Green photosensitive resin composition and color filter formed therefrom

Abstract

The embodiment of the present invention provides a green photosensitive resin composition, comprising: (A) a colorant; (B) an alkali-soluble resin; (C) a polymerizable unsaturated compound; (D) a photopolymerization initiator; and (E) a solvent, wherein the colorant (A) comprises a blue colorant (A1) and a yellow colorant (A2), and the combination of the blue colorant (A1) and the yellow colorant (A2) meets the color selection penetration of ≥50%, wherein the color selection penetration is defined as:

Description

Technical Field

[0001] The present disclosure relates to a green photosensitive resin composition and its application. Background Art

[0002] In various display devices (such as liquid crystal display devices) and sensing devices (such as charge-coupled devices (CCDs) and complementary metal-oxide-semiconductor (CMOS) sensing devices), in order to display or sense light of a specific color, a color filter in the device is required. Generally speaking, a green photosensitive resin composition required for a color filter can be prepared, the resin composition is formed into a layer on a substrate, and then the desired pattern is obtained through exposure and development to form a color filter.

[0003] After the low-temperature process, the color filter made of the green photosensitive resin composition has poor light resistance, which affects the color performance of the color filter and further has a great impact on the chromaticity of the color panel after the process.

[0004] Therefore, although the existing green photosensitive resin composition generally meets various requirements, it is not satisfactory in all aspects, so there is still a need for improvement of the green photosensitive resin composition. Summary of the invention

[0005] The embodiment of the present invention provides a green photosensitive resin composition, comprising: (A) a colorant; (B) an alkali-soluble resin; (C) a polymerizable unsaturated compound; (D) a photopolymerization initiator; and (E) a solvent, wherein the colorant (A) comprises a blue colorant (A1) and a yellow colorant (A2), and the combination of the blue colorant (A1) and the yellow colorant (A2) meets the color selection penetration of ≥50%, wherein the color selection penetration is defined as:

[0006]

[0007] The embodiment of the present invention further provides a color filter formed by the green photosensitive resin composition.

[0008] In order to make the features of the present disclosure clear and easy to understand, embodiments are specifically cited below and described in detail with reference to the accompanying drawings. For other precautions, please refer to the technical field. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Various aspects of the present disclosure will be described in detail below with reference to the accompanying drawings.

[0010] Figure 1is an exemplary penetration map depicted according to some embodiments of the present disclosure. DETAILED DESCRIPTION

[0011] The following is a detailed description of the green photosensitive resin composition and color filter provided in this case. It should be understood that the following description provides many different embodiments or examples for implementing different modes of some embodiments of the present disclosure. The specific elements and arrangements described below are only for the purpose of simply and clearly describing some embodiments of the present disclosure. Of course, these are only used for example and are not intended to limit the present disclosure.

[0012] In the text, the terms "about", "approximately", and "substantially" generally mean within 5%, preferably within 3%, more preferably within 1%, or within 2%, or within 1%, or within 0.5% of a given value or range. The quantities given here are approximate quantities, that is, in the absence of specific description of "about", "approximately", and "substantially", the meanings of "about", "approximately", and "substantially" can still be implied.

[0013] The color filter made of the green photosensitive resin composition that directly uses the green colorant is prone to poor light resistance due to the low temperature process, which affects the color performance of the color filter and further affects the chromaticity of the color panel. To solve the above problem, the present invention uses a combination of a blue colorant and a yellow colorant to replace the traditional green colorant. The color filter made of the green photosensitive resin composition has good light resistance after the low temperature process.

[0014] In addition, the present invention establishes a set of judgment methods for selecting the composition of blue colorant and yellow colorant, so that the green photosensitive resin composition can maintain good transmittance even after low temperature process. The transmittance of the green photosensitive resin composition will be evaluated by two parameters: (1) the integral value of the transmittance value after irradiation with light source at wavelengths of 380nm to 780nm and (2) the integral value of the light source transmittance value at wavelengths of 380nm to 780nm. In this specification, the transmittance value T% of the green photosensitive resin composition is obtained by making a color chip and measuring it with a colorimeter.

[0015] An embodiment of the present invention provides a green photosensitive resin composition, comprising:

[0016] (A) coloring agent;

[0017] (B) alkali-soluble resin;

[0018] (C) polymerizable unsaturated compounds;

[0019] (D) a photopolymerization initiator; and

[0020] (E) a solvent,

[0021] The colorant (A) includes a blue colorant (A1) and a yellow colorant (A2), wherein the combination of the blue colorant (A1) and the yellow colorant (A2) is evaluated by color selection transmittance. The color selection transmittance is ≥50%, which can maintain high transparency after a low-temperature process, thereby optimizing the performance and suppressing the reduction of the image quality of the display device.

[0022] The color selection penetration is defined as:

[0023]

[0024] In detail, the green photosensitive resin composition of the embodiment of the present invention comprises: 10 to 45 weight % of a colorant (A); 5 to 30 weight % of an alkali-soluble resin (B); 1 to 30 weight % of a polymerizable unsaturated compound (C); 0.1 to 2.5 weight % of a photopolymerization initiator (D); and 35 to 80 weight % of a solvent (E).

[0025] In a specific embodiment, the green photosensitive resin composition includes: 10 to 30 weight % of a colorant (A); 10 to 30 weight % of an alkali-soluble resin (B); 1 to 20 weight % of a polymerizable unsaturated compound (C); 0.1 to 1.5 weight % of a photopolymerization initiator (D); and 35 to 70 weight % of a solvent (E).

[0026] The embodiment of the present invention selects the blue colorant (A1) and the yellow colorant (A2) in the green photosensitive resin composition by selecting the color transmittance greater than or equal to 50%, so as to ensure that the green photosensitive resin composition has good transmittance.

[0027] First, let’s explain the color selection penetration:

[0028] [Color selection penetration]

[0029] By measuring the color selective transmittance of the combination of the blue colorant (A1) and the yellow colorant (A2) in the green photosensitive resin composition of the present invention, it is examined whether the green photosensitive resin composition can maintain high transparency after the low temperature process. Specifically, the color selective transmittance is defined as:

[0030]

[0031] And refer to Figure 1 Explain the selection of penetration. Figure 1 It is the transmission spectrum of the light source, the green photosensitive resin composition, and the green photosensitive resin composition after the light source irradiates the green photosensitive resin composition in the visible light wavelength range (380-780nm). Figure 1In the formula, the light source penetration value, color penetration value, and color penetration value × light source penetration value are used to represent the numerator. [Color penetration value × light source penetration value] means Figure 1 The integral value of the transmittance value of the green photosensitive resin composition after the light source in the visible light wavelength range is within the range of 20-35, and the denominator is The light source penetration value is Figure 1 The integrated value of the light source in the visible light wavelength range.

[0032] According to some embodiments of the present invention, the color selective transmittance of the green photosensitive resin composition is greater than or equal to 50%, preferably greater than or equal to 55%, and more preferably greater than or equal to 60% and less than or equal to 85%. The color selective transmittance greater than or equal to 50% can enable the green photosensitive resin composition to maintain high transparency after a low-temperature process, thereby optimizing the performance and suppressing the degradation of the image quality of the display device.

[0033] When the color selection transmittance is less than 50%, the color filter formed by the green photosensitive resin composition will require a higher power light source to make the light transmitted by the panel visible to human eyes, which consumes a large cost.

[0034] The following is a detailed description of each component in the green photosensitive resin composition:

[0035] [(A) Colorant]

[0036] According to some embodiments of the present invention, the colorant (A) includes a blue colorant (A1) and a yellow colorant (A2). On the other hand, the colorant (A) may include a pigment (P), a dye (Q), or a combination thereof. Therefore, the blue colorant (A1) may include a blue pigment (A1-P), a blue dye (A1-Q), or a combination thereof, and the yellow colorant (A2) may include a yellow pigment (A2-P), a yellow dye (A2-Q), or a combination thereof.

[0037] In some embodiments, the wavelength of the blue colorant (A1) is 380-600 nm, and the wavelength of the yellow colorant (A2) is 480-780 nm.

[0038] In some embodiments, the pigment (P) may be an organic pigment or an inorganic pigment commonly used in the field of printing ink or inkjet ink.

[0039] In some embodiments, the organic pigment may be, for example, a water-soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, an isoindoline pigment, a perylene pigment, a pyrene pigment, a dioxazine pigment, anthraquinone pigment, a dianthraquinone pigment, anthrapyrimidine pigment, anthraquinone pigment, anthranthrone pigment, indanthrone pigment, flavanthrone pigment, pyranthrone pigment, diketopyrrolopyrrole pigment, etc., but is not limited thereto.

[0040] In some embodiments, the inorganic pigment may be a metal compound such as a metal oxide or a metal coordination compound, and specifically, may be an oxide or a composite metal oxide of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, etc.

[0041] Specifically, the organic pigments and inorganic pigments may be, for example, CI pigment yellow (A2-P) and CI pigment blue (A1-P) among compounds classified as pigments under the Color Rendering Index (published by The society of Dyers and Colourists). More specifically, they may be, for example, pigments with the following Color Rendering Index (CI) numbers, but are not limited thereto, and they may be used individually or in combination of two or more.

[0042] In some embodiments, the blue pigment (A1-P) may be, for example, a phthalocyanine pigment or other suitable substances. Specifically, for example, CI pigment blue 15, CI pigment blue 15:1, CI pigment blue 15:2, CI pigment blue 15:3, CI pigment blue 15:4, CI pigment blue 15:6, CI pigment blue 16, CI pigment blue 21, CI pigment blue 22, CI pigment blue 28, CI pigment blue 60, CI pigment blue 64, CI pigment blue 76, CI pigment blue 80 and other blue pigments may be used, but are not limited thereto.

[0043] In some embodiments, the pigment (P) may be a known pigment, for example, a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colourists).

[0044] In some embodiments, the yellow pigment (A2-P) may be, for example, a monoazo pigment, a monoazo lake pigment, a disazo pigment, an anthraquinone pigment, a monoazo pyrazolone pigment, a condensed azo pigment, an isoindoline pigment, a benzimidazolone pigment, an azomethine metal complex pigment, a quinophthalone pigment, a quinoxaline pigment, and the like. Specifically, for example, CI Pigment Yellow 1, CI Pigment Yellow 2, CI Pigment Yellow 3, CI Pigment Yellow 4, CI Pigment Yellow 5, CI Pigment Yellow 6, CI Pigment Yellow 10, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 18, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 32, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 35:1, CI Pigment Yellow 36, CI Pigment Yellow 36:1, CI Pigment Yellow 37, CI Pigment Yellow 37:1, CI Pigment Yellow 40, CI Pigment Yellow 42, CI Pigment Yellow 43, CI Pigment Yellow 53, CI Pigment Yellow 55, and CI Pigment Yellow 60 can be used. 、CI Pigment Yellow 61、CI Pigment Yellow 62、CI Pigment Yellow 63、CI Pigment Yellow 65、CI Pigment Yellow 73、CI Pigment Yellow 74、CI Pigment Yellow 77、CI Pigment Yellow 81、CI Pigment Yellow 83、CI Pigment Yellow 86、CI Pigment Yellow 93、CI Pigment Yellow 94、CI Pigment Yellow 95、CI Pigment Yellow 97、CI Pigment Yellow 98、CI Pigment Yellow 100、CI Pigment Yellow 101、CI Pigment Yellow 104、CI Pigment Yellow 106、CI Pigment Yellow 108、CI Pigment Yellow 109、CI Pigment Yellow 110、CI Pigment Yellow 113、CI Pigment Yellow 114、CI Pigment Yellow 115、CI Pigment Yellow 116、CI Pigment Yellow 117、CI Pigment Yellow 118、CI Pigment Yellow 119、CI Pigment Yellow 120、CIPigment Yellow 123, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 161, CI Pigment Yellow 162, CI Pigment Yellow 164, CI Pigment Yellow 166, CI Pigment Yellow 167, CI Yellow pigments include, but are not limited to, pigment yellow 168, CI pigment yellow 169, CI pigment yellow 170, CI pigment yellow 171, CI pigment yellow 172, CI pigment yellow 173, CI pigment yellow 174, CI pigment yellow 175, CI pigment yellow 176, CI pigment yellow 177, CI pigment yellow 179, CI pigment yellow 180, CI pigment yellow 181, CI pigment yellow 182, CI pigment yellow 185, CI pigment yellow 187, CI pigment yellow 188, CI pigment yellow 193, CI pigment yellow 194, CI pigment yellow 199, CI pigment yellow 213, and CI pigment yellow 214.

[0045] In some embodiments, the content of the pigment (P) is 20 to 90% by weight, preferably 40 to 90% by weight, based on the total weight of the solid components in the colorant (A). If the content of the pigment is within the range of 20 to 90% by weight, it has the advantages of low viscosity, excellent storage stability, high dispersion efficiency, and effective improvement of contrast.

[0046] In some embodiments, dye (Q) can be selected from acid dyes with acidic groups such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, etc. and their derivatives. In addition, azo, xanthene, phthalocyanine acid dyes and their derivatives can also be selected. Preferably, the compounds of dyes classified as blue series and yellow series in the color rendering index (published by The Society of Dyers and Colourists) or the blue dyes (A1-Q) and yellow dyes (A2-Q) recorded in the known dyes in the dyeing notes (dying and weaving company) are used. These dyes can be used alone or in combination of two or more.

[0047] In some embodiments, the yellow dye (A2-Q) and the blue dye (A1-Q) may be CI solvent dyes, wherein the CI solvent yellow dye (A2-Q) may be, for example, solvent 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, etc., but is not limited thereto; the CI solvent blue dye (A1-Q) may be, for example, solvent 5, 35, 36, 37, 44, 59, 67, 70, etc., but is not limited thereto.

[0048] In some embodiments, the blue dye (A1-Q) may be a CI acid dye, for example, CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, etc., but is not limited thereto.

[0049] In some embodiments, the yellow dye (A2-Q) and the blue dye (A1-Q) may be CI direct dyes, wherein the CI direct blue dye (A1-Q) may be, for example, CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195 4, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc., but are not limited thereto; CI direct yellow dye (A2-Q) is, for example, CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, etc., but are not limited thereto.

[0050] In some embodiments, the blue dye (A1-Q) may be a CI mordant dye, for example, CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, etc., but is not limited thereto.

[0051] According to some embodiments of the present invention, the content of the dye (Q) is preferably 0.5 to 80% by weight, more preferably 5 to 60% by weight, relative to the total weight of the solid components in the colorant (A). When the content of the dye in the aforementioned photosensitive agent is within the aforementioned range, after pattern formation, the problem of reduced reliability due to dye dissolution caused by organic solvents can be prevented, and excellent sensitivity is preferred.

[0052] In some embodiments, the blue colorant (A1) is preferably B16, B15:6, and the yellow colorant (A2) is preferably Y139, Y139E, Y150, Y185.

[0053] In some embodiments, the weight ratio of the yellow colorant (A2) to the blue colorant (A1) is 35:65-65:35, more preferably 40:60-60:40.

[0054] According to some embodiments of the present invention, the content of the colorant (A) is preferably 10 to 45 weight %, more preferably 10 to 30 weight %, based on the total weight of the green photosensitive resin composition.

[0055] When the content of the colorant (A) is within the above range, the color density of the pixel is sufficient even when a thin film is formed, and the defect property of the non-pixel portion does not decrease during development, so the generation of residue can be suppressed.

[0056] [Alkali-soluble resin (B)]

[0057] In some embodiments, the alkali-soluble resin (B) is a copolymer, which can improve the solvent resistance of the green photosensitive resin composition, and comprises a monomer (a), a monomer (b), a monomer (c), or a combination thereof, wherein the monomer (a) is a structural unit derived from an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, the monomer (b) is a structural unit derived from a cyclic ether structure having 2 to 4 carbon atoms and an olefinic unsaturated bond, and the monomer (c) is a structural unit different from the monomer (a) and the monomer (b). In the copolymer, the above structural units may contain one or more.

[0058] In some embodiments, monomer (a) can be, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1, Unsaturated dicarboxylic acids such as 4-cyclohexenedicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1 ]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing a carboxyl group; unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like; unsaturated mono[(meth)acryloxyalkyl] esters of polycarboxylic acids having a valence of 2 or more such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate; unsaturated acrylic esters containing a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid, etc., but are not limited thereto.

[0059] In some embodiments, monomer (a) is preferably acrylic acid, methacrylic acid, maleic anhydride, etc., considering copolymerization reactivity and solubility of the obtained resin in alkaline aqueous solution.

[0060] In some embodiments, monomer (b) refers to a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0061] In addition, in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0062] In some embodiments, monomer (b) can include, for example, a monomer (b1) having an ethylene oxide or propylene oxide group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b1)"), a monomer (b2) having an oxetane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b2)"), a monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b3)"), and the like.

[0063] In some embodiments, monomer (b1) can include, for example, a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (b1-1)"), and a monomer (b1-2) having a structure in which alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (b1-2)").

[0064] In some embodiments, monomer (b1-1) can be exemplified by glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis( 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tri(glycidyloxymethyl)styrene, 2,3,5-tri(glycidyloxymethyl)styrene, 2,3,6-tri(glycidyloxymethyl)styrene, 3,4,5-tri(glycidyloxymethyl)styrene, 2,4,6-tri(glycidyloxymethyl)styrene, etc., but are not limited thereto.

[0065] In some embodiments, monomer (b1-2) can be listed as epoxypropyl methacrylate, vinyl cyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., CELLOXIDE 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER M100; manufactured by Daicel Corporation), but is not limited thereto.

[0066] In certain embodiments, monomer (b2) is more preferably a monomer with oxetane and (methyl) acryloyloxy. As monomer (b2), for example, 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, but are not limited thereto.

[0067] In some embodiments, monomer (b3) is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group. As monomer (b3), specifically, tetrahydrofurfuryl acrylate (e.g., VISCOATV#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc. can be cited.

[0068] In some embodiments, monomer (b) is preferably monomer (b1) in terms of further improving the reliability of the color filter in terms of light resistance, chemical resistance, etc. Furthermore, monomer (b1-2) is more preferred in terms of excellent storage stability of the green photosensitive resin composition.

[0069] In some embodiments, monomer (c) can include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate. 2，6 ] decane-8-yl ester (in the technical field, as a common name, it is called "dicyclopentyl (meth)acrylate", sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 2，6(Meth)acrylates such as decen-8-yl ester (in the technical field, it is commonly known as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate; (meth)acrylates containing a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1 ]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy Bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexyl dicarbonyl imide derivatives such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc., but are not limited thereto.

[0070] In some embodiments, from the aspects of copolymerization reactivity and light resistance, monomer (c) is preferably styrene, vinyltoluene, methyl (meth)acrylate, tricyclodecyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc.

[0071] In some embodiments, in the embodiment where the monomer (c) is a structural unit having an ethylenically unsaturated bond, it is preferably a structural unit having a (meth)acryloyl group. The alkali-soluble resin (B) having such a structural unit can be obtained by reacting a polymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b) with a monomer having a group reactive with the aforementioned structural unit and an ethylenically unsaturated bond.

[0072] In some embodiments, the structural unit having an ethylenically unsaturated bond may be, for example, a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, a structural unit obtained by adding 2-hydroxyethyl (meth)acrylate to a maleic anhydride unit, a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, and a structural unit obtained by adding carboxylic anhydride to a structural unit having a hydroxyl group.

[0073] In some embodiments, the monomer of the alkali-soluble resin (B) is preferably methyl methacrylate, methacrylic acid, tricyclodecyl methacrylate, glycidyl methacrylate, benzyl methacrylate, N-benzyl maleimide, or a combination thereof.

[0074] According to some embodiments of the present invention, (B) includes 2 to 45 wt % of structural units from (a); 2 to 60 wt % of structural units from (b); and 1 to 80 wt % of structural units from (c).

[0075] According to some embodiments of the present invention, the weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000.

[0076] According to some embodiments of the present invention, the acid value (solid content conversion value) of the alkali-soluble resin (B) is preferably 10 to 300 mg-KOH / g, or 20 to 250 mg-KOH / g, or 20 to 200 mg-KOH / g, or 20 to 170 mg-KOH / g, or 30 to 170 mg-KOH / g. Here, the acid value is a measured value of the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin (B), and can be obtained by titration using a potassium hydroxide aqueous solution, for example.

[0077] According to some embodiments of the present invention, the content of the alkali-soluble resin (B) is preferably 5 to 30 weight %, more preferably 10 to 30 weight %, based on the total weight of the green photosensitive resin composition.

[0078] When the content of the alkali-soluble resin (B) is within the above range, a photosensitive pattern can be formed, and there is a tendency that the resolution and residual film rate of the photosensitive pattern are improved.

[0079] [Polymerizable unsaturated compound (C)]

[0080] In some embodiments, the polymerizable unsaturated compound (C) is a monomer that can be polymerized by active free radicals and / or acids generated by the photopolymerization initiator (D), such as but not limited to ethylenically unsaturated bonds having polymerizable properties, such as (meth)acrylate compounds. Here, the compounds described in brackets mean that the presence and absence of the words in the brackets are included, for example, the aforementioned (meth)acrylate compounds include acrylate compounds and methacrylate compounds.

[0081] For example, the monomer of the polymerizable unsaturated compound (C) may include but is not limited to at least one selected from the group consisting of the following options: polymerizable compounds having one ethylenically unsaturated bond, such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl pyrrolidone; polymerizable compounds having two ethylenically unsaturated bonds, such as 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate; and trimethylolpropane tri(meth)acrylate, dipentaerythritol hexaacrylate, tri( The polymerizable unsaturated compound (C) may be a polymerizable compound having three ethylenically unsaturated bonds, such as pentaerythritol methacrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, dipentaerythritol modified with ethylene glycol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, dipentaerythritol modified with propylene glycol hexa(meth)acrylate, pentaerythritol caprolactone-modified pentaerythritol tetra(meth)acrylate, and dipentaerythritol caprolactone-modified hexa(meth)acrylate. In some embodiments, the polymerizable unsaturated compound (C) is, for example, a compound having an ethylenically unsaturated double bond.

[0082] Examples of commercially available products of the polymerizable unsaturated compound (C) include KAYARAD (green trademark), DPHA (Nippon Kayaku Co., Ltd.), A-TMM-3LM-N (Shin-Nakamura Chemical Co., Ltd.), and A9500 (Shin-Nakamura Chemical Co., Ltd.).

[0083] The weight average molecular weight of the polymerizable unsaturated compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

[0084] In some embodiments, the content of the polymerizable unsaturated compound (C) is preferably 1 to 30 weight %, more preferably 1 to 20 weight %, based on the total weight of the green photosensitive resin composition.

[0085] When the content of the polymerizable unsaturated compound (C) is within the above range, the residual film rate during color pattern formation and the chemical resistance of the color filter can be improved.

[0086] [Photopolymerization initiator (D)]

[0087] In some embodiments of the present invention, the photopolymerization initiator (D) may be any compound that can generate active free radicals, acids, etc. under the action of light, thereby initiating a photopolymerization reaction.

[0088] For example, the photopolymerization initiator (D) may include but is not limited to at least one selected from the group consisting of: oxime compounds, O-acyloxime compounds, alkylphenyl ketone compounds, bisimidazole compounds, triazine compounds, acyl phosphine oxides, benzoin compounds, diphenyl ketone compounds, quinone compounds, 10-butyl-2-chloroacridone, benzyl, methyl phenylformate, acetophenone compounds, and titanocene compounds.

[0089] In some embodiments, the photopolymerization initiator (D) preferably comprises at least one selected from the group consisting of: oxime compounds, O-acyl oxime compounds, alkyl phenyl ketone compounds, biimidazole compounds, acetophenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds. For example, when O-acyl oxime compounds are used as the photopolymerization initiator (D), OXE-01 (BASF), Commercially available products include OXE-02 (from BASF) and N-1919 (from ADEKA).

[0090] In some embodiments, oxime photoinitiators include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), 1,2-butanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), 1,2-butanedione-1-[4-(phenylthio)phenyl]-2-(O-acetyl oxime), 1,2-octanedione-1-[4-(methylthio)phenyl]-2-(O-benzoyl oxime), 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), -(O-(4-methylbenzoyl oxime)), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-acetate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazole-3-yl]-1-(O-acetyl oxime), etc.

[0091] In some embodiments, the O-acyl oxime compound has a compound with a partial structure represented by formula (d1). Hereinafter, * represents a bonding end.

[0092]

[0093] In some embodiments, the O-acyl oxime compound may be exemplified by N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1 -[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imide, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imide, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imide, etc., but not limited thereto. Commercially available products such as IRGACURE OXE01, OXE02 (both manufactured by BASF), and N-1919 (manufactured by ADEKA Corporation) can be used. Among them, the O-acyl oxime compound is preferably at least one selected from N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine is more preferred. These O-acyl oxime compounds tend to provide a color filter with high brightness.

[0094] In some embodiments, the alkyl phenyl ketone compound has a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

[0095]

[0096] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one, etc. Commercially available products such as IRGACURE 369, 907, and 379 (all manufactured by BASF) can be used.

[0097] Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzil dimethyl ketal.

[0098] In terms of light sensitivity, the alkyl phenyl ketone compound is preferably a compound having a partial structure represented by formula (d2).

[0099] In some embodiments, the triazine compound can be 2,4-bistrichloromethyl-6-4-methoxyphenyl-1,3,5-triazine, 2,4-bistrichloromethyl-6-4-methoxynaphthyl-1,3,5-triazine, 2,4-bistrichloromethyl-6-piperonyl-1,3,5-triazine, 2,4-bistrichloromethyl-6-4-methoxyphenyl-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(5-methylfuroxyl)-1,3,5-triazine, triazine, 2,4-bistrichloromethyl-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc., but are not limited thereto.

[0100] In some embodiments, the acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide, but is not limited thereto. Commercially available products such as IRGACURE (registered trademark 819, manufactured by BASF) may be used.

[0101] In some embodiments, the biimidazole compound can be 2,2'-bis(2-chlorophenyl)-4,4',5,5-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5-tetraphenylbiimidazole (for example, see Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5-tetra(alkoxyphenyl) The invention also includes, but is not limited to, imidazole compounds in which the phenyl group at the 4,4',5,5-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), and imidazole compounds in which the phenyl group at the 4,4',5,5-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Publication No. 7-10913, etc.), etc.

[0102] In some embodiments, the acetophenone-based compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane-1-one, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, etc., but are not limited thereto.

[0103] In some embodiments, other polymerization initiators may include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, and titanocene compounds, but are not limited thereto.

[0104] In some embodiments, the photopolymerization initiator (D) is preferably an oxime compound.

[0105] According to some embodiments of the present invention, the content of the photopolymerization initiator (D) is preferably 0.1 to 2.5 weight %, more preferably 0.1 to 1.5 weight %, based on the total weight of the green photosensitive resin composition.

[0106] When the content of the photopolymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be shortened, so the productivity of the color filter can be improved.

[0107] [Solvent (E)]

[0108] In some embodiments, the solvent (E) may include but is not limited to at least one selected from the group consisting of the following options: ester solvent (herein means a solvent containing -COO- but not -O- in the molecule), ether solvent (herein means a solvent containing -O- but not -COO- in the molecule), ether ester solvent (herein means a solvent containing -COO- and -O- in the molecule), ketone solvent (herein means a solvent containing -CO- but not -COO- in the molecule), alcohol solvent (herein means a solvent containing OH but not -O-, -CO- and -COO- in the molecule), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc.

[0109] In some embodiments, the ester solvent may be, for example, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone, but is not limited thereto.

[0110] In some embodiments, the ether solvent can be, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc., but is not limited to these.

[0111] In some embodiments, the ketone solvent may be, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone, but is not limited thereto.

[0112] In some embodiments, as the alcohol solvent, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, and the like may be listed, but are not limited thereto.

[0113] In some embodiments, as the aromatic hydrocarbon solvent, benzene, toluene, xylene, and 1,3,5-trimethylbenzene may be cited, but are not limited thereto.

[0114] In some embodiments, as the amide solvent, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like may be cited, but are not limited thereto.

[0115] In some embodiments, from the aspects of coating and drying properties, the solvent is preferably an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm. The solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone and N,N-dimethylformamide, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N-methylpyrrolidone, ethyl lactate and ethyl 3-ethoxypropionate.

[0116] According to some embodiments of the present invention, the content of the solvent (E) is preferably 35 to 80 weight %, more preferably 35 to 70 weight %, based on the total weight of the green photosensitive resin composition.

[0117] When the content of the solvent (E) is within the above range, the flatness during coating becomes good, and when a color filter is formed, there is no shortage of color density, so that the display characteristics tend to become good.

[0118] [Additives (F)]

[0119] In some embodiments, the green photosensitive resin composition may further include an additive (F). The additive (F) may include an antioxidant, a filler, other polymer compounds, a curing agent, a pigment dispersant, an adhesion promoter, an ultraviolet absorber, an anti-flocculating agent, and the like.

[0120] In some embodiments, the antioxidant can improve the thermal stability by preventing oxidation of the green photosensitive resin composition. The antioxidant comprises a primary antioxidant, a secondary antioxidant, or a combination thereof, wherein the primary antioxidant prevents oxidation by directly participating in oxidation, and the secondary antioxidant is used to prevent excessive consumption of the primary antioxidant.

[0121] In some embodiments, the antioxidant includes a phenolic antioxidant, or a phenolic antioxidant is used in combination with one or more compounds selected from phosphate antioxidants and sulfur-containing antioxidants, wherein the phenolic antioxidant belongs to the aforementioned primary antioxidant, and the phosphate antioxidant and the sulfur-containing antioxidant belong to the aforementioned secondary antioxidant. In some embodiments, the antioxidant is preferably a primary antioxidant 4,4'-butylbis(6-tert-butyl-m-cresol) (BBMS).

[0122] As the filler, specifically, glass, silica, alumina, etc. can be used, but the filler is not limited thereto.

[0123] As for the above-mentioned other polymer compounds, specifically, curable resins such as epoxy resin and maleimide resin, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane can be used, but it is not limited thereto.

[0124] The aforementioned curing agent is used to improve deep curing and mechanical strength, and specifically, epoxy compounds, multifunctional isocyanate compounds, melamine compounds, oxetane compounds, etc. can be used, but it is not limited to this. Regarding the aforementioned epoxy compound, specifically, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins or brominated derivatives of these epoxy resins, other aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene (co) polymer epoxides, (meth) acrylate glycidyl ester (co) polymers, triglycidyl isocyanurate, etc. can be used, but it is not limited to this. As the oxetane compound, specifically, carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylate bisoxetane and the like can be used, but the present invention is not limited thereto.

[0125] A curing auxiliary compound can be used together with the curing agent, and the auxiliary compound can cause the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound to ring-open polymerize. As for the aforementioned curing auxiliary compound, polycarboxylic acids, polycarboxylic acid anhydrides, acid generators, etc. can be used. The aforementioned polycarboxylic acid anhydrides can use compounds commercially available as epoxy resin curing agents. As commercially available aforementioned epoxy resin curing agents, for example, they can be: trade name (ADEKA curing agent EH-700) (manufactured by ADEKA Industries (Co., Ltd.), trade name (RIKACID HH) (manufactured by Shin Nippon Chemical Co., Ltd.), trade name (MH-700) (manufactured by Shin Nippon Chemical Co., Ltd.), etc.

[0126] The curing agents exemplified above may be used alone or in combination of two or more.

[0127] As the pigment dispersant, a commercially available surfactant can be used. Specifically, a surfactant selected from the group consisting of silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic and amphoteric surfactants can be used alone or as a mixture thereof. More specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, and the like can be used. In addition, trade names KP (Shin-Etsu Chemical Co., Ltd.), (POLYFLOW) (Kyoeisha Chemical Co., Ltd.), (EFTOP) (Co., Ltd.), (MEGAFAC) (DAINIPPON INK AND CHEMICALS, INCORPORATED (Co., Ltd.)), (Flourad) (Sumitomo 3M Co., Ltd.), (Asahi guard), Surflon (Surflon) (the above, Asahi Glass Co., Ltd.), (SOLSPERSE) (Lubrisol), EFKA (EFKA Chemical Co., Ltd.), PB821 (Ajinomoto Co., Ltd.), Disperbyk-series (BYK-chemi), and the like can also be used.

[0128] Regarding the aforementioned adhesion promoter, specifically, one selected from the group consisting of the following adhesion promoters, either alone or in mixture, may be used: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

[0129] As for the aforementioned ultraviolet absorber, specifically, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc. can be used, but it is not limited thereto.

[0130] As for the aforementioned deflocculant, specifically, sodium polyacrylate and the like may be used, but it is not limited thereto.

[0131] In some embodiments, the content of the additive (F) is preferably less than 0.1 wt %, more preferably 0.05-0.1 wt %, based on the total weight of the green photosensitive resin composition.

[0132] When the content of the additive (F) is within the above range, various properties such as thermal stability, dispersion, curing, and ultraviolet absorption can be provided without affecting the original properties of the green photosensitive resin composition.

[0133] [Color filter]

[0134] Another embodiment of the present disclosure is a color filter, which can be formed by a cured product of the green photosensitive resin composition according to any of the above embodiments. For example, the green photosensitive resin composition according to any of the above embodiments can be formed into the color filter by photolithography, inkjet, or printing, but the present disclosure is not limited thereto.

[0135] As a method for forming a color filter (color filter pattern) by a cured product of the green photosensitive resin composition of the present case, photolithography, inkjet method, printing method, etc. can be cited. Among them, photolithography is preferred. Photolithography is a method in which the green photosensitive resin composition is applied to a substrate, dried to form a photosensitive composition layer, and the photosensitive composition layer is exposed and developed via light shielding. In the photolithography method, by not using light shielding and / or not developing during exposure, a photosensitive coating film as a cured product of the photosensitive composition layer can be formed. The photosensitive pattern and photosensitive coating film formed in this way can be used as the color filter of the present invention.

[0136] The film thickness of the color filter is not particularly limited and can be appropriately adjusted according to the purpose and application, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm, and even more preferably 1.5 to 3.5 μm.

[0137] As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silicon dioxide on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, or a product formed with a thin film of aluminum, silver, or a silver / copper / palladium alloy on the above substrates can be used. Another color filter layer, a resin layer, a transistor, a circuit, etc. can be formed on these substrates.

[0138] The formation of each color pattern (pixel) by photolithography can be carried out under known or conventional devices and conditions. For example, a green photosensitive resin composition can be first coated on a substrate, and then dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as solvents and dry to obtain a smooth green photosensitive resin composition layer. Examples of coating methods include spin coating, slit coating, and slit and spin coating.

[0139] Next, the green photosensitive resin composition layer is exposed with a light source having a wavelength of 365 nm through a light shield for forming a target photosensitive pattern. Since parallel light can be uniformly irradiated to the entire exposure surface, light shielding and accurate alignment of the substrate on which the green photosensitive resin composition layer is formed can be performed, it is preferable to use an exposure device such as a shield aligner and a stepper.

[0140] The exposed green photosensitive resin composition layer is contacted with a developer to form a photosensitive pattern on the substrate. By developing, the unexposed portion of the green photosensitive resin composition layer is dissolved in the developer and removed. As the developer, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight. Furthermore, the developer may contain a surfactant. The developing method may be any one of a rotary immersion method, an immersion method, and a spray method. Furthermore, the substrate may be tilted at any angle during development. It may be washed with water after development.

[0141] The dose of the aforementioned exposure process is not particularly limited. In some embodiments, the present invention can be exposed at an exposure dose of 50 to 100 mJ.

[0142] Furthermore, the obtained photosensitive pattern is preferably post-baked. The post-baking temperature is preferably 80° C. to 250° C., or 100° C. to 240° C. The post-baking time is preferably 1 to 120 minutes.

[0143] The cured product of the green photosensitive resin composition of the present invention can be used to prepare a color filter, which is a color filter or color filter that can be used in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

[0144] Hereinafter, the present disclosure will provide several embodiments and comparative examples to more specifically illustrate the effects that can be achieved by the green photosensitive resin composition according to the embodiments of the present disclosure, as well as the characteristics of the green photosensitive resin composition prepared by applying the present disclosure. However, the following embodiments and comparative examples are only for illustrative purposes and should not be interpreted as limiting the implementation of the present disclosure.

[0145] [Preparation Example 1] Alkali-soluble resin (B1)

[0146] 213.6 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the temperature was raised to 90° C. while stirring while replacing with nitrogen. Then, 4.0 g of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture consisting of 30.0 g (0.30 mol) of methyl methacrylate, 11.0 g (0.05 mol) of tricyclodecyl methacrylate and 46.9 g (0.65 mol) of methacrylic acid, and the mixture was dropped into the flask from the dropping funnel, and the mixture was stirred at 95° C. for about 1 hour to carry out copolymerization reaction to produce a copolymer. Next, after replacing the nitrogen in the flask with air, 78.2 g (0.55 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added, and a ring-opening addition reaction was carried out at 120° C. for about 6 hours to produce a copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to the reaction solution to obtain a copolymer solution having a solid content concentration of 38% by mass (weight average molecular weight 7,000).

[0147] [Preparation Example 2] Alkali-soluble resin (B2)

[0148] 213.6 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the temperature was raised to 90° C. while stirring while replacing with nitrogen. Then, 4.0 g of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture consisting of 19.8 g (0.10 mol) of N-benzylmaleimide, 44.1 g (0.25 mol) of benzyl methacrylate, 35.1 g (0.35 mol) of methyl methacrylate and 25.9 g (0.30 mol) of methacrylic acid, and the mixture was dropped into the flask from the dropping funnel, and the mixture was stirred at 95° C. for about 2 hours to carry out copolymerization reaction, thereby producing a copolymer. Next, after replacing the nitrogen in the flask with air, 28.6 g (0.20 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added, and a ring-opening addition reaction was carried out at 120° C. for about 6 hours to produce a copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to the reaction solution to obtain a copolymer solution having a solid content concentration of 39% by mass (weight average molecular weight 17,000).

[0149] The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (B) was measured by gel permeation chromatography (GPC method) under the following conditions.

[0150] Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

[0151] Column: TSK-GELG2000HXL

[0152] Column temperature: 40℃

[0153] Solvent: THF

[0154] Flow rate: 1.0mL / min

[0155] Solid content concentration of the test liquid: 0.001 to 0.01 mass%

[0156] Injection volume: 50μL

[0157] Detector: RI

[0158] Standard substances for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation).

[0159] [Example 1-10] Green photosensitive resin composition

[0160] 15 wt % of the colorant (A), 12 wt % of the alkali-soluble resin (B1) obtained in Preparation Example 1, 12 wt % of the alkali-soluble resin (B2) obtained in Preparation Example 2, 10 wt % of the polymerizable unsaturated compound (C) dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.), 1 wt % of the photopolymerization initiator (D) (trade name: PBG-345; manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 50 wt % of the solvent (E) propylene glycol monomethyl ether acetate (PGMEA; purchased from Youhe Trading Co., Ltd.), and less than 0.1 wt % of the additive (F) 4,4′-butylbis(6-tert-butyl-m-cresol) (BBM-S) were mixed, dispersed, and dissolved to obtain a green photosensitive resin composition, wherein the difference between Examples 1-10 is that the compositions of the blue colorant (A1) and the yellow colorant (A2) are different, and their compositions are as shown in Table 1.

[0161] [Comparative Example 1-3] Green photosensitive resin composition

[0162] Except that the compositions of the blue colorant (A1) and the yellow colorant (A2) of Comparative Example 1-3 are different and a green colorant (AG) is used, the rest is the same as that of Example 1-10 to obtain a green photosensitive resin composition.

[0163] The composition of the colorant (A) in the following embodiments and comparative examples is shown in Table 1, wherein the colorant (A) is 100% by weight, and the types of the various components selected are described as follows.

[0164]

[0165] In Table 1, each component represents the following compound:

[0166] B16, B15:6: CI Pigment Blue 16, CI Pigment Blue 15:6 (A1)

[0167] Y185, Y150, Y139, Y139E: CI Pigment Yellow 185, CI Pigment Yellow 150, CI Pigment Yellow 139, CI Pigment Yellow 139E (A2)

[0168] G-63, G36, G-59: CI Pigment Green 63, CI Pigment Green 36, CI Pigment Green-59 (AG)

[0169] In Table 1, the meanings of the values ​​are as follows:

[0170] Value A: [Color penetration value × light source penetration value]

[0171] Value B: Light source penetration value

[0172] T%(A / B): value A / value B, that is

[0173] λ527±3: The peak value of the transmission spectrum obtained after irradiating the green photosensitive resin composition with a light source whose peak of the transmission spectrum is 527nm

[0174] ΔE* ab : Color difference before and after light fastness test

[0175] [Testing of green photosensitive resin composition]

[0176] (1) The green photosensitive resin compositions of Examples 1-10 and Comparative Examples 1-3 were made into color sheets and their transmittance was measured by a colorimeter to obtain the transmittance values ​​(T%) of the green photosensitive resin compositions of Examples 1-10 and Comparative Examples 1-3 in the visible light wavelength range (refer to Figure 1In addition, the transmittance of a green light source with a peak value of 527nm in the visible light wavelength range and the transmittance of a green photosensitive resin composition after irradiating a green light source with a wavelength of 527nm in the visible light wavelength range are measured. Next, the obtained transmittance spectrum is used to evaluate the transmittance and the peak value difference in step (2) and (3), wherein the results obtained in steps (2) and (3) are recorded in Table 1.

[0177] (2) Selective transmittance: First, calculate the value A and value B shown in Table 1, wherein the values ​​A and B represent the integral value of the transmittance of the green photosensitive resin composition irradiated by the light source in the transmittance spectrum in the visible light wavelength range, and the integral value of the light source in the visible light wavelength range, respectively. Finally, the selective transmittance (value A / value B) is obtained. The selective transmittance is preferably greater than or equal to 50%, so that the green photosensitive resin composition can maintain high transparency after the low-temperature process.

[0178] (3) The difference in peak value of the transmission spectrum between the light source and the green photosensitive resin composition after being irradiated with the light source: For example, Figure 1 As shown in the example, the peak of the light source transmittance obtained by the transmission spectrum obtained in step (1) is 527nm, and the peak of the transmittance of the green photosensitive resin composition after irradiation with the light source is 529nm. The difference between the peak values ​​of the two is preferably within ±3nm, which conforms to the following formula 2:

[0179] λ-3nm≤λ1≤λ+3nm (Formula 2)

[0180] in

[0181] λ1: Peak value of the transmittance of the colorant (A) with the light source (nm)

[0182] λ: Peak value of the light source's penetration value (nm)

[0183] A peak value difference within ±3nm indicates that the color is not distorted.

[0184] [Production of color filters]

[0185] The green photosensitive resin compositions of Examples 1-10 and Comparative Examples 1-3 are coated on a glass substrate with a thickness of 0.4-0.7 mm (film thickness 2-3 um) by spin coating, and then the green photosensitive resin composition is pre-baked at 80-90° C. for 120 seconds using a heating plate, and then the green photosensitive resin composition is exposed using a light source with a wavelength of 365 nm by photolithography, and then developed using an alkaline developer of KOH. Finally, the produced pattern film is post-baked at 90° C. for 30-60 minutes for heat treatment, and after cooling, it is covered with an OCA light-sensitive transparent material by spin coating or lamination and cured using a light source with a wavelength of 365 nm to obtain a color filter containing the desired pattern.

[0186] [Light resistance test]

[0187] The manufactured color filter was placed in an exposure machine and irradiated with a light source of 365nm wavelength for 48 hours. The optical properties were measured before and after the light resistance test to judge the light resistance of the material. ab The light resistance evaluation is recorded in Table 1.

[0188] Use a colorimeter to locate the position of the colored pattern sheet before the NMP test, and measure the color value (L*, a*, b*) of the colored pattern sheet after it is immersed in the solvent. Define ΔE* according to the CIELAB color space ab , calculate the color difference ΔE* ab , the formula is as follows:

[0189]

[0190] L1*: Brightness before lightfastness test;

[0191] L2*: lightness after lightfastness test;

[0192] a1*, b1*: Chromaticity index before light fastness test;

[0193] a2*, b2*: Chromaticity index after light fastness test.

[0194] [evaluate]

[0195] In practical application, after being placed in an exposure machine for 48 hours for light resistance test, the color difference ΔE* can be measured according to Table 2. ab Evaluate its light fastness.

[0196] [Table 2]

[0197]

[0198] ◎: Best, color difference ΔE* before and after light fastness test ab Less than 3.

[0199] O: Better, color difference ΔE* before and after light fastness test ab In the range of 3 to 3.5.

[0200] Δ: Good, color difference ΔE* before and after light fastness test ab The range is greater than 3.5 and less than or equal to 5.

[0201] X: Poor, color difference ΔE* before and after light fastness test ab Greater than 5.

[0202] As can be seen from Table 1, Examples 1-10 select the composition of the blue colorant and the yellow colorant by selecting a transmittance (value A / value B) greater than or equal to 50%, so that the green photosensitive resin composition formed therefrom has a transmittance as good as that of the green photosensitive resin composition prepared by conventionally using the green colorant. Therefore, the green photosensitive resin composition prepared by conventionally using the green colorant can be substituted.

[0203] As can be seen from Table 1, Examples 1-10 adjust the composition of the blue colorant and the yellow colorant so that the difference between the peak value of the green photosensitive resin composition and the peak value of the light source 527nm falls within ±3nm, indicating that the color is not distorted, and therefore the color performance is good.

[0204] As can be seen from Table 1 and Table 2, in Examples 1-10, the blue colorant and the yellow colorant replace the traditional green colorant, so that the color difference (ΔE* ab ) is less than 5, and has good light resistance after low temperature process.

[0205] In contrast, it can be seen from Table 1 and Table 2 that although Comparative Examples 1-3 used blue colorants and yellow colorants, they also used traditional green colorants, which resulted in a color difference (ΔE*) of the color filters after the light resistance test. ab ) is greater than 5, and has poor light resistance after low temperature process.

[0206] It can be seen from Table 1 and Table 2 that Examples 1, 9, and 10 use the same blue colorant and yellow colorant, and the difference lies in the ratio of the blue colorant to the yellow colorant, which is 65:35, 50:50, and 35:65, respectively. The green photosensitive resin composition within the above ratio has a transmittance greater than or equal to 50%, and the peak value difference is within ±3. Moreover, the color filter made from the green photosensitive resin composition has a color difference value less than 5 after the light resistance test. In other words, it has good transmittance, color performance, and light resistance.

[0207] In summary, by selecting the composition of the blue colorant and the green colorant based on the selective transmittance, the green photosensitive resin composition and the color filter formed therefrom can have good transmittance, color expression, and light resistance.

[0208] Several embodiments are summarized above so that those with ordinary knowledge in the art to which the present invention belongs can better understand the concepts of the embodiments of the present invention. Those with ordinary knowledge in the art to which the present invention belongs should understand that they can design or modify other processes and structures based on the embodiments of the present invention to achieve the same purposes and / or advantages as the embodiments introduced herein. Those with ordinary knowledge in the art to which the present invention belongs should also understand that such equivalent processes and structures do not deviate from the spirit and scope of the present invention, and they can make various changes, substitutions and replacements without violating the spirit and scope of the present invention.

Claims

1. A green photosensitive resin composition comprising: (A) coloring agent; (B) alkali-soluble resin; (C) polymerizable unsaturated compounds; (D) a photopolymerization initiator; as well as (E) a solvent, The colorant (A) includes a blue colorant (A1) and a yellow colorant (A2), and the combination of the blue colorant (A1) and the yellow colorant (A2) meets the color selection penetration of ≥50%, wherein the blue colorant (A1) is CI Pigment Blue 16, CI Pigment Blue 15:6, or a combination thereof, and the yellow colorant (A2) is CI Pigment Yellow 185, CI Pigment Yellow 150, CI Pigment Yellow 139, CI Pigment Yellow 139E, or a combination thereof, wherein the color selection penetration is defined as: 2 . The green photosensitive resin composition as claimed in claim 1 , wherein the color selective transmittance of the green photosensitive resin composition is ≥55%. 3 . The green photosensitive resin composition as claimed in claim 2 , wherein the color selective transmittance of the green photosensitive resin composition is ≤85%.

4. The green photosensitive resin composition according to claim 1, wherein In the range of 20-35. 5 . The green photosensitive resin composition as claimed in claim 1 , wherein the wavelength of the blue colorant (A1) is 380-600 nm and the wavelength of the yellow colorant (A2) is 480-780 nm. 6 . The green photosensitive resin composition as claimed in claim 1 , wherein a weight ratio of the yellow colorant (A2) to the blue colorant (A1) is 35:65-65:

35.

7. The green photosensitive resin composition according to claim 1, wherein the color transmittance value of the colorant (A) satisfies the following formula: λ-3nm≦λ1≦λ+3nm (Formula 2) in λ1: The peak value of the transmittance of the colorant (A) when matched with the light source, in nm λ: The peak value of the light source's penetration value, in nm.

8. The green photosensitive resin composition according to claim 1, comprising: 10 to 45 wt% of the colorant (A); 5 to 30 wt% of the alkali-soluble resin (B); 1 to 30 wt% of the polymerizable unsaturated compound (C); 0.1 to 2.5 wt% of the photopolymerization initiator (D); and 35 to 80 wt% of the solvent (E). 9 . The green photosensitive resin composition as claimed in claim 8 , further comprising 0.05-0.1 wt % of an additive (F). 10 . The green photosensitive resin composition as claimed in claim 9 , wherein the additive (F) is an antioxidant.

11. The green photosensitive resin composition as claimed in claim 1, wherein the colorant (A) comprises a pigment, a dye, or a combination thereof; and / or the monomer of the alkali-soluble resin (B) comprises methyl methacrylate, methacrylic acid, tricyclodecyl methacrylate, glycidyl methacrylate, benzyl methacrylate, N-benzylmaleimide, or a combination thereof.

12. A color filter formed from the green photosensitive resin composition according to any one of claims 1 to 11.

13. The color filter as claimed in claim 12, wherein the color difference of the color filter is ΔE* ab <5.

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