 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 these examples. [Examples]

[0157] (Example of combination) Synthesis Example 1: Compound represented by chemical formula 4-1 2-[(4-Bromophenoxy)methyl]oxirane (20 mol), Pd(OAc)2 (0.002 mmol), sodium t-butoxide (30 mmol), and 2-aminoheptane (20 mmol) were placed in toluene (toluene) solvent and stirred at room temperature for 30 minutes. Then, P(t-Bu)3 (0.004 mmol) was added and the mixture was stirred at 110°C for 15 hours. Ethyl acetate was added to this solution and washed twice with water to extract the organic layer. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain intermediate 1.

[0158] Intermediate 1 (20 mmol), Pd(OAc)2 (0.002 mmol), sodium t-butoxide (30 mmol), and 1-bromobenzene (20 mmol) were placed in toluene (toluene) solvent and stirred at room temperature for 30 minutes. Then, P(t-Bu)3 (0.004 mmol) was added and the mixture was stirred at 110°C for 15 hours. Ethyl acetate was added to this solution and washed twice with water to extract the organic layer. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain intermediate 2.

[0159] Intermediate 2 (60 mmol) and 3,4-dihydroxy-3-cyclobutyne-1,2-dione (30 mmol) were added to toluene (200 mL) and butanol (200 mL) and refluxed. The resulting water was removed using a Dean-Stark distillation apparatus. After stirring for 12 hours, the green reaction product was subjected to vacuum distillation and purified by column chromatography to obtain intermediate 3.

[0160] Intermediate 3 (5 mmol) is dissolved in 600 mL of chloroform, and then triethylamine (50 mmol) is added. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60 mL of chloroform and added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the mixture is removed by vacuum distillation and separated by column chromatography to obtain the compound represented by the following chemical formula 4-1.

[0161] [ka] [Chemical formula 4-1] Maldi-Tof MS: 1291.62 m / z

[0162] Synthesis Example 2: Compound represented by chemical formula 5-1 The procedure was carried out in the same manner as in Synthesis Example 1, except that 3,6-bis(aminomethyl)-1,2,4,5-tetrafluorobenzene was used instead of p-xylylenediamine, to obtain the compound represented by the following chemical formula 5-1.

[0163] [ka] [Chemical formula 5-1] Maldi-Tof MS: 1435.45 m / z

[0164] Comparative Synthesis Example 1: Compound represented by chemical formula C-1 2,4-dimethyldiphenylamine (10 mol), 1,2-epoxycyclohexane (12 mol), and sodium hydride (12 mol) were placed in N,N-dimethylformamide and heated at 90°C, stirring for 24 hours. Ethyl acetate was added to this solution and washed twice with water to extract the organic layer. The extracted organic layer was subjected to vacuum distillation and separated by column chromatography to obtain intermediate 4.

[0165] Intermediate 4 (10 mmol), iodomethane (15 mmol), and sodium hydride (15 mmol) were placed in N,N-dimethylformamide and stirred at room temperature for 24 hours. Ethyl acetate was added to this solution and washed twice with water to extract the organic layer. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain intermediate 5.

[0166] Intermediate 5 (60 mmol) and 3,4-dihydroxy-3-cyclobutyne-1,2-dione (30 mmol) were added to toluene (200 mL) and butanol (200 mL) and refluxed. The resulting water was removed using a Dean-Stark distillation apparatus. After stirring for 12 hours, the green reaction product was distilled under reduced pressure and purified by column chromatography to obtain intermediate 6.

[0167] Intermediate 6 (5 mmol) is dissolved in 600 mL of chloroform, and then triethylamine (50 mmol) is added. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60 mL of chloroform and added dropwise simultaneously at room temperature for 5 hours. After 12 hours, the mixture is distilled under reduced pressure and separated by column chromatography to obtain the compound represented by the following chemical formula C-1.

[0168] JPEG2026116771000023.jpg3344 [Chemical formula C-1] Maldi-Tof MS: 1230.59 m / z

[0169] Manufacturing of photosensitive resin compositions The photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-8 were prepared by mixing the materials according to the compositions shown in Tables 1 and 2 below.

[0170] Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture was stirred at room temperature (20°C) for 30 minutes. Then, the binder resin, photopolymerizable compound, and additives were added and the mixture was stirred at room temperature for 60 minutes. Next, a green dye and / or pigment dispersion was added to the resulting reaction mixture as a coloring agent and the mixture was stirred at room temperature for 30 minutes. The photosensitive colored resin composition was prepared by removing impurities by filtering twice through a 0.45 μm PP syringe filter.

[0171] [Table 1]

[0172] [Table 2]

[0173] The substances used in Tables 1 and 2 above are as follows:

[0174] (B) Photopolymerizable monomers (B-1) Dipenta Elite Litol Hexaacrylate (DPHA, Manufacturer: Nippon Kayaku Co., Ltd.) (B-2) DGE-4A (Kyoeisha) (C) Photopolymerization initiator (C-1) PBG-304 (Tronli) (C-2)SPI03 (Manufacturer: Sanyo Co., Ltd.) (D) Binder resin SP-RY-99 (Manufacturer: Showa Denko) (E) Solvent (E-1) Propylene glycol monomethyl ether acetate (PGMEA) (Manufacturer: Daicel) (E-2) Gamma-butyrolactone (Manufacturer: Daicel) Antioxidant Methylhydroquinone (Manufacturer: Sigma Aldrich) additives F554 (Manufacturer: DIC)

[0175] Evaluation 1: Spectral characteristics (transmittance) Each manufactured composition was spin-coated onto glass specimens (10 × 10 cm) to a thickness of 0.4 to 1.0 μm, three times each, and then baked on a 90°C hot plate for 3 minutes. Next, the specimens were exposed to 200 mJ using a UV exposure unit and then baked on a 230°C hot plate for 5 minutes. The spectra of the three manufactured specimens were measured using a chromatometer, and the thickness was measured using an alpha step. The measured values ​​were calculated to obtain transmittance values ​​at a thickness of 0.5 μm. The transmittance values ​​at specific wavelengths are shown in Table 3 below.

[0176] Evaluation 2: Chemical resistance (color change) The color specimens prepared in Evaluation 1 were cut into 5cm x 5cm pieces and immersed in 500ml of PGMEA (propylene glycol methyl ether acetate) at 40°C for 10 minutes. The color values ​​before and after immersion in PGMEA were measured using a chromatometer (MCPD, Otsuka Co., Ltd.). The △Eab* value, a measure of color change, was calculated using formula 1 below, and the results are shown in Table 3 below.

[0177] [Formula 1] ΔEab* = {(ΔL*) 2 +(Δa*) 2 +(Δb*) 2} × 1 / 2 (The smaller the ΔEab* value, the better the heat resistance and chemical resistance)

[0178] Rating 3: Resistance to change in light transmittance The specimens prepared in Evaluation 1 were coated with SiO2 to a thickness of 500 nm and irradiated with a xenon lamp for 350 hours. The change in transmittance of the specimens at different wavelengths (400-700 nm) before and after exposure was measured. The value with the largest change was selected. The final results are shown in Table 3 below.

[0179] [Table 3]

[0180] According to Table 3 above, the compositions of Examples 1 to 8 have lower transmittance in the wavelength range of 480 nm and below and 630 nm to 700 nm, and higher transmittance in the 480 nm to 620 nm range compared to the compositions of Comparative Examples 1 to 8. This not only improves the sensor sensitivity of image sensors manufactured using these compositions, but also demonstrates superior heat resistance and chemical resistance.

[0181] 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 and the detailed description of the invention, 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 coloring agent comprises a green dye and a yellow pigment. The aforementioned green dye comprises a first green dye and a second green dye. The first green dye comprises a core-shell compound consisting of a core represented by the following chemical formula 1 and a shell surrounding the core represented by the following chemical formula 2. The second green dye comprises a core-shell compound consisting of a core represented by the following chemical formula 1 and a shell surrounding the core represented by the following chemical formula 3. Based on solid content, the first green dye is present in a greater weight than the second green dye. A photosensitive resin composition in which, on a solid content basis, the first green dye is present in an amount less than nine times the weight of the second green dye. 【Chemistry 1】 [Chemical formula 1] 【Chemistry 2】 [Chemical formula 2] 【Transformation 3】 [Chemical formula 3] (Among the above chemical formulas 1 to 3, L １ and L ２ Each of these is independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. R １ and R ２ Each of these is an epoxy group independently, R ３ and R ４ Each of these is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. L ａ and L ｂ Each of these is independently a single-bonded, substituted, or unsubstituted alkylene group having 1 to 20 carbon atoms. R ａ is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or *-C(=O)OR ０ (R ０ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), and m and n² are each independent integers between 1 and 10. n1 is an integer between 1 and 4.

2. The aforementioned R ３ is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms. The aforementioned R ４ The photosensitive resin composition according to claim 1, wherein is a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms.

3. The photosensitive resin composition according to claim 1, wherein the aforementioned chemical formula 2 is represented by the following chemical formula 2-1. 【Chemistry 4】 [Chemical formula 2-1]

4. The photosensitive resin composition according to claim 1, wherein the aforementioned chemical formula 3 is represented by the following chemical formula 3-1. 【Transformation 5】 [Chemical formula 3-1] (In the above chemical formula 3-1, R ｂ ~R ｅ Each of these is independently a halogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

5. The first green dye has a maximum absorption wavelength (λ) at 640 nm to 650 nm. ｍａｘ The second green dye has a maximum absorption wavelength (λ) at 660 nm to 670 nm. ｍａｘ The photosensitive resin composition according to claim 1, having ).

6. The photosensitive resin composition according to claim 1, wherein the first green dye is represented by the following chemical formula 4-1 or chemical formula 4-2. 【Transformation 6】 [Chemical formula 4-1] 【Transformation 7】 [Chemical formula 4-2]

7. The photosensitive resin composition according to claim 1, wherein the second green dye is represented by any one of the following chemical formulas 5-1 to 5-3. 【Transformation 8】 [Chemical formula 5-1] 【Chemistry 9】 [Chemical formula 5-2] 【Chemistry 10】 [Chemical formula 5-3]

8. The photosensitive resin composition according to claim 1, wherein the green dye and yellow pigment are contained in an amount of 40% to 55% by weight, based on the total amount of solids constituting the photosensitive resin composition.

9. The photosensitive resin composition is, with respect to the total amount of solids constituting the photosensitive resin composition, The aforementioned (A) coloring agent 40% to 60% by weight, The above (B) photopolymerizable compound 5% to 30% by weight, The above (C) photopolymerization initiator 0.1% to 20% by weight, and The above (D) binder resin 0.5% to 25% by weight A photosensitive resin composition according to claim 1, comprising the above.

10. A photosensitive resin film manufactured using the photosensitive resin composition according to any one of claims 1 to 9.

11. The photosensitive resin film according to claim 10, wherein the photosensitive resin film is a negative photoresist.

12. A color filter comprising a photosensitive resin film according to claim 10.

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