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

Abstract

A photosensitive resin composition, a photosensitive resin film manufactured using the composition, and a color filter are disclosed, wherein the photosensitive resin composition comprises a green dye and a yellow pigment.

Description

[0001] Citations of relevant applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0202848, filed on December 31, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to photosensitive resin compositions, photosensitive resin films manufactured using said compositions, and color filters. Background Technology

[0004] An image sensor is a semiconductor that converts photons into electrons and displays them on a display device or stores them in a storage device. Based on manufacturing and application methods, image sensors are classified into charge-coupled device (CCD) image sensors and complementary metal-oxide-semiconductor (CMOS) image sensors. Image sensors also incorporate color filters, which include filter segments that additively mix the primary colors of red, green, and blue.

[0005] One method for realizing color filters is the pigment dispersion method, which involves repeating a series of processes such as coating a photopolymerizable composition containing a colorant onto a transparent substrate with a black matrix, exposing a pattern with the desired shape, and then curing it after removing the unexposed areas with a solvent. Typically, the coloring photosensitive resin composition used in color filters manufactured according to the pigment dispersion method contains a pigment dispersion (pigment dispersion) as 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 these characteristics, is widely used in the manufacture of LCDs, such as those for mobile phones, laptops, monitors, and TVs. However, in recent years, there has been a need for improved performance and superior pattern contours in the photosensitive resin compositions used in pigment dispersion method color filters. In particular, properties such as high brightness, high contrast, and high absorption efficiency are urgently required.

[0006] Color filters made from pigment-based photosensitive resin compositions are limited in terms of brightness and contrast due to pigment particle size. Furthermore, for color imaging devices used in image sensors, smaller dispersion particle size and higher coloring power are required to form intricate patterns. To meet these needs, efforts are underway to provide photosensitive resin compositions that incorporate non-particulate dyes instead of pigments to achieve color filters with improved spectral properties such as light absorption efficiency (coloring power) and brightness. In addition, numerous studies have been conducted to improve the insufficient heat resistance, chemical resistance, and lightfastness compared to pigments. Summary of the Invention

[0007] One embodiment provides a photosensitive resin composition having excellent spectral characteristics and sensor sensitivity and capable of forming a thin film.

[0008] Another embodiment provides a photosensitive resin film manufactured using the said photosensitive resin composition.

[0009] Another embodiment provides a color filter that includes the photosensitive resin film.

[0010] 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, the green dye comprising a first green dye and a second green dye, the first green dye comprising 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 comprising 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 comprising a weight based on a solids content greater than that of the second green dye, and comprising a weight based on a solids content less than nine times that of the second green dye.

[0011] [Chemical Formula 1]

[0012]

[0013] [Chemical Formula 2]

[0014]

[0015] [Chemical Formula 3]

[0016]

[0017] In chemical formulas 1 to 3

[0018] L 1 and L 2 Each is independently a substituted or unsubstituted C1 to C20 alkylene group, R 1 and R 2 Each is an epoxy group independently.

[0019] R 3 and R 4 Each is independently a substituted or unsubstituted C1 to C20 alkyl group.

[0020] L a and L bEach is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0021] R a It is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a *-C(=O)OR 0 (where R) 0 (Substituted or unsubstituted C1 to C20 alkyl groups)

[0022] m and n2 are each an independent integer from 1 to 10.

[0023] n1 is an integer from 1 to 4.

[0024] In chemical formula 1, R 3 It can be a substituted or unsubstituted C1 to C3 alkyl group, and R 4 It can be a substituted or unsubstituted C3 to C20 alkyl group.

[0025] Chemical formula 2 can be represented by chemical formula 2-1.

[0026] [Chemical Formula 2-1]

[0027]

[0028] Chemical formula 3 can be represented by chemical formula 3-1.

[0029] [Chemical Formula 3-1]

[0030]

[0031] In chemical formula 3-1,

[0032] R b To R e Each is independently a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0033] The first green dye and the second green dye can be contained in a weight ratio of 3:1 to 7:1.

[0034] The first green dye can have a maximum absorption wavelength (λ) in the range of 640 nm to 650 nm. max ).

[0035] The second green dye can have a maximum absorption wavelength (λ) in the range of 660 nm to 670 nm. max ).

[0036] The first green dye may be represented by chemical formula 4-1 or chemical formula 4-2.

[0037] [Chemical Formula 4-1]

[0038]

[0039] [Chemical Formula 4-2]

[0040]

[0041] The second green dye can be represented by chemical formulas 5-1 to 5-3.

[0042] [Chemical Formula 5-1]

[0043]

[0044] [Chemical Formula 5-2]

[0045]

[0046] [Chemical Formula 5-3]

[0047]

[0048] Based on the total amount of solids constituting the photosensitive resin composition, the total content of the green dye and yellow pigment can be from 40 wt% to 55 wt%.

[0049] Based on the total amount of solids constituting the photosensitive resin composition, the photosensitive resin composition may contain 40 wt% to 60 wt% of (A) a colorant; 5 wt% to 30 wt% of (B) a photopolymerizable compound; 0.1 wt% to 20 wt% of (C) a photopolymerization initiator; and 0.5 wt% to 25 wt% of (D) a binder resin.

[0050] The photosensitive resin composition may also contain additives such as malonic acid, 3-amino-1,2-propanediol, silane coupling agents, leveling agents, surfactants, antioxidants, or combinations thereof.

[0051] Another embodiment provides a photosensitive resin film manufactured using the said photosensitive resin composition.

[0052] The photosensitive resin film can be a negative photoresist.

[0053] The photosensitive resin film may have The thickness and transmittance of less than or equal to 9% at 450nm, greater than or equal to 90% at 550nm, less than or equal to 15% at 630nm, less than or equal to 4% at 650nm and less than or equal to 60% at 700nm.

[0054] Another embodiment provides a color filter that includes the photosensitive resin film.

[0055] Another embodiment provides an image sensor that includes the color filter.

[0056] Another embodiment provides a display device that includes the image sensor.

[0057] Other embodiments of the present invention are included in the following detailed description.

[0058] According to one embodiment, the photosensitive resin composition has excellent spectral characteristics, so when a color filter is implemented, a color filter for an image sensor with excellent sensor sensitivity and thin film, such as a green color filter for an image sensor, as well as an image sensor and display device, can be realized without deteriorating tinting strength, lightfastness and chemical resistance. Detailed Implementation

[0059] Embodiments of the present invention are described in detail below. However, these embodiments are exemplary, and this disclosure is not limited thereto.

[0060] As used herein, unless otherwise specifically defined, “substituted” means that at least one hydrogen atom of a compound is replaced by one of the following: a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amino group, an imino group, an azide group, a formamidinyl group, a hydrazine group, a hydrazine group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocyclic alkyl group, a C2 to C20 heterocyclic alkenyl group, a C2 to C20 heterocyclic alkynyl group, or a combination thereof.

[0061] As used herein, unless otherwise specifically defined, “heterocycloalkyl,” “heterocycloalkenyl,” “heterocycloynyl,” and “heterocycloalkylene group” means a cyclic compound of cycloalkyl, cycloalkenyl, cycloynyl, and heterocycloalkylene containing at least one N, O, S, or P.

[0062] As used herein, unless otherwise specifically defined, “(meth)acrylate” means both “acrylate” and “methacrylate”.

[0063] As used herein, unless otherwise defined, the term “composite” means blend or copolymer. Additionally, “copolymer” refers to block copolymer to random copolymer, and “polymer” refers to block copolymer to random copolymer.

[0064] In the chemical formulas of this specification, unless otherwise specifically defined, hydrogen bonds are indicated at the locations where chemical bonds are not drawn.

[0065] As used herein, unless otherwise specifically defined, "*" indicates a connection point of the same or different atoms or chemical formulas.

[0066] As used herein, unless otherwise defined, “particle size” can refer to the diameter of a particle, and the diameter of a particle can be the Z-mean of the particle size as measured by dynamic light scattering.

[0067] For green color filters used in image sensors, the transmittance should be low in the wavelength ranges of 380nm to 480nm and 630nm to 700nm, and high in the wavelength range of 480nm to 630nm, thereby improving sensor sensitivity. Additionally, to achieve a transmittance of less than or equal to 0.5μm... For ultrathin films, the absorption intensity of the color material should be very excellent, so that a small amount of color material can exhibit low transmittance in the desired area. In this invention, to achieve a green color filter with excellent sensor sensitivity and thin-film implementation, two types of squaraine-based green dyes are used in combination with yellow pigment. These squaraine-based green dyes have both encapsulation structures and thermosetting functional groups, and respectively have maximum absorption wavelengths (λ) of 640 nm to 650 nm and 660 nm to 670 nm. max Compared to pigment-based coloring compositions, the coloring compositions for green filters exhibit superior spectral characteristics (green absorption and transmission wavelengths) and, due to their thermosetting functional groups, can display chemical resistance properties similar to those of pigment-based coloring compositions. Furthermore, their lightfastness under deposition conditions is superior to that of general green coloring compositions containing phthalocyanine green pigments. Additionally, compared to photosensitive resin compositions for color filters using existing pigment dispersions, the photosensitive resin compositions using this composition exhibit superior tinting strength even at ultrafilm thicknesses of 0.5 μm or less, and also display heat resistance and chemical resistance properties equivalent to or higher than those of general pigment dispersions.

[0068] (Photosensitive resin composition)

[0069] 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.

[0070] In this document, the green dye comprises a first green dye and a second green dye, the first green dye comprising a core-shell compound consisting of a core represented by chemical formula 1 and a shell surrounding the core represented by chemical formula 2, and the second green dye comprising 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 comprising a weight based on a solids content greater than that of the second green dye, and the first green dye comprising a weight based on a solids content less than 9 times that of the second green dye.

[0071] [Chemical Formula 1]

[0072]

[0073] [Chemical Formula 2]

[0074]

[0075] [Chemical Formula 3]

[0076]

[0077] In chemical formulas 1 to 3

[0078] L 1 and L 2 Each is independently a substituted or unsubstituted C1 to C20 alkylene group.

[0079] R 1 and R 2 Each is an epoxy group independently.

[0080] R 3 and R 4 Each is independently a substituted or unsubstituted C1 to C20 alkyl group.

[0081] L a and L b Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0082] R a It is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a *-C(=O)OR 0 (where R) 0 (Substituted or unsubstituted C1 to C20 alkyl groups)

[0083] m and n2 are each an independent integer from 1 to 10, and

[0084] n1 is an integer from 1 to 4.

[0085] (A) Coloring agent

[0086] One embodiment of the photosensitive resin composition is a hybrid photosensitive resin composition, wherein both pigments and dyes are used as colorants. Generally, hybrid photosensitive resin compositions possess excellent spectral properties such as brightness and tinting strength, but lack durability such as heat resistance, chemical resistance, and lightfastness. To improve this, attempts have been made to modify the structure of the dyes, introduce crosslinking reactive groups, and combine cationic dyes with anionic compounds. However, under ultrathin film conditions of 0.5 μm or lower, the absorption intensity of the colorant is low, and it is difficult to achieve low transmittance in the desired area using only a small amount of colorant.

[0087] According to one embodiment, the colorant contained in the photosensitive resin composition is a colorant made by mixing two different green dyes with a yellow pigment, while controlling the structure of the two green dyes and the mixing weight ratio between the two green dyes, thereby improving the light absorption intensity of the colorant under ultra-thin film conditions of 0.5 μm or lower, and easily achieving low transmittance in the desired area even when present in small amounts.

[0088] In other words, the hybrid colorant having the above composition can be used with dispersants and dispersing binders to improve the solubility of dyes, the dispersibility and dispersion stability of pigments, and at the same time enhance tinting strength. Therefore, when a photosensitive resin composition containing the above-mentioned colorant is implemented as a color filter, image sensor, and display device, it can exhibit further improved tinting strength (color gamut) and contrast.

[0089] In chemical formula 1, R 1 and R 2 Each group independently functions as a thermosetting functional group and can be, for example, an epoxy group. With R... 1 and R 2 Compared to other types of thermosetting functional groups such as (meth)acrylate groups, in which R 1 and R 2 When each component is an epoxy group, it is easier to control the maximum absorption wavelength, thus allowing for advantageous maintenance of low transmittance in the desired region even when present in small quantities.

[0090] For example, in chemical formula 1, R 3 It can be a substituted or unsubstituted C1 to C3 alkyl group and R 4 It can be a substituted or unsubstituted C3 to C20 alkyl group. For example, in formula 1, R 3 It can be a substituted or unsubstituted C1 to C4 alkyl group and R 4It can be a substituted or unsubstituted C5 to C20 alkyl group. Formula 1 is a squaric acid compound, and its solubility in solvents can be improved when the number of carbon atoms constituting the alkyl group directly attached to the nitrogen atom is 6 or more.

[0091] For example, chemical formulas 2 and 3 can surround the squaric acid compound represented by chemical formula 1, thus giving the green dye an encapsulation structure. In this way, lightfastness can be greatly improved.

[0092] Meanwhile, the first green dye has a shell comprising an unsubstituted benzene ring and an unsubstituted pyridine ring, while the second green dye has a shell comprising 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, tinting strength and durability can be significantly improved.

[0093] For example, chemical formula 2 can be represented by chemical formula 2-1.

[0094] [Chemical Formula 2-1]

[0095]

[0096] Chemical formula 3 can be represented by chemical formula 3-1.

[0097] [Chemical Formula 3-1]

[0098]

[0099] In chemical formula 3-1,

[0100] R b To R e Each is independently a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0101] For example, in chemical formula 3-1, R b To R e Each atom can be a halogen atom, for example, a fluorine atom or a chlorine atom.

[0102] For example, the first green dye and the second green dye can be contained in a weight ratio of 3:1 to 7:1. In this case, not only can a photosensitive resin film with the desired transmittance at the desired wavelength be manufactured even under ultrathin film conditions, but chemical resistance can also be significantly improved without deteriorating lightfastness.

[0103] For example, the first green dye may have a maximum absorption wavelength (λ) in the range of 640 nm to 650 nm. maxFurthermore, the second green dye can have a maximum absorption wavelength (λ) in the range of 660 nm to 670 nm. max When the maximum absorption wavelength of the two types of green dyes is controlled as described above, the solubility of the hybrid colorant in the solvent can be improved.

[0104] For example, the first green dye can be represented by chemical formula 4-1 or chemical formula 4-2.

[0105] [Chemical Formula 4-1]

[0106]

[0107] [Chemical Formula 4-2]

[0108]

[0109] For example, the second green dye can be represented by any one of chemical formulas 5-1 to 5-3.

[0110] [Chemical Formula 5-1]

[0111]

[0112] [Chemical Formula 5-2]

[0113]

[0114] [Chemical Formula 5-3]

[0115]

[0116] Based on the total amount of solids constituting the photosensitive resin composition, the total content of the green dye and the yellow pigment can be 40 wt% to 55 wt%, for example 40 wt% to 50 wt%, for example 40 wt% or greater but less than 47 wt%, for example 40 wt% to 46 wt%, for example 42 wt% to 46 wt%. In this case, even in small amounts, the colorant can improve tinting strength and contrast, while also enhancing the dispersibility and dispersion stability of the colorant.

[0117] Yellow pigments can be isoindoline pigments in the color index, such as CI Yellow Pigment 185, CI Yellow Pigment 139, etc.; quinoline phthaloyl ketone pigments, such as CI Yellow Pigment 138; nickel complex pigments, such as CI Yellow Pigment 150. They can be used alone or in mixtures of two or more, but the present invention is not limited thereto.

[0118] Besides yellow pigments, colorants can also include blue, red, purple, and black pigments.

[0119] The red pigment may be 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. in the color index. They may be used alone or in a mixture of two or more, but the present invention is not limited thereto.

[0120] The purple pigment may be Violet Pigment 23 (V.23), Violet Pigment 29, Dioxazine Violet, First Violet B, Methyl Violet Lake, Indanethrene Brilliant Violet, etc., as listed in the color index. They may be used alone or in mixtures of two or more, but the present invention is not limited thereto.

[0121] The blue pigment may be a copper phthalocyanine pigment in the color index, 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, CI Blue Pigment 16. They may be used alone or in mixtures of two or more, but the present invention is not limited thereto.

[0122] Black pigments can be aniline black, perylene black, titanium black, carbon black, etc., as listed in the color index. They can be used alone or in mixtures of two or more, but the present invention is not limited thereto.

[0123] The colorant may also include a dispersant and a dispersing binder.

[0124] The dispersant helps the pigment to be uniformly dispersed in the dispersion, and nonionic, anionic, or cationic dispersants can be used. Specifically, polyalkylene glycols or their esters, polyoxyalkylene oxides, polyol ester epoxy alkyl adducts, alcohol epoxy alkyl adducts, sulfonates, sulfonates, carboxylic esters, carboxylates, alkylamide epoxy alkyl adducts, alkylamines, etc., can be used alone or in combination of two or more.

[0125] The pigment can be contained in the form of a dispersion in a photosensitive resin composition used for a color filter. This pigment dispersion may also include the pigment, dispersant, dispersing solvent, and dispersing binder.

[0126] As a dispersion solvent used in the pigment dispersion, ethylene glycol acetate, ethyl celex, propylene glycol monomethyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, γ-butyrolactone, propylene glycol monomethyl ether, etc., can be used, and γ-butyrolactone, propylene glycol monomethyl ether acetate, or mixtures thereof can be used as desired.

[0127] Dispersants and binders can use acrylic resins, such as those containing carboxyl groups, which can not only improve the stability of pigment dispersions but also improve the patterning ability of pixels.

[0128] In addition to the two types of green dyes, colorants can also contain metal complex dyes.

[0129] Metal complex dyes can be compounds that have maximum absorbance in the wavelength range of 200 nm to 650 nm, and if the compound has absorbance in the above range to match the color coordinate of the dye combination, then metal complex dyes of all colors that are soluble in organic solvents can be used.

[0130] Specifically, the metal complex dye may be a green dye with maximum absorbance in the wavelength range of 530 nm to 680 nm, a yellow dye with maximum absorbance in the wavelength range of 200 nm to 400 nm, an orange dye with maximum absorbance in the wavelength range of 300 nm to 500 nm, a red dye with maximum absorbance in the wavelength range of 500 nm to 650 nm, or a combination thereof.

[0131] The metal complex dye may be a direct dye, acid dye, basic dye, acid mordant dye, sulfur dye, vat dye, azo dye, disperse dye, reactive dye, oxidative dye, oil-soluble dye, azo dye, anthraquinone dye, indigo dye, carbocation dye, phthalocyanine dye, nitro dye, quinoline dye, cyaninedye, polymethyst dye, or a combination thereof.

[0132] The metal complex dye may include at least one metal ion selected from the following: Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd and Fe.

[0133] The metal complex dye may be a complex of at least one of the following with a metal ion: CI solvent dyes, such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.; 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, etc.; CI direct dyes, such as CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.; CI basic dyes, such as CI Basic Green 1. 1) etc.; CI mordant dyes, such as CI Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 etc.; CI green pigments, such as Pigment Green 7, 36, 58 etc.; 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.

[0134] The metal complex dye may have a solubility greater than or equal to about 5, specifically about 5 to about 10, in the solvent used in the photosensitive resin composition according to some embodiments (i.e., the solvent described below). The solubility can be obtained by measuring the amount (g) of dye dissolved in 100g of solvent. If the solubility of the metal complex dye is within the above range, compatibility and tinting strength with other components constituting the photosensitive resin composition according to some embodiments can be ensured, and dye precipitation can be prevented.

[0135] The solvent may be, for example, γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ethylene glycol acetate (EGA), cyclohexanone, 3-methoxy-1-butanol, or combinations thereof.

[0136] Because of its specific range, it can be usefully used in color filters that exhibit high brightness and high contrast in the desired color coordinates, such as those for LCDs and LEDs.

[0137] Based on the total solids content constituting the photosensitive resin composition, the colorant can be included in amounts of 40 wt% to 60 wt%, for example 30 wt% to 50 wt%, for example 35 wt% to 50 wt%, for example 40 wt% to 50 wt%. When the colorant is included within the above range, chemical resistance and maximum absorption wavelength can be controlled within an appropriate range, high brightness and contrast can be displayed at the desired color coordinates, and coloring effect and developability can be improved.

[0138] (B) Photopolymerizable compounds

[0139] The photopolymerizable compound may be a monofunctional or polyfunctional ester of (meth)acrylic acid comprising at least one olefinic unsaturated double bond.

[0140] The photopolymerizable compound has alkene-based unsaturated double bonds, thus it can form patterns with excellent heat resistance, light resistance and chemical resistance by inducing full polymerization during exposure in the patterning process.

[0141] Specific examples of photopolymerizable compounds may 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, etc. Pentaerythritol tetra(meth)acrylate, 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, tri(meth)acryloyloxyethyl phosphate, phenolic epoxy(meth)acrylate, etc.

[0142] Examples of commercially available photopolymerizable compounds are shown below. Monofunctional (meth)acrylates may include Aronix. Aronix Aronix (Toagosei Chemistry Industry Co., Ltd.); KAYARAD KAYARAD (Nippon Kayaku Co.,Ltd.); (Osaka Organic Chemical Ind., Ltd.), etc. Examples of bifunctional (meth)acrylates may include Aronix. Aronix Aronix (Toagosei ChemistryIndustry Co.,Ltd.)、KAYARAD KAYARAD KAYARAD (NipponKayaku Co.,Ltd.)、 V-335 (Osaka Organic Chemical Ind., Ltd.), etc. Examples of trifunctional (meth)acrylates may include Aronix. Aronix Aronix Aronix Aronix Aronix Aronix (Toagosei Chemistry Industry Co., Ltd.); KAYARAD KAYARAD KAYARAD KAYARAD KAYARAD (Nippon Kayaku Co.,Ltd.); (Osaka YukiKayaku Kogyo Co.Ltd.), etc. These can be used alone or as a mixture of two or more.

[0143] Photopolymerizable compounds can be treated with acid anhydrides to improve their developability.

[0144] Based on the total solids content constituting the photosensitive resin composition, the photopolymerizable compound may be included in an amount of 5 wt% to 30 wt%, specifically 10 wt% to 25 wt%, for example 15 wt% to 20 wt%. If the photopolymerizable compound within the above range is included, sufficient curing occurs during exposure in the patterning process, resulting in excellent reliability and excellent developability using alkaline developers.

[0145] (C) Photopolymerization initiator

[0146] The photopolymerization initiator can be a commonly used initiator in photosensitive resin compositions, such as acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, triazine compounds, oxime compounds, or combinations thereof.

[0147] Examples of the acetophenone compounds may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropyl-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-but-1-one, etc.

[0148] Examples of benzophenone compounds include benzoyl benzoate, benzoyl benzoate methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0149] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0150] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0151] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-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, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthol-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-helianyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0152] Examples of 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]ethyl ketone, O-ethoxycarbonyl-α-oxoamine-1-phenylprop-1-one, etc. Specific examples of o-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, 1-(4-phenylhydrothiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylhydrothiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylhydrothiophenyl)-octane-1-one-oxime-O-acetate, and 1-(4-phenylhydrothiophenyl)-but-1-one-oxime-O-acetate.

[0153] In addition to the compounds mentioned above, the photopolymerization initiator may include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, etc.

[0154] The photopolymerization initiator can be used with photosensitizers that can induce a chemical reaction by absorbing light and being excited, and then transferring their energy.

[0155] Examples of photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, and dipentaerythritol tetra-3-mercaptopropionate.

[0156] Based on the total solids content constituting the photosensitive resin composition, the photopolymerization initiator may be included in an amount from 0.1 wt% to 20 wt%, for example, from 1 wt% to 10 wt%. If the photopolymerization initiator within this range is included, sufficient photopolymerization occurs during exposure in the patterning process, resulting in excellent reliability; improved heat resistance, light resistance, chemical resistance, resolution, and close-contact properties of the pattern; and prevention of transmittance reduction caused by unreacted initiator.

[0157] (D) Adhesive resin

[0158] The adhesive resin may include acrylic resin.

[0159] The acrylic resin is a copolymer of a first olefinic unsaturated monomer and a second olefinic unsaturated monomer that can be copolymerized therewith, and is a resin comprising at least one repeating acrylic unit.

[0160] The first olefinic unsaturated monomer may be an olefinic unsaturated monomer comprising at least one carboxyl group, and examples of said monomer may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and combinations thereof.

[0161] Based on the total amount of the acrylic adhesive resin, the first olefinic unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, for example, 10 wt% to 40 wt%.

[0162] The second olefinic unsaturated monomer can be an aromatic vinyl compound, such as styrene, α-methylstyrene, vinyltoluene, vinylbenzene methyl ether, etc.; an unsaturated carboxylic acid ester compound, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, etc.; an unsaturated carboxylic acid aminoalkyl ester compound, such as 2-aminoethyl methacrylate, 2-dimethylaminoethyl methacrylate, etc.; a carboxylic acid vinyl ester compound, such as vinyl acetate, vinyl benzoate, etc.; an unsaturated carboxylic acid glycidyl ester compound, such as glycidyl methacrylate, etc.; a cyanide compound, such as methacrylonitrile, etc.; an unsaturated amide compound, such as methacrylamide, etc.; etc., and the second olefinic unsaturated monomer can be used alone or as a mixture of two or more.

[0163] Specific examples of the acrylic resin may be (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., but are not limited thereto, and these may be used alone or as a mixture of two or more.

[0164] The adhesive resin may include epoxy resins.

[0165] The adhesive resin may have its heat resistance improved by further including an epoxy resin. The epoxy resin may be, for example, phenolic epoxy resin, tetramethylbiphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, or a combination thereof, but is not limited thereto.

[0166] Furthermore, the binder resin, including the epoxy resin, ensures the dispersion stability of colorants such as pigments, which will be described subsequently, and helps to form pixels with the desired resolution during development.

[0167] Based on the total amount of the adhesive resin, the epoxy resin may be included in an amount of about 1 wt% to about 10 wt%, for example, about 5 wt% to about 10 wt%. Including epoxy resins within the above range can significantly improve film residue ratio and chemical resistance.

[0168] The epoxy equivalent weight of the epoxy resin can be from about 150 g / eq to about 200 g / eq. If the adhesive resin includes an epoxy resin with an epoxy equivalent weight within the above range, it has an advantageous effect on improving the curing degree of the formed pattern and fixing the colorant in the structure in which the pattern is formed.

[0169] The adhesive resin can be dissolved in solid form in a solvent, which will be described later, to form a photosensitive resin composition. In this case, based on the total amount of the adhesive resin solution dissolved in the solvent, the adhesive resin in solid form can be from about 0.1 wt% to about 30 wt%, for example from about 20 wt% to about 30 wt%.

[0170] Furthermore, based on the total solids content constituting the photosensitive resin composition, the binder resin may be included in an amount of 0.5 wt% to 25 wt%, specifically 1 wt% to 20 wt%, for example 1 wt% to 10 wt%. If the binder resin within the above range is included, excellent surface smoothness can be obtained due to excellent developability and improved crosslinking properties during filter manufacturing.

[0171] (E) Solvent

[0172] Solvents can be materials that are compatible with colorants, binder resins, photopolymerizable compounds, and photopolymerization initiators but do not react with them.

[0173] Examples of solvents can include alcohols, such as methanol and ethanol; ethers, such as dichloroethyl ether, n-butyl ether, diisopentyl ether, methyl phenyl ether, tetrahydrofuran, etc.; glycol ethers, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; selenoacetic acid, such as methyl selenoacetic acid, ethyl selenoacetic acid, and diethyl selenoacetic acid; carbitol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates, such as... Propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons, such as toluene, xylene, etc.; ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-acetone, methyl n-butyl ketone, methyl n-pentanone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid esters, such as methyl lactate, ethyl lactate, etc.; oxyacetic acid alkyl esters, such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkoxyacetic acid alkyl esters, such as methyl methoxyacetate, methoxy... Ethyl ethyl acetate, methoxyethyl acetate, methyl ethoxyethyl acetate, ethyl ethoxyacetate, etc.; alkyl 3-oxypropionic acid esters, such as methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.; alkyl 3-alkoxypropionic acid esters, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxypropionic acid esters, such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.; alkyl 2-alkoxypropionic acid esters, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, alkyl 2-alkoxypropionate, etc. - Ethyl ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-O-2-methylpropionates, such as methyl 2-O-2-methylpropionate, ethyl 2-O-2-methylpropionate, etc.; 2-alkoxy-2-methylalkylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc., monooxymonocarboxylic acid alkyl esters; esters, such as 2-hydroxyethylpropionate, 2-hydroxy-2-methylethylpropionate, hydroxyethyl acetate, 2-hydroxy-3-methylmethylbutyrate, etc.; ketonate esters, such as ethyl pyruvate, etc. In addition, high-boiling-point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformaniline, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl celazine, etc. can also be used.

[0174] Considering compatibility and reactivity, the solvent may be propylene glycol monomethyl ether acetate (PGMEA), n-butyl acetate (n-BA), ethylene glycol dimethyl ether, or a combination thereof.

[0175] Based on the total amount of the photosensitive resin composition, the solvent may be included in the balance, for example, 40 wt% to 90 wt%, or 45 wt% to 70 wt%. The solvent may be included in an amount of 3 to 7 times the total solids content of the photosensitive resin composition. If the solvent within the above range is included, a coating film exhibiting excellent coatability and excellent flatness of the photosensitive resin composition can be obtained.

[0176] (F) Other additives

[0177] The photosensitive resin composition may also contain at least one additive selected from the following: malonic acid, 3-amino-1,2-propanediol, coupling agent, leveling agent, surfactant, antioxidant, or a combination thereof, thereby avoiding stains or spots during coating, adjusting leveling properties, or preventing pattern residue due to undeveloped areas.

[0178] The additives can be easily adjusted according to the desired physical properties.

[0179] The coupling agent may be a silane coupling agent, and examples of such silane coupling agents may include trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate-propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(epoxycyclohexyl)ethyltrimethoxysilane, which may be used alone or in mixtures of two or more types.

[0180] Based on 100 parts by weight of the photosensitive resin composition, the silane coupling agent can be used specifically in amounts from 0.01 parts by weight to 1 part by weight.

[0181] Additionally, if necessary, the photosensitive resin composition for color filters may also contain surfactants, such as fluorinated surfactants.

[0182] Examples of fluorinated surfactants may include, but are not limited to, F-482, F-484 and F-478 of DIC Co., Ltd.

[0183] Based on the total amount of the photosensitive resin composition, the surfactant may be included in an amount of 0.01 wt% to 5 wt%, and more preferably in an amount of 0.01 wt% to 2 wt%. If it is outside the above range, it may undesirably cause problems with the generation of foreign matter after development.

[0184] In addition, without impairing the physical properties, a certain amount of other additives, such as antioxidants and stabilizers, can be added to the photosensitive resin composition.

[0185] The antioxidant may include hydroquinone compounds, catechol compounds, or combinations thereof, but is not necessarily limited thereto. According to one embodiment, because the photosensitive resin composition also contains hydroquinone compounds, catechol compounds, or combinations thereof, room-temperature crosslinking can be prevented during exposure after printing (coating) the photosensitive resin composition.

[0186] For example, the hydroquinone compounds, catechol compounds, or combinations thereof may include hydroquinone, methyl hydroquinone, methoxy hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, tert-butylcatechol, 4-methoxycatechol, pyrogallol, 2,6-di-tert-butyl-4-cresol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylamine-O,O')aluminum, or combinations thereof, but are not necessarily limited thereto.

[0187] The hydroquinone compounds, catechol compounds, or combinations thereof can be used in the form of dispersions, and antioxidants in dispersion form can be included in amounts from 0.001 wt% to 3 wt%, for example, from 0.1 wt% to 2 wt%, based on the total solids content constituting the photosensitive resin composition. When antioxidants within the above range are included, the problem of aging at room temperature can be solved, while preventing decreased sensitivity and surface peeling.

[0188] (Photosensitive resin film, color filter and display device)

[0189] According to another embodiment, a photosensitive resin film manufactured using a photosensitive resin composition according to one embodiment is provided.

[0190] One embodiment of the photosensitive resin film is generally divided into positive photoresist and negative photoresist.

[0191] In one embodiment, the photosensitive resin film can be a negative photoresist. This has the advantage of not causing the photoresist to stain and obtaining relatively higher photosensitivity than a positive photoresist.

[0192] For example, the photosensitive resin film may have The thickness and transmittance at 450 nm less than or equal to 9%, at 550 nm greater than or equal to 90%, at 630 nm less than or equal to 15%, at 650 nm less than or equal to 4%, and at 700 nm less than or equal to 60%. When the photosensitive resin film has the above-mentioned wavelength-specific transmittance at the above thickness, it can easily realize an ultrathin film with excellent sensor sensitivity.

[0193] According to another embodiment, a color filter manufactured using the above-described photosensitive resin composition is provided.

[0194] The method for manufacturing a color filter according to one embodiment is shown below.

[0195] The above-mentioned photosensitive resin composition is coated on a glass substrate by a suitable method such as spin coating, roller coating, spray coating, etc., to form a photosensitive resin composition layer with a thickness of 0.3 μm to 0.5 μm.

[0196] Subsequently, a substrate having a photosensitive resin composition layer is irradiated with light to form the pattern required for the color filter. Irradiation can be performed using UV, electron beam, or X-rays as the light source, and UV irradiation can be performed in the region of, for example, 190 nm to 450 nm and, for example, 200 nm to 400 nm. Irradiation can be further performed by using a photoresist mask. After the irradiation process in this manner, the photosensitive resin composition layer exposed to the light source is treated with a developer. Here, the unexposed areas in the photosensitive resin composition layer dissolve and form a pattern for the color filter. This process can be repeated the same number of times as the desired color to obtain a color filter with the desired pattern. In addition, if the image pattern obtained by development in the above process is cured by reheating or irradiating it with photochemical rays, crack resistance, solvent resistance, etc., can be improved.

[0197] According to another embodiment, an image sensor including the color filter described above is provided.

[0198] According to another embodiment, a display device including the above-described image sensor is provided.

[0199] The display device may be a liquid crystal display (LCD).

[0200] The invention will be described in more detail below with reference to embodiments. However, the following embodiments are merely preferred embodiments of the invention, and the invention is not limited to these embodiments.

[0201] (synthesis example)

[0202] Synthesis Example 1: Compounds represented by chemical formula 4-1

[0203] 2-[(4-bromophenoxy)methyl]ethylene oxide (20 mol), Pd(OAc)₂ (0.002 mmol), sodium tert-butoxide (30 mmol), and 2-aminoheptane (20 mmol) were added to toluene solvent, and the mixture was 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. Subsequently, ethyl acetate was added to the solution, and the mixture was washed twice with water to extract the organic layer. The extracted organic layer was purified by vacuum distillation and column chromatography to obtain intermediate 1.

[0204] Intermediate 1 (20 mmol), Pd(OAc)2 (0.002 mmol), sodium tert-butoxide (30 mmol), and 1-bromobenzene (20 mmol) were added to toluene solvent, and the mixture was 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. Subsequently, ethyl acetate was added to the solution, and the mixture was washed twice with water to extract the organic layer. The extracted organic layer was purified by vacuum distillation and column chromatography to obtain intermediate 2.

[0205] Intermediate 2 (60 mmol) and 3,4-dihydroxy-3-cyclobutyn-1,2-dione (30 mmol) were added to toluene (200 mL) and butanol (200 mL), then refluxed, and the resulting water was removed using a Dean-Stark distillation apparatus. After stirring for 12 hours, the resulting green product was distilled under reduced pressure and purified by column chromatography to obtain intermediate 3.

[0206] Intermediate 3 (5 mmol) was dissolved in 600 mL of chloroform, and triethylamine (50 mmol) was added to it. Subsequently, 2,6-pyridine dicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and then added dropwise simultaneously at room temperature for 5 hours. After 12 hours, vacuum distillation was performed, and the compound represented by chemical formula 4-1 was obtained by column chromatography.

[0207] [Chemical Formula 4-1]

[0208]

[0209] Maldi-tof MS: 1291.62 m / z

[0210] Synthesis Example 2: Compounds represented by chemical formula 5-1

[0211] The compound represented by chemical formula 5-1 was obtained 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-xylenediamine.

[0212] [Chemical Formula 5-1]

[0213]

[0214] Maldi-tof MS: 1435.45 m / z

[0215] Comparative Synthesis Example 1: Compounds represented by chemical formula C-1

[0216] 10 mol of 2,4-dimethyldiphenylamine, 12 mol of 1,2-epoxycyclohexane, and 12 mol of sodium hydride were added to N,N-dimethylformamide, and the mixture was heated at 90 °C for 24 hours. Subsequently, ethyl acetate was added to the solution, and the mixture was 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 4.

[0217] Intermediate 4 (10 mmol), iodomethane (15 mmol), and sodium hydride (15 mmol) were added to N,N-dimethylformamide and stirred at room temperature for 24 hours. Ethyl acetate was then added to the solution, followed by washing 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.

[0218] Intermediate 5 (60 mmol) and 3,4-dihydroxy-3-cyclobutyn-1,2-dione (30 mmol) were added to toluene (200 mL) and butanol (200 mL), then refluxed, and the resulting water was removed using a Dean-Stark distillation apparatus. After stirring for 12 hours, the green product was distilled under reduced pressure and purified by column chromatography to obtain intermediate 6.

[0219] Intermediate 6 (5 mmol) was dissolved in 600 mL of chloroform, and triethylamine (50 mmol) was added to it. 2,6-pyridine dicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and then added dropwise simultaneously at room temperature for 5 hours. After 12 hours, vacuum distillation was performed, and the compound represented by chemical formula C-1 was obtained by column chromatography.

[0220] [Chemical formula C-1]

[0221]

[0222] Maldi-tof MS: 1230.59 m / z

[0223] Preparation of photosensitive resin compositions

[0224] Each photosensitive resin composition according to Examples 1 to 8 and Comparative Examples 1 to 8 was prepared to have the composition shown in Tables 1 and 2.

[0225] Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature (20°C) for 30 minutes. A binder resin, a photopolymerizable compound, and additives were then added, and the mixture was stirred at room temperature for 60 minutes. Subsequently, a green dye and / or pigment dispersion was added as a colorant to the resulting product, and the mixture was stirred at room temperature for 30 minutes. Each photosensitive coloring resin composition was then prepared by removing impurities through two filtrations using a 0.45 μm PP syringe filter.

[0226] (Table 1)

[0227] (Unit: parts by weight)

[0228]

[0229] (Table 2)

[0230] (Unit: parts by weight)

[0231]

[0232]

[0233] The materials used in Tables 1 and 2 are shown below.

[0234] (B) Photopolymerizable monomers

[0235] (B-1) Dipentaerythritol hexaacrylate (DPHA, manufacturer: Nippon Kayaku Co., Ltd.)

[0236] (B-2)DGE-4A(Gongyoungsa Co.,Ltd.)

[0237] (C) Photopolymerization initiator

[0238] (C-1)PBG-304(Tronly)

[0239] (C-2)SPI03 (Manufacturer: Samyang Corporation)

[0240] (D) Adhesive resin

[0241] SP-RY-99 (Manufacturer: Showa Denko)

[0242] (E) Solvent

[0243] (E-1) Propylene glycol monomethyl ether acetate (PGMEA) (Manufacturer: Daicel)

[0244] (E-2)γ-Butyrolactone (Manufacturer: Daicel)

[0245] antioxidants

[0246] Methylhydroquinone (manufacturer: Sigma Aldrich)

[0247] additive

[0248] F554 (Manufacturer: DIC Co., Ltd.)

[0249] Evaluation 1: Spectral characteristics (transmittance)

[0250] Each composition was spin-coated to a thickness of 0.4 to 1.0 μm onto three glass specimens (10 × 10 cm) and then baked on a hot plate at 90 °C for 3 minutes. Subsequently, the coated specimens were exposed to 200 mJ using a UV light exposer and then baked on a hot plate at 230 °C for 5 minutes. The spectra of the three specimens were measured, and the thickness was measured using an Alpha Step. The results were used to calculate the transmittance at a thickness of 0.5 μm. The transmittance at specific wavelengths is shown in Table 3.

[0251] Evaluation 2: Chemical resistance (discoloration)

[0252] The colored sample prepared in Evaluation 1 was cut into 5cm × 5cm pieces and then 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 colorimeter (MCPD, Otsuka Electronics Co., Ltd.). ΔEab*, the color change standard, was calculated according to Equation 1, and the results are shown in Table 3.

[0253] [Equation 1]

[0254] ΔEab*={(ΔL*) 2 +(Δa*) 2 +(Δb*) 2 ×1 / 2 (The smaller the ΔEab* value, the better the heat resistance and chemical resistance)

[0255] Evaluation 3: Changes in light transmittance

[0256] SiO2 was deposited on the sample of Evaluation 1 to The sample was thick and irradiated with a xenon lamp for 350 hours. Transmittance changes before and after exposure were measured at different wavelengths (400 to 700 nm). The largest change was selected. The final results are shown in Table 3.

[0257] (Table 3)

[0258]

[0259]

[0260] Referring to Table 3, compared with the compositions of Comparative Examples 1 to 8, the compositions of Examples 1 to 8 have low transmittance in wavelength ranges less than or equal to 480 nm and 630 nm to 700 nm, and high transmittance in the region of 480 nm to 620 nm. Furthermore, when an image sensor is manufactured using the compositions, not only is the sensor sensitivity improved, but also excellent heat resistance and chemical resistance are achieved.

[0261] Although the invention has been described in conjunction with exemplary embodiments which are now considered to be practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A photosensitive resin composition comprising: (A) Coloring agent, (B) Photopolymerizable compounds, (C) Photopolymerization initiator, (D) Adhesive resin, and (E) Solvent; in, The colorant contains 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. Based on the solids content, the first green dye is contained in an amount greater than the weight of the second green dye, and Based on solids content, the first green dye is contained in a weight less than nine times the weight of the second green dye: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In chemical formulas 1 to 3 L 1 and L 2 Each is independently a substituted or unsubstituted C1 to C20 alkylene group, R 1 and R 2 Each is an epoxy group independently. R 3 and R 4 Each is independently a substituted or unsubstituted C1 to C20 alkyl group. L a and L b Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group. R a It is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a *-C(=O)OR 0 , where R 0 It is a substituted or unsubstituted C1 to C20 alkyl group. m and n2 are each an independent integer from 1 to 10, and n1 is an integer from 1 to 4.

2. The photosensitive resin composition according to claim 1, wherein, R 3 It is a substituted or unsubstituted C1 to C3 alkyl group, and R 4 It is a substituted or unsubstituted C3 to C20 alkyl group.

3. The photosensitive resin composition according to claim 1, wherein, Chemical formula 2 is represented by chemical formula 2-1: [Chemical Formula 2-1] 4. The photosensitive resin composition according to claim 1, wherein, Chemical formula 3 is represented by chemical formula 3-1: [Chemical Formula 3-1] In chemical formula 3-1, R b To R e Each is independently a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

5. The photosensitive resin composition according to claim 1, wherein, The first green dye has a maximum absorption wavelength in the range of 640 nm to 650 nm, and the second green dye has a maximum absorption wavelength in the range of 660 nm to 670 nm.

6. The photosensitive resin composition according to claim 1, wherein, The first green dye is represented by chemical formula 4-1 or chemical formula 4-2: [Chemical Formula 4-1] [Chemical Formula 4-2] 7. The photosensitive resin composition according to claim 1, wherein, The second green dye is represented by any one of chemical formulas 5-1 to 5-3: [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] 8. The photosensitive resin composition according to claim 1, wherein, Based on the total amount of solids constituting the photosensitive resin composition, the total content of the green dye and yellow pigment is 40 wt% to 55 wt%.

9. The photosensitive resin composition according to claim 1, wherein, Based on the total amount of solids constituting the photosensitive resin composition, the photosensitive resin composition comprises: The colorant, 40 wt% to 60 wt%, The photopolymerizable compound is present in amounts ranging from 5 wt% to 30 wt%. 0.1 wt% to 20 wt% of the photopolymerization initiator, and The adhesive resin is 0.5 wt% to 25 wt%.

10. A photosensitive resin film, said photosensitive resin film being 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 the photosensitive resin film of claim 10 or 11.

Images