Low-temperature colored photosensitive resin composition, colored coating, color filter and image display device

Abstract

The invention relates to the technical field of colored photosensitive resin compositions, in particular to a low-temperature colored photosensitive resin composition, a colored coating, a color filter and an image display device. The low-temperature colored photosensitive resin composition includes a colorant mixture, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Wherein the binder resin is composed of a first binder resin and a second binder resin, and the first binder resin comprises an unsaturated carboxylic acid glycidyl ester compound; the second binder resin comprises an isocyanate compound and an unsaturated carboxylic acid glycidyl ester compound; the weight ratio of the first binder resin to the second binder resin is (9-7): (1-3). Pattern loss or damage caused by a solvent when the color filter is prepared by a low-temperature process can be effectively reduced, and the characteristics of the color filter can be fully exerted; meanwhile, the roughness of the surface of the color filter is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of colored photosensitive resin compositions, and in particular to a low-temperature colored photosensitive resin composition, a colored coating, a color filter, and an image display device. Background Art

[0002] Color filters can be placed on top of liquid crystal display (LCD) devices or white organic light-emitting diode (White-OLED) display devices to achieve the desired color for each pixel. The color filter can include a black matrix and coloring patterns corresponding to RGB pixels.

[0003] In order to reduce external light reflection, a polarizing plate or an anti-reflection plate is provided on the display panel of the LCD device. However, since the polarizing plate and the anti-reflection plate have relatively rigid characteristics, the overall flexibility of the display device may be reduced. In recent years, with the gradual commercialization of foldable or bendable flexible display devices, the use of optical components with poor flexibility, such as polarizing plates or anti-reflection plates, may be reduced. However, if the use of the above-mentioned optical components is reduced, the image contrast and visibility may be reduced due to external light reflection. Therefore, a colored photosensitive resin composition can be used. In this case, the color filter can achieve sufficient anti-reflection properties. Even if the use of the above-mentioned optical components is reduced, the flexibility of the display device can be improved while ensuring image quality.

[0004] However, when color filters are produced using a low-temperature process using a colored photosensitive resin composition in the prior art, the solvents used in subsequent processes can cause pattern loss or damage, resulting in a loss of the color filter's proper properties. Furthermore, when color filters are produced using the prior art colored photosensitive resin composition, the surface roughness of the color filters is excessive, making them difficult to use.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The present invention aims to provide a low-temperature coloring photosensitive resin composition, a coloring coating, a color filter, and an image display device. The low-temperature coloring photosensitive resin composition provided in embodiments of the present invention not only effectively reduces pattern loss or damage caused by solvents during low-temperature color filter production, fully utilizing the color filter's properties, but also improves the surface roughness of the color filter.

[0007] The present invention is achieved in that: In a first aspect, the present invention provides a low-temperature coloring photosensitive resin composition comprising the following components: (A) Colorant mixture; (B) a binder resin, the binder resin comprising a first binder resin and a second binder resin, the first binder resin comprising an unsaturated carboxylic acid glycidyl ester compound; the second binder resin comprising an isocyanate compound and an unsaturated carboxylic acid glycidyl ester compound; the weight ratio of the first binder resin to the second binder resin being (9-7):(1-3); (C) a photopolymerizable compound; (D) photopolymerization initiator; (E) Solvent.

[0008] In an optional embodiment, the isocyanate compound in the second binder resin is selected from at least one of the compounds described in the following formulas 1-1 to 1-5: Formula 1-1; Formula 1-2; Formula 1-3; Formula 1-4; Formula 1-5.

[0009] In an optional embodiment, the first binder resin further comprises at least one or more than two selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid ester compounds and maleimide compounds; The second binder resin further comprises at least one or more than two selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, and maleimide compounds.

[0010] In an alternative embodiment, the binder resin has a weight average molecular weight of 3,000 to 200,000, preferably 15,000 to 150,000.

[0011] In an optional embodiment, the amount of the colorant mixture is 10-40 parts, preferably 20-40 parts, based on 100 parts by weight of the low-temperature coloring photosensitive resin composition; Preferably, the amount of the binder resin is 1-40 parts; preferably 1-30 parts, more preferably 5-30 parts; Preferably, the amount of the photopolymerizable compound is 1-30 parts, preferably 1-20 parts, more preferably 2-10 parts; Preferably, the amount of the photopolymerization initiator is 0.1-8 parts, preferably 0.3-5 parts; Preferably, the amount of the solvent is 40-80 parts, preferably 40-70 parts.

[0012] In an optional embodiment, the low-temperature coloring photosensitive resin composition further comprises one or more additives selected from the group consisting of a polymer compound, a curing agent, a surfactant, an adhesion enhancer, an antioxidant, an ultraviolet absorber, and an anti-agglomeration agent.

[0013] In an optional embodiment, based on 100 parts by weight of the low-temperature coloring photosensitive resin composition, the amount of the additive is 0.01-10 parts, preferably 0.05-2 parts.

[0014] In a second aspect, the present invention provides a colored coating, which is prepared using the low-temperature colored photosensitive resin composition described in the aforementioned embodiment.

[0015] In a third aspect, the present invention provides a color filter comprising the colored coating described in the aforementioned embodiment.

[0016] In a fourth aspect, an embodiment of the present invention provides an image display device, which includes the color filter described in the above embodiment.

[0017] The present invention has the following beneficial effects: The low-temperature coloring photosensitive resin composition provided by the present invention alleviates the problems of pattern detachment and surface roughness during low-temperature color filter production. The resulting color filter exhibits excellent surface roughness under low-temperature curing conditions while also meeting solvent resistance requirements. When the surface roughness meets these standards, the target chromaticity is achieved while maintaining stable light transmittance, significantly improving the visual recognition of the color filter. DETAILED DESCRIPTION

[0018] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0019] In a first aspect, embodiments of the present invention provide a low-temperature coloring photosensitive resin composition comprising a colorant mixture, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Specifically, the components of the low-temperature coloring photosensitive resin composition are selected as follows: (A) Colorant mixture In the embodiment of the present invention, the pixel colors presented by the colored pattern of the color filter formed by the low-temperature colored photosensitive resin composition include the following colorant mixture.

[0020] In the embodiment of the present invention, the low-temperature coloring photosensitive resin composition for forming a color filter showing red pixels includes a red colorant mixture, which may include two or more red colorants, a yellow colorant, and a green colorant.

[0021] It should be noted that in order to distinguish the names of the low-temperature coloring photosensitive resin compositions for color filters that present pixels of different colors, the names of the low-temperature coloring photosensitive resin compositions are adaptively adjusted according to the colors presented. For example, a low-temperature coloring photosensitive resin composition that forms a color filter that presents red pixels is also referred to as a red pixel composition.

[0022] Specifically, the red colorant mixture included in the red pixel composition may include a mixture of CIpigment Red 177 and CIpigment Red 254. The weight ratio of CIpigment Red 177 to CIpigment Red 254 is (0.25 to 0.6):1, preferably (0.40 to 0.55):1, and more preferably (0.50 to 0.55):1.

[0023] Furthermore, the weight ratio of the red colorant to the yellow colorant in the red colorant mixture is (0.1 to 0.3):1, preferably (0.1 to 0.25):1, and more preferably (0.1 to 0.2):1.

[0024] The weight ratio of the red colorant to the green colorant in the red colorant mixture is (0.05 to 0.2):1, preferably (0.05 to 0.15):1, and more preferably (0.05 to 0.1):1.

[0025] Furthermore, when the low-temperature coloring photosensitive resin composition is used as a color filter for forming green pixels, that is, a green pixel composition, it comprises a green colorant mixture, and the green colorant mixture may include a green colorant, a yellow colorant, and a blue colorant.

[0026] Further, the green colorant included in the green colorant mixture is CIpigment Green 58; the yellow colorant included may include CIpigment Yellow 185 and CIpigment Yellow 139; and the blue colorant included may include CIpigment Blue 16.

[0027] Furthermore, the weight ratio of the green colorant to the yellow colorant in the green colorant mixture is (1.0 to 5.5):1, preferably (1.5 to 5.0):1, and more preferably (2.0 to 4.5):1.

[0028] Furthermore, the weight ratio of the green colorant to the blue colorant in the green colorant mixture may be (1.0 to 2.0):1, preferably (1.0 to 1.7):1, and more preferably (1.1 to 1.5):1.

[0029] Furthermore, when the low-temperature coloring photosensitive resin composition is used as a color filter for forming blue pixels, that is, a blue pixel composition, it contains a blue colorant mixture, and the blue colorant mixture may include a blue colorant, a purple colorant, and a green colorant.

[0030] The blue colorant included in the blue colorant mixture may include CIpigment Blue 16 and / or CIpigment Blue 15:6, preferably CIpigment Blue 16; the violet colorant included may include CIpigment Violet 23. Specifically, the weight ratio of the purple colorant to the blue colorant in the blue colorant mixture may be (0.1 to 0.5):1, preferably (0.1 to 0.4):1, and more preferably (0.2 to 0.7):1.

[0031] The colorant mixture may further include additional pigments or dyes within a range that does not affect the coloring characteristics according to the color and the refractive index and absorption coefficient characteristics of the pixel or the coloring pattern described below.

[0032] Specifically, the pigments include but are not limited to the following colorants: CI Pigment Yellow 1, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83,86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154,166, 173, 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64,65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 180,192, 215, 216, 224, 242, 264, 265; CI Pigment Blue 15, 16, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 29, 32, 36, 38; CI Pigment Green 7, 36, 58, 59; CI Pigment Brown 23, 25. The dyes include but are not limited to the following colorants: CI Solvent Yellow 2, 14, 16, 33, 34, 44, 56, 82, 93, 94, 98, 116,135; CI Solvent Orange 1, 3, 7, 63; CI Solvent Red 1, 2, 3, 8, 18, 23, 24, 27, 35, 43, 45, 48, 49, 91:1, 119, 135, 140, 196, 197; CI Solvent Violet 8, 9, 13, 26, 28, 31, 59; CI Solvent Blue 4, 5, 25, 35, 36, 38, 70; CI Solvent Green 3, 5, 7.

[0033] Furthermore, the colorant mixture can be used in the form of a colorant dispersion. For example, the colorant mixture can be used after being dispersed in the form of a color paste in a pigment dispersant and a pigment solvent.

[0034] Specifically, the pigment dispersant in the embodiment of the present invention includes, for example, cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants.

[0035] Furthermore, the pigment dispersant content can be about 10% to 50% by weight of the total solid content of the colorant mixture. Within this range, excessive viscosity increases can be suppressed, and problems such as pigment aggregation and composition gelation can be prevented.

[0036] Furthermore, based on 100 parts by weight of the low-temperature coloring photosensitive resin composition, the amount of the colorant mixture is 10-40 parts, preferably 20-40 parts. Within this range, degradation of pattern characteristics can be prevented while providing improved coloring / brightness characteristics.

[0037] (B) binder resin; The binder resin provided by the embodiment of the present invention provides mechanical durability and pattern forming properties of the colored coating. The binder resin can provide a matrix for the colored coating and provide photosensitivity.

[0038] Specifically, the binder resin includes a first binder resin, and the first binder resin includes at least one or more than two selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid glycidyl ester compounds, and maleimide compounds.

[0039] The binder resin includes a second binder resin, which must contain an isocyanate compound. The second binder resin also includes at least one or more of the group consisting of an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid glycidyl ester compound, and a maleimide compound.

[0040] The weight ratio of the first binder resin to the second binder resin is (9-7):(1-3); for example, any value between (9-7):(1-3) such as 9:1, 8:2, and 7:3.

[0041] The isocyanate compound is selected from at least one of the compounds described in the following formulas 1-1 to 1-5: Formula 1-1; Formula 1-2; Formula 1-3; Formula 1-4; Formula 1-5.

[0042] Furthermore, the binder may include a copolymer formed by an alkali-soluble carboxyl-containing monomer and a reactive monomer copolymerizable with the carboxyl-containing monomer.

[0043] Specifically, the carboxyl group-containing monomer may include an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid. For example, the carboxyl group-containing monomer may be selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. These monomers may be used alone or in combination of two or more.

[0044] Specifically, the reactive monomers provided in the embodiments of the present invention include, but are not limited to, aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene.

[0045] Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, 2-methoxy Unsaturated carboxylic acid ester compounds such as ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, isobornyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol mono(meth)acrylate, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate.

[0046] Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 2-dimethylaminopropyl (meth)acrylate, 3-aminopropyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate and glycidyl methacrylate. Carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amide compounds such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; maleimide compounds such as N-benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0047] Isocyanate compounds such as 2-isocyanateethyl(meth)acrylate, 2-(2-isocyanateethoxy)ethyl(meth)acrylate, 2-[(3,5-dimethylpyrazolyl)formamido]ethyl(meth)acrylate, and 2-(O-[1'-methylpropyleneamino]formamido)ethyl(meth)acrylate.

[0048] These compounds may be used alone or in combination of two or more.

[0049] In the embodiments of the present invention, the term "(meth)acryloyl-" is used to collectively refer to groups having "methacryloyl-", "acryloyl-" or both. The acid value of the adhesive resin provided in the embodiment of the present invention can be appropriately adjusted according to the resolution requirement of the development process. For example, the acid value of the adhesive resin can be 20 to 200 KOH mg / g, preferably 50 to 150 KOH mg / g. Within the above range, the solubility of the adhesive resin in the developer can be improved, and the sensitivity of the exposure process can also be improved. In the embodiments of the present invention, the term "acid value" refers to the amount (mg) of potassium hydroxide required to neutralize 1 gram of polymer. The weight average molecular weight (Mw) of the adhesive resin provided in the embodiment of the present invention is about 3,000 to 200,000, preferably about 5,000 to 150,000. Within the above molecular weight range, the binder resin can ensure mechanical stability and development characteristics of the colored pattern.

[0050] Furthermore, the binder resin is used in an amount of 1-40 parts, preferably 1-30 parts, and more preferably 5-30 parts, per 100 parts by weight of the low-temperature coloring photosensitive resin composition. Within this range, pattern stability and developer solubility can be ensured while improving resolution and residual film properties.

[0051] (C) a photopolymerizable compound; The photopolymerizable compound provided in the embodiments of the present invention is a compound that can be polymerized under the action of light and a photopolymerization initiator described below, and examples thereof include monofunctional monomers, difunctional monomers, and other multifunctional monomers.

[0052] Specifically, the monofunctional monomer includes, but is not limited to, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. The bifunctional monomers include, but are not limited to, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A bis(acryloyloxyethyl) ether, and 3-methylpentanediol di(meth)acrylate. The multifunctional monomers include, but are not limited to, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Among them, tetrafunctional and higher multifunctional monomers are more preferably used.

[0053] Furthermore, the photopolymerizable compounds provided by embodiments of the present invention can improve the developability, sensitivity, adhesion, and surface defects of photosensitive resin compositions used to form light-shielding layers on the front surfaces of display devices by mixing two or more photopolymerizable compounds having different functional group structures or functional group quantities. The type of such compounds is not particularly limited and any type commonly used in the art can be used.

[0054] Furthermore, the amount of the photopolymerizable compound used is 1-30 parts, preferably 1-20 parts, and more preferably 2-10 parts, per 100 parts by weight of the low-temperature colorable photosensitive resin composition. Within this range, ideal pixel-level strength and surface smoothness can be achieved. If the photopolymerizable compound content is below this range, pixel-level strength may decrease; if it exceeds this range, surface smoothness may be affected. Therefore, it is preferably controlled within the above range.

[0055] (D) photopolymerization initiator; The photopolymerization initiator provided in the embodiments of the present invention is not particularly limited in type as long as it can polymerize the (C) photopolymerizable compound by exposure to radiation such as visible light, ultraviolet light, extreme ultraviolet light, electron beams, and X-rays.

[0056] Furthermore, the photopolymerization initiator may include, but is not limited to, acetophenone initiators, benzophenone initiators, benzoin initiators, thioxanthone initiators, triazine initiators, oxime ester initiators, and the like.

[0057] Specifically, acetophenone initiators include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane-1-one, etc.

[0058] Benzophenone initiators include, but are not limited to, benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone. Benzoin initiators include, but are not limited to, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Thioxanthone initiators include, but are not limited to, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Triazine initiators include, but are not limited to, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. Oxime ester initiators include, but are not limited to, O-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one, and commercially available products thereof include OXE-01 and OXE-02 from BASF.

[0059] Furthermore, in order to improve the sensitivity of the low-temperature colored photosensitive resin composition according to the embodiment of the present invention, the photopolymerization initiator may further contain a photopolymerization initiation auxiliary.

[0060] Specifically, photopolymerization initiator aids include amine-based initiators and alkoxyanthracene-based photopolymerization initiator aids. The amount of photopolymerization initiator used is 0.1 to 8 parts, preferably 0.3 to 5 parts, per 100 parts by weight of the low-temperature coloring photosensitive resin composition. Within this range, the curability of the colored pattern is improved, while preventing pattern loss during the development process and avoiding wrinkles caused by excessive cross-linking reactions.

[0061] (E) solvent; The solvent provided in the embodiment of the present invention is an organic solvent that can dissolve the adhesive resin and provide coating performance for the colored photosensitive resin composition.

[0062] Specifically, the solvent includes ether solvents, acetate solvents, aromatic hydrocarbon solvents, ketone solvents, alcohol solvents and ester solvents.

[0063] The above-mentioned ether solvents include, but are not limited to, ethylene glycol monoalkyl ether compounds, diethylene glycol dialkyl ether compounds, and propylene glycol monomethyl ether.

[0064] The above-mentioned acetate solvents include but are not limited to methyl cellosolve acetate, ethyl cellosolve acetate, alkyl acetates, alkoxyalkyl acetates, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol methyl ether acetate, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, dipropylene glycol methyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monoalkyl ether acetates, propylene glycol monoacetate, propylene glycol diacetate and propylene glycol monoalkyl ether acetates, etc.

[0065] The above aromatic hydrocarbon solvents include but are not limited to benzene, toluene, xylene and mesitylene. The ketone solvents include but are not limited to methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone (MIBK) and cyclohexanone. The above-mentioned alcohol solvents include but are not limited to ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol and 4-hydroxy-4-methyl-2-pentanone.

[0066] The amount of solvent used can be adjusted appropriately based on the sufficient solubility of the adhesive resin and the coating properties of the composition, and may be included as the balance component of the colored photosensitive resin composition. The "balance" described in the embodiments of the present invention is an open-ended expression, meaning a variable quantity that can be adjusted based on the added ingredients and additives.

[0067] For example, based on 100 parts by weight of the low-temperature coloring photosensitive resin composition, the amount of solvent used is 40-80 parts, preferably 40-70 parts.

[0068] (F) additives; The low-temperature coloring photosensitive resin composition provided by the embodiment of the present invention further includes one or more additives selected from the group consisting of a polymer compound, a curing agent, a surfactant, an adhesion enhancer, an antioxidant, an ultraviolet absorber, and an anti-agglomeration agent to improve coating properties or adhesion.

[0069] The polymer compound includes, but is not limited to, thermosetting resins such as epoxy resin and maleimide resin; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane.

[0070] Curing agents are used to achieve deep curing and improve mechanical strength, including but not limited to epoxy compounds, multifunctional isocyanate compounds, melamine compounds, and oxetane compounds.

[0071] The epoxy compounds in the above-mentioned curing agent include but are not limited to bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, and brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxide, isoprene (co)polymer epoxide, glycidyl (meth)acrylate (co)polymer and triglycidyl isocyanurate, etc.

[0072] The oxetane compound in the above curing agent includes but is not limited to carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane and cyclohexanedicarboxylic acid bisoxetane.

[0073] The above-mentioned curing agent can be used in combination with a curing aid that undergoes a ring-opening polymerization reaction between the epoxy group of the epoxy compound and the oxetane backbone of the oxetane compound. Such curing aids include, but are not limited to, polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators. Among these, commercially available epoxy resin curing agents can be used as polycarboxylic acid anhydrides. Specific examples include "Adeka Hardener EH-700" (manufactured by ADEKA Co., Ltd.), "Rikacid HH" (manufactured by Shin Nippon Rika Co., Ltd.), and "MH-700" (manufactured by Shin Nippon Rika Co., Ltd.). These curing agents can be used alone or as a mixture of two or more.

[0074] The above-mentioned surfactants can be used to further improve the film-forming properties of the low-temperature coloring photosensitive resin composition. For example, silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric surfactants can be used, among which silicone surfactants or fluorine surfactants are preferred.

[0075] The above-mentioned silicone surfactants include but are not limited to commercially available products: DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 of Dow Corning Toray Silicone; TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 of GE Toshiba Silicones.

[0076] The above-mentioned fluorine-based surfactant low-temperature coloring photosensitive resin composition includes Megafac F554, F-470, F-471, F-475, F-482 and F-489 from Dainippon Ink & Chemicals Co., Ltd. (DIC); BM-1000 and BM-1100 from BM Chemie; and Fluorad FC-135, FC-170C, and FC-430 from Sumitomo 3M. The above-mentioned surfactants also include: polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc.; commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoei Chemical Co., Ltd.), Ftergent (Tochem Products), Megafac (Dainippon Ink and Chemicals Co., Ltd.), Fluorad (Sumitomo 3M Co., Ltd.), Asahiguard, Saffron (Asahi Glass Co., Ltd., Solsperse (Lubrizol Corporation), EFKA (EFKA Chemicals Co., Ltd.), PB821 (Ajinomoto Co., Ltd.), etc.

[0077] The surfactants exemplified above may be used alone or in combination of two or more.

[0078] The adhesion enhancer is an additive used to improve coating and adhesion to the substrate, and may include a silane coupling agent having a reactive substituent selected from carboxyl, methacryloyl, isocyanate, epoxy, and combinations thereof. Silane coupling agents include, but are not limited to, 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-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethoxysilyl benzoate, vinyltriacetoxysilane, and γ-isocyanatepropyltriethoxysilane.

[0079] The antioxidants include but are not limited to 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

[0080] The above-mentioned ultraviolet absorbers include, but are not limited to, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenones.

[0081] The anti-agglomeration agent includes but is not limited to sodium polyacrylate and the like.

[0082] Furthermore, based on 100 parts by weight of the low-temperature coloring photosensitive resin composition, the amount of the additive is 0.01-10 parts, preferably 0.05-2 parts.

[0083] The present invention also provides a method for preparing the low-temperature coloring photosensitive resin composition, comprising: dissolving the colorant mixture in a solvent to prepare a coloring solution; and then adding the adhesive resin, the photopolymerizable compound, and the photopolymerization initiator to the coloring solution to prepare the low-temperature coloring photosensitive resin composition according to the present invention.

[0084] Alternatively, the colorant mixture may be dissolved or dispersed in the above solvent. In an embodiment, the coloring solution may be prepared more conveniently by adding the above pigment dispersant.

[0085] The colorant mixture is dissolved in a first solution in the solvent; the adhesive resin, the photopolymerizable compound, and the photopolymerization initiator are mixed in a second solution in the solvent. The first solution and the second solution are then mixed to prepare the low-temperature coloring photosensitive resin composition.

[0086] <Coloring Coating, Color Filter, and Image Display Device> The embodiments of the present invention also provide a colored coating prepared using the low-temperature colored photosensitive resin composition, and a color filter containing the colored coating.

[0087] For example, the low-temperature coloring photosensitive resin composition of the above-described embodiments is applied to a glass substrate or a semiconductor substrate such as a silicon wafer to form a colored coating. For example, the composition can be applied to the substrate by spin coating, slit coating, or inkjet printing, followed by a pre-bake or soft-bake process to form the colored coating. Subsequently, the colored coating is patterned by exposure and development processes to form a colored pattern. A color filter containing the colored pattern can thus be prepared. The colored coating can be selectively exposed using a photomask and a light source (such as a g-line or i-line). Subsequently, a development process is performed to remove the unexposed portions of the colored coating to form a colored pattern. To enhance the mechanical stability of the colored pattern, a post-exposure baking (PEB) process can also be performed.

[0088] The low-temperature coloring photosensitive resin composition can be provided as a curable low-temperature curing composition by passing through PEB at a temperature of 100° C. or lower.

[0089] As a developer for the development process, an aqueous solution of an alkaline compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide (TMAH) can be used.

[0090] Colored patterns can be formed independently corresponding to the three colors of RGB to prepare a color filter. In an embodiment, the red pattern in the above colored patterns corresponds to the red pixels of the image display device, and a black matrix can be provided between adjacent colored patterns.

[0091] The color filter in the embodiment of the present invention may include a red pixel pattern formed by the low-temperature coloring photosensitive resin composition containing the red colorant mixture. In the embodiment of the present invention, the red pixel pattern has a reflectivity of less than 2.0 at a wavelength of 620 nm, the green pixel pattern has a reflectivity of less than 3.0 at a wavelength of 520 nm, and the blue pixel pattern has a reflectivity of less than 1.7 at a wavelength of 450 nm.

[0092] As described above, by adjusting the mixing ratio and content of the colorant according to the pixel color, the reflectivity of the colored pattern can be reduced. This allows the color filter to achieve coloring characteristics while also suppressing external light reflection. Therefore, in a liquid crystal display (LCD) device, even if the upper polarizer and / or anti-reflection plate provided on the liquid crystal panel is omitted, sufficient image presentation effect and anti-reflection characteristics can still be provided by using the above-mentioned color filter.

[0093] Furthermore, by omitting the upper polarizer and / or anti-reflection plate, the flexibility of the image display device can be further improved, thereby making it easier to realize an image display device with high foldable, bendable, and rollable properties. An embodiment of the present invention provides an image display device including the color filter. The image display device includes the color filter disposed on a display panel.

[0094] In an embodiment of the present invention, the display panel may be a liquid crystal display (LCD) device panel. In this case, a backlight module may be provided below the display panel. In another embodiment, the display panel may be a white organic light emitting diode (W-OLED) panel. In some embodiments, the low-temperature coloring photosensitive resin composition can also be used as a color filter of a solid-state imaging device, such as a CMOS image sensor (CIS).

[0095] The features and performance of the present invention are further described in detail below with reference to the embodiments.

[0096] Pigment Synthesis Examples 1-8 Pigment Synthesis Examples 1-8 provide methods for preparing pigments, as follows: Pigment Synthesis Example 1: Preparation of Red Pigment Dispersion (A-1(R1)) 13.0 wt.% CIpigment Red 177 as a red pigment, 6.0 wt.% LPN-6919 (manufactured by BYK) as a pigment dispersant, 8.0 wt.% 4-hydroxy-4-methyl-2-pentanone, and 73.0 wt.% propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed in a bead mill for 12 hours to prepare a red pigment dispersion A-1 (R1). Pigment Synthesis Example 2: Preparation of Red Pigment Dispersion (A-2(R2)) 13.0 weight percent of CIpigment Red 179 as a red pigment, 6.0 weight percent of LPN-6919 (manufactured by BYK) as a pigment dispersant, 8.0 weight percent of 4-hydroxy-4-methyl-2-pentanone, and 73.0 weight percent of propylene glycol monomethyl ether acetate as solvents were mixed and dispersed in a bead mill for 12 hours to prepare a red pigment dispersion A-2 (R2). Pigment Synthesis Example 3: Preparation of Green Pigment Dispersion (A-3(G)) 13.0 wt. of CIpigment Green 7 as a green pigment, 6.0 wt. of LPN-6919 (BYK) pigment dispersant, 8.0 wt. of 4-hydroxy-4-methyl-2-pentanone, and 73.0 wt. of propylene glycol monomethyl ether acetate as a solvent were ground and dispersed in a bead mill for 12 hours to prepare a green pigment dispersion A-3(G).

[0097] Pigment Synthesis Example 4: Preparation of Blue Pigment Dispersion (A-4(B1)) 13.0 wt. of CIpigment Blue 16 was used as a blue pigment, 6.0 wt. of LPN-6919 (BYK) was used as a dispersant, 8.0 wt. of 4-hydroxy-4-methyl-2-pentanone, and 73.0 wt. of propylene glycol monomethyl ether acetate were used as solvents. The mixture was dispersed in a bead mill for 12 hours to prepare a blue pigment dispersion A-4 (B1).

[0098] Pigment Synthesis Example 5: Preparation of Blue Pigment Dispersion (A-5(B2)) 13.0 wt. of CIpigment Blue 15:6 was used as a blue pigment, 6.0 wt. of LPN-6919 (BYK) was used as a dispersant, 8.0 wt. of 4-hydroxy-4-methyl-2-pentanone, and 73.0 wt. of propylene glycol monomethyl ether acetate were used as solvents. The mixture was dispersed in a bead mill for 12 hours to obtain a blue pigment dispersion A-5 (B2). Pigment Synthesis Example 6: Preparation of Purple Pigment Dispersion (A-6(V)) 13.0 wt.% CIpigment Violet 23 as a violet pigment, 6.0 wt.% LPN-6919 (manufactured by BYK) as a dispersant, 8.0 wt.% 4-hydroxy-4-methyl-2-pentanone, and 73.0 wt.% propylene glycol monomethyl ether acetate as a solvent were ground and dispersed in a bead mill for 12 hours to prepare a violet pigment dispersion A-6(V).

[0099] Pigment Synthesis Example 7: Preparation of Yellow Pigment Dispersion (A-7(Y1)) 13.0 wt.% CIpigment Yellow 185 as a yellow pigment, 6.0 wt.% LPN-6919 (manufactured by BYK) as a dispersant, 8.0 wt.% 4-hydroxy-4-methyl-2-pentanone, and 73.0 wt.% propylene glycol monomethyl ether acetate as a solvent were ground and dispersed in a bead mill for 12 hours to prepare a yellow pigment dispersion A-7 (Y1).

[0100] Pigment Synthesis Example 8: Preparation of Yellow Pigment Dispersion (A-8(Y2)) 13.0 wt.% CIpigment Yellow 139 as a yellow pigment, 6.0 wt.% LPN-6919 (BYK) as a dispersant, 8.0 wt.% 4-hydroxy-4-methyl-2-pentanone, and 73.0 wt.% propylene glycol monomethyl ether acetate as a solvent were ground and dispersed in a bead mill for 12 hours to prepare a yellow pigment dispersion A-8(Y2) having a particle size distribution D90 ≤ 200 nm.

[0101] Binder resin synthesis example 1-2 Binder Resin Synthesis Examples 1-2 provide a method for synthesizing a binder resin, as follows: Binder Resin Synthesis Example 1: Preparation of the First Binder Resin (denoted as B1) To a reactor equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet, 100 weight percent propylene glycol monomethyl ether acetate, 100 weight percent propylene glycol monomethyl ether, 5 weight percent AIBN, 15 weight percent vinyltoluene, 20 weight percent 2-phenylthioethyl acrylate, 10 weight percent methacrylate, and 30 weight percent methacrylic acid were added in sequence. A nitrogen atmosphere was established. The reaction system was heated to 80°C with continuous stirring and allowed to react for 6 hours.

[0102] After adding 15 wt% of glycidyl methacrylate to the resultant, the temperature was raised to 110° C. and the reaction was carried out for 4 hours to finally obtain an adhesive resin with a solid content of 32.5 wt%.

[0103] The solid content and acid value of the synthesized binder resin were 68.3 mgKOH / g, and the weight average molecular weight (Mw) was about 13,950 as measured by GPC.

[0104] Binder Resin Synthesis Example 2: Preparation of the Second Binder Resin (denoted as B2) To a reactor equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet, 100 weight percent propylene glycol monomethyl ether acetate, 100 weight percent propylene glycol monomethyl ether, 5 weight percent AIBN, 15 weight percent vinyltoluene, 10 weight percent 2-(O-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 25 weight percent methacrylate, and 25 weight percent methacrylic acid were added in sequence. A nitrogen atmosphere was established. The reaction system was heated to 80°C with continuous stirring and allowed to react for 6 hours.

[0105] After adding 15 wt% of glycidyl methacrylate to the resultant, the temperature was raised to 110° C. and the mixture was reacted for 4 hours to finally obtain a binder resin with a solid content of 29.9 wt%.

[0106] The solid content and acid value of the synthesized binder resin were 35.7 mgKOH / g, and the weight average molecular weight (Mw) was about 11,050 as measured by GPC.

[0107] Examples 1-3 and Comparative Examples 1-8 Examples 1-3 and Comparative Examples 1-8 each provide a low-temperature coloring photosensitive resin composition, the composition of which is shown in Table 1. The colorant dispersion and binder resin in Table 1 are selected from the pigment synthesis examples and binder resin synthesis examples described above. The values ​​in Table 1 are in weight percent.

[0108] Table 1 Composition of low-temperature coloring photosensitive resin composition

[0109] The specific components used in Table 1 are as follows. (C): KAYARAD DPHA (manufactured by Nippon Shinmoto Chemical Co., Ltd.) (D): Compounds of the following chemical formula

[0110] (E-1): Megaface EFS-801, manufactured by Dainippon Ink & Chemicals Co., Ltd. (DIC Corporation) (E-2): γ-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) (F-1): PGDA (propylene glycol diacetate) (F-2): PGMEA (propylene glycol monomethyl ether acetate) Experimental example Preparation of color filters: The low-temperature coloring photosensitive resin composition of each embodiment and comparative example was applied to the surface of a 5 cm × 5 cm glass substrate (EAGLE XG, manufactured by Corning Incorporated) by spin coating, and then kept on a 90°C hot plate for 2 minutes to form a coloring layer.

[0111] A test photomask with a line / space pattern of 5 μm to 50 μm was placed on the film, and the distance between the test photomask and the film was set to 100 μm before irradiation with ultraviolet light. The ultraviolet light source used was a 1kW high-pressure mercury lamp that includes g-line, h-line, and i-line, with a power of 100 mJ / cm 2 The illumination was carried out with an intensity of 100 nm and no special optical filters were used.

[0112] After UV irradiation, the colored layer was immersed in a KOH aqueous solution (pH 10.5) for 2 minutes. The glass substrate was then rinsed with distilled water, dried with nitrogen, and baked in a 90°C oven for 60 minutes to produce a color filter with a colored pattern. The resulting colored pattern had a thickness of 2.5 μm.

[0113] Solvent resistance evaluation Color filters prepared from the compositions described in the Examples and Comparative Examples were immersed in a PGMEA solvent at 23°C for 10 minutes, and the color difference before and after evaluation was compared. Specifically, the color difference change was calculated using the following mathematical formula (1) in a three-dimensional colorimetric system defined by L*, a*, and b*. A smaller value indicates a more reliable color filter.

[0114] When the △E*ab value is ≤3.0, it is determined to be within the range of color difference that is imperceptible to the human eye. △E*ab =[(△L*)^2+ (△a*)^2+(△b*)^2](1 / 2) Surface roughness evaluation The surface roughness of the color filters prepared from the compositions of the above examples and comparative examples was measured using atomic force microscopy (AFM). A surface roughness (Ra) of 3.0 Å was used as the standard: values ​​≥ 3.0 Å were considered "good" and values ​​< 3.0 Å were considered "good." The results are shown in Table 2.

[0115] Table 2 Test results

[0116] As shown in Table 2, color filters prepared using the colored photosensitive resin compositions described in Examples 1 to 3 of the present invention exhibit excellent surface roughness under low-temperature curing conditions while also meeting solvent resistance requirements. When these surface roughness standards are met, the target chromaticity is achieved while maintaining stable transmittance, significantly improving the visual recognition of the color filter.

[0117] As shown in Table 2, although Comparative Examples 1, 3, and 5, which have insufficient second binder content, meet the surface roughness requirements, they exhibit significant color difference after the solvent resistance test.

[0118] As shown in Table 2, when the second binder content in Comparative Examples 2, 4, and 6 is too high, the surface roughness requirement is not met, resulting in the target process characteristics not being achieved.

[0119] As can be seen from Table 2, when the content of the photopolymerizable compound in Comparative Example 7 is too high and the content of the photoinitiator in Comparative Example 8 is too high, the surface roughness condition cannot be met, resulting in failure to achieve the expected process characteristics.

[0120] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A low-temperature coloring photosensitive resin composition, characterized in that It includes the following ingredients: (A) Colorant mixture; (B) a binder resin, the binder resin comprising a first binder resin and a second binder resin, the first binder resin comprising an unsaturated carboxylic acid glycidyl ester compound; the second binder resin comprising an isocyanate compound and an unsaturated carboxylic acid glycidyl ester compound; the weight ratio of the first binder resin to the second binder resin being (9-7):(1-3); (C) a photopolymerizable compound; (D) photopolymerization initiator; (E) Solvent.

2. The low-temperature coloring photosensitive resin composition according to claim 1, wherein The isocyanate compound in the second binder resin is selected from at least one of the compounds described in the following formulas 1-1 to 1-5: Formula 1-1; Formula 1-2; Formula 1-3; Formula 1-4; Formula 1-5.

3. The low-temperature coloring photosensitive resin composition according to claim 1, characterized in that The first binder resin further comprises at least one or more than two selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid ester compounds and maleimide compounds; The second binder resin further comprises at least one or more than two selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, and maleimide compounds.

4. The low-temperature coloring photosensitive resin composition according to any one of claims 1 to 3, characterized in that The weight average molecular weight of the binder resin is 3,000 to 200,000, preferably 15,000 to 150,000.

5. The low-temperature coloring photosensitive resin composition according to any one of claims 1 to 3, characterized in that The low-temperature coloring photosensitive resin composition is calculated as 100 parts by weight, and the amount of the colorant mixture is 10-40 parts; preferably 20-40 parts; Preferably, the amount of the binder resin is 1-40 parts; preferably 1-30 parts, more preferably 5-30 parts; Preferably, the amount of the photopolymerizable compound is 1-30 parts, preferably 1-20 parts, more preferably 2-10 parts; Preferably, the amount of the photopolymerization initiator is 0.1-8 parts, preferably 0.3-5 parts; Preferably, the amount of the solvent is 40-80 parts, preferably 40-70 parts.

6. The low-temperature coloring photosensitive resin composition according to any one of claims 1 to 3, characterized in that The low-temperature coloring photosensitive resin composition further includes one or more additives selected from the group consisting of a polymer compound, a curing agent, a surfactant, an adhesion enhancer, an antioxidant, an ultraviolet absorber, and an anti-agglomeration agent.

7. The low-temperature coloring photosensitive resin composition according to claim 6, characterized in that Based on 100 parts by weight of the low-temperature coloring photosensitive resin composition, the amount of the additive is 0.01-10 parts, preferably 0.05-2 parts.

8. A colored coating, characterized in that: The photosensitive resin composition is prepared by using the low-temperature coloring photosensitive resin composition according to any one of claims 1 to 7.

9. A color filter, characterized in that: It comprises the colored coating according to claim 8.

10. An image display device, characterized in that: It comprises the color filter according to claim 9.

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