A photosensitive resin composition and its application

Abstract

The present invention relates to a photosensitive resin composition and its application. The photosensitive resin composition includes an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and optionally a colorant, an auxiliary agent, and a solvent. The alkali-soluble resin has a structure shown in Formula I. In the photosensitive resin composition of the present invention, an alkali-soluble resin containing an unsaturated vinyl structure shown in Formula I is selected, so that crosslinking polymerization between resins is easier to form a network macromolecular chain during the exposure stage of the photosensitive resin composition, increasing the degree of polymerization at the bottom of the photoresist. Even during 100 s of development, there is no problem of undercutting, and it has good development latitude, excellent edge straightness, and very excellent film residue, and also has good heat resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of photocuring, and particularly relates to a photosensitive resin composition and its application. Background Art

[0002] A liquid crystal panel is a main component of a TFT-LCD, which is composed of a thin film transistor array substrate (Array Substrate) and a color filter substrate (Color Filter Substrate). The color filter substrate is a color filter composed of upper and lower substrates, a black matrix, and pixel regions of various colors such as red (R), green (G), and blue (B).

[0003] Generally, a color filter is manufactured by a lithography method. First, a black photosensitive resin composition is coated on a substrate, dried, and then exposed and developed to form a black matrix cathode ray tube. Then, for photosensitive resin compositions of various colors such as red, green, and blue, coating, drying, exposure, and development are repeatedly performed to form pixel regions of various colors at specific positions, thereby manufacturing a color filter.

[0004] The photosensitive resin composition undergoes free radical polymerization during the exposure stage. However, due to the certain thickness of the color film, good polymerization occurs at the top while insufficient polymerization occurs at the bottom. In the subsequent development process, the developer erodes the photoresist with poor polymerization at the bottom of the pattern, causing the pattern to be severely trapezoidal, and then resulting in an undercut problem.

[0005] Especially during mass production, due to changes in external temperature, developer concentration, etc., the developer often overly erodes the photoresist with poor polymerization at the bottom of the pattern, resulting in an undercut phenomenon. Therefore, it is necessary to improve the development latitude of the photosensitive resin composition so that there is no undercut problem even during 100 s of development to cope with changes in external temperature, developer concentration, etc.

[0006] CN106980230A discloses a photosensitive resin composition containing components such as a photopolymerizable compound and an oxime-based photoinitiator, which has good sensitivity, and can inhibit the formation of an undercut in the developed pattern even when the photosensitive resin composition contains a light-shielding agent or the exposure amount is insufficient, as well as a color filter and a display device using the photosensitive resin composition. However, there is still an undercut during 100 s of development.

[0007] CN1800885A discloses a radiation-sensitive composition for forming a colored layer, which contains a colorant, an alkali-soluble resin, a polyfunctional monomer or a combination thereof with a monofunctional monomer, and an O-acyloxime type photo radical generator. This composition can provide that there is no undissolved residue during development, no scum is generated at the image edge, and there are no pattern edge defects, undercuts, and black matrices even at low exposure levels. However, there are still undercuts during 100 s development, and the development latitude needs to be further improved.

[0008] Therefore, there is an urgent need in the art to develop a new type of photosensitive resin composition to solve the problem of undercuts and improve the development latitude. Summary of the Invention

[0009] Aiming at the deficiencies of the prior art, one of the purposes of the present invention is to provide a photosensitive resin composition, which can improve the degree of polymerization at the bottom of the color film, has no undercut problem even during 100 s development, and has good development latitude.

[0010] To achieve this purpose, the present invention adopts the following technical solutions:

[0011] The present invention provides a photosensitive resin composition, which includes an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator;

[0012] The alkali-soluble resin has the structure shown in Formula I;

[0013]

[0014] In Formula I, R1 and R2 each independently selected from -OH or acrylate group, and at least one of R1 and R2 is an acrylate group;

[0015] In Formula I, R3 is selected from any one of C1-C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, etc.) alkyl, C6-C30 (such as C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc.) aryl or carboxyl group;

[0016] In Formula I, R4 is selected from any one of -H, C1-C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, etc.) alkyl or C6-C30 (such as C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc.) aryl or a group formed by connecting any one or at least two of them;

[0017] In Formula I, R5 and R6 are each independently selected from -H or -CORCOOH, and at least one of R5 and R6 is -CORCOOH. R is selected from C1-C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, etc.) alkylene or C6-C30 (such as C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc.) arylene;

[0018] In Formula I, R7, R8 and R9 are each independently selected from -H or methyl;

[0019] In Formula I, (p + m) / (p + m + n + o) = 10-80%, such as 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, etc., n / (p + m + n + o) = 0-30%, such as 5%, 8%, 10%, 15%, 18%, 20%, 24%, 26%, 28%, etc., o / (p + m + n + o) = 0-20%, such as 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, etc.

[0020] In the photosensitive resin composition of the present invention, an alkali-soluble resin containing an unsaturated vinyl structure shown in Formula I is selected, so that the crosslinking polymerization between resins during the exposure stage is easier to form a network macromolecular chain, increasing the degree of polymerization at the bottom of the photoresist. Even when developing for 100 s, there is no problem of undercutting, and it has good developing latitude, excellent edge straightness and film residue, and good heat resistance.

[0021] Preferably, the alkali-soluble resin has the structure shown in Formula II;

[0022]

[0023] R1, R2, R3, R4, R7, R8, R9, p, m, n and o all have the same meanings as in Formula I.

[0024] Preferably in the present invention, one of R5 and R6 is -H and the other is -CORCOOH, which can improve the edge straightness of pixels while ensuring the alkali solubility of the resin.

[0025] Preferably, the alkali-soluble resin has the structure shown in Formula III;

[0026]

[0027] R1, R2, p, m, n and o all have the same meanings as in Formula I.

[0028] Preferably, p < m.

[0029] Preferably, the content of carboxyl groups in the alkali-soluble resin of the present invention is higher than the content of hydroxyl groups (i.e., p < m), so that excellent alkali solubility can be achieved, thereby ensuring the development rate.

[0030] Preferably, p / (p + m + n + o) = 10 - 30%, such as 11%, 12%, 15%, 17%, 19%, 20%, 22%, 24%, 26%, 28%, etc., m / (p + m + n + o) = 20 - 50%, such as 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, etc.

[0031] Preferably, n / (p + m + n + o) = 10 - 20%, o / (p + m + n + o) = 10 - 20%.

[0032] Preferably, both R1 and R2 are selected from acrylate groups.

[0033] Preferably, both R1 and R2 in the present invention are acrylate groups, introducing more double bonds into the resin, so that the resin composition can more easily undergo crosslinking polymerization during the exposure stage, increasing the degree of polymerization at the bottom of the photoresist, and further improving the development latitude.

[0034] Preferably, the photosensitive resin composition comprises the following components by solid weight parts:

[0035]

[0036] The alkali-soluble resin is 1 - 30 parts by weight, such as 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, etc., preferably 5 - 25 parts by weight.

[0037] When the content of the unsaturated vinyl structure resin is within the above range, there is no problem of undercut even during 100s development, and it has more excellent development latitude, and both heat resistance and reliability are improved.

[0038] The colorant is 10 - 70 parts by weight, such as 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, etc., preferably 20 - 60 parts by weight.

[0039] The colorant of the present invention can be selected according to the use of the color filter. The above colorant can be any one of pigments, dyes or natural pigments. As the above pigment, a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colourists) can be used. As the colorant of the present invention, an organic pigment is preferably used in consideration of excellent heat resistance and color rendering properties.

[0040] Specific examples of the preferred pigments that can be used in the present invention include yellow pigments such as C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 16, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 125, C.I. Pigment Yellow 128, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment Yellow 173, C.I. Pigment Yellow 194, C.I. Pigment Yellow 214; orange pigments such as C.I. Pigment Orange 13, C.I. Pigment Orange 31, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 42, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Orange 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange 71, C.I. Pigment Orange 73; red pigments such as C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Red 265; blue pigments such as C.I. Pigment Blue 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 60; purple pigments such as C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38; green pigments such as C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58; brown pigments such as C.I. Pigment Brown 23, C.I. Pigment Brown 25.Preferably, it contains one or more pigments selected from C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 209, C.I. Pigment Red 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15:6, and C.I. Pigment Green 36. The above-mentioned organic pigments and inorganic pigments can be used alone or in combination of two or more. For example, when forming a red pixel, it preferably contains C.I. Pigment Red 254 and C.I. Pigment Yellow 139; when forming a green pixel, it preferably contains C.I. Pigment Green 58, C.I. Pigment Yellow 150, or C.I. Pigment Yellow 138; when forming a blue pixel, it preferably contains C.I. Pigment Blue 15:6.

[0041] If the colorant is within the above range, the color density when making a color filter is sufficient, and the composition polymer can be contained in the necessary amount in the composition, so that a pattern with sufficient mechanical strength can be formed.

[0042] The photo-polymerizable compound is 10 to 60 parts by weight, such as 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, etc., preferably 15 to 40 parts by weight.

[0043] In the present invention, the photo-polymerizable compound includes monofunctional monomers and polyfunctional monomers.

[0044] Examples of the monofunctional monomer include: (meth)acrylamide, hydroxymethyl (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)butyl acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylate of phthalic acid derivatives. These monofunctional monomers can be used alone or in combination of two or more.

[0045] Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., benzylidene diisocyanate), the reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, the condensate of polyol and N-hydroxymethyl (meth)acrylamide, and other polyfunctional monomers such as triacryloyl formal. These polyfunctional monomers can be used alone or in combination of two or more kinds.

[0046] Among them, as the above-mentioned photo-polymerizable compound, a polyfunctional polymerizable compound having two or more functional groups is preferably used, and in particular, a polyfunctional polymerizable compound having five or more functional groups is preferably used.

[0047] When the photo-polymerizable compound is within the above specific content range, a good pattern property, sufficient heat resistance and chemical resistance can be obtained for the formed pattern.

[0048] The photo-polymerization initiator is 0.1 to 5 parts by weight, such as 0.2 part by weight, 0.4 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, etc., and preferably 0.2 to 3 parts by weight.

[0049] As the photopolymerization initiator of the present invention, as long as it can polymerize the above-mentioned photopolymerizable compound and the above-mentioned alkali-soluble resin, there is no particular limitation. From the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc., it is preferably to contain at least one compound selected from acetophenone-based, benzophenone-based, thioxanthone-based, and oxime-based compounds, and a light stabilizer can be used in combination.

[0050] Examples of the preferred acetophenone-based compounds of the present invention include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]propan-1-one, etc., and more preferably 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one. In addition, a plurality of acetophenone-based compounds and other photopolymerization initiators can also be used in combination.

[0051] Examples of the above-mentioned benzophenone-based compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

[0052] Examples of the thioxanthone-based compounds can be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0053] Examples of the oxime-based compounds may be O-acyl oxime-based compounds, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxoamino-1-phenylpropan-1-one, and the like. Specific examples of the O-acyl oxime-based compounds may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octan-1-one oxime-O-acetate, and 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate. For example, the photopolymerization initiator of the photosensitive resin composition according to the examples may be an oxime-based compound. As commercially available examples of the above photopolymerization initiator, OXE01, OXE-02, etc. of BASF Corporation can be cited, but it is not limited thereto.

[0054] When the content of the photopolymerization initiator is within the above specific content range, sufficient curing is carried out during the exposure in the pattern formation process to ensure excellent reliability. The pattern may have excellent heat resistance, light resistance, chemical resistance, resolution, and close contact properties, and the transmittance deterioration can be prevented due to the non-reactive initiator.

[0055] The amount of the auxiliary agent is 0.1 to 3 parts by weight, such as 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 2.7 parts by weight, 2.9 parts by weight, etc., and preferably 0.5 to 2 parts by weight.

[0056] The photosensitive resin composition of the present invention may be added various auxiliary agents as needed. Specifically, sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersion aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-flocculants, thermal polymerization inhibitors, defoamers, surfactants, etc. can be cited.

[0057] The solid content of the photosensitive resin composition is 10 to 30%, such as 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, etc., and preferably 15 to 20%. The solid content refers to the percentage of all solid components (coloring agents, alkali-soluble resins, photopolymerizable compounds, photopolymerization initiators, and auxiliary agents) in the photosensitive resin composition in the total mass of the composition.

[0058] The solid content of the photosensitive resin composition of the present invention is adjusted by adding a solvent. Examples of the solvents used include: (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate; other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-acetoacetate; aromatic hydrocarbons such as toluene, xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These solvents can be used alone or in combination of two or more.

[0059] Among the above solvents, considering solubility and dispersibility, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are preferred, and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferably used.

[0060] Preferably, the total solid amount of the colorant, alkali-soluble resin, photopolymerizable compound, photoinitiator, and additive is 100 parts by weight.

[0061] Preferably, the photosensitive resin composition comprises the following components in parts by weight of solids:

[0062]

[0063] Preferably, the photosensitive resin composition comprises the following components by solid weight parts:

[0064]

[0065] The solid weight parts refer to the added amount of the actual solid substance and do not include the solvent. For example, in the actual preparation process, the alkali-soluble resin is added to the system in the form of a resin solution, and the above weight parts refer to the amount of the resin in the resin solution rather than the amount of the resin solution.

[0066] The photosensitive resin composition provided by the present invention can be obtained by mixing all the above components in a blender. It can also be filtered with a filter to make the prepared photosensitive resin composition uniform.

[0067] The pattern formation of the photosensitive resin composition provided by the present invention can be selected from, but not limited to, the following methods:

[0068] Spin-coat the photosensitive resin composition provided by the present invention on a substrate and pre-bake it on a clean hot plate at 90 °C for 120 seconds.

[0069] After cooling the above-mentioned coated film substrate to room temperature, make the distance between it and the photomask made of quartz glass be 180 μm, and use an exposure machine to expose it with an exposure dose of 40 mJ / cm 2 (based on 365 nm) to form a photolithographic pattern of the mask pattern on the coated film substrate.

[0070] Immerse the above-mentioned coated film substrate in an aqueous developer containing 0.04% potassium hydroxide at 25 °C for 50 seconds for development, wash it with water, and then post-bake it in an oven at 230 °C for 20 minutes.

[0071] The second object of the present invention is to provide an application of the photosensitive resin composition described in the first object, and the photosensitive resin composition is applied to a color filter.

[0072] The third object of the present invention is to provide a color filter, and the color filter contains the photosensitive resin composition described in the first object.

[0073] The fourth object of the present invention is to provide a liquid crystal panel, and the liquid crystal panel contains the color filter described in the third object.

[0074] Compared with the prior art, the present invention has the following beneficial effects:

[0075] In the photosensitive resin composition of the present invention, an alkali-soluble resin containing an unsaturated vinyl structure represented by Formula I is selected, so that the crosslinking polymerization between resins during the exposure stage of the photosensitive resin composition is easier to form a network macromolecular chain, increasing the degree of polymerization at the bottom of the photoresist. Even during 100 s of development, there is no problem of undercutting. It has good development latitude, excellent edge straightness and film residue, good heat resistance, a film reduction rate of 3.09 - 3.35%, ΔEab of 0.48 - 0.67, a good development latitude of -0.69 to -0.29, and the linear deviation at the pattern edge is less than 1 μm or even less than 0.5 μm. By observing the pixels in the same area under an optical microscope at 1000 times magnification, there is no residual film. Description of the Drawings

[0076] Figure 1 It is a SEM image (5000 times magnification) of the photosensitive resin composition of Example 1 during 100 s of development.

[0077] Figure 2 It is a SEM image (20000 times magnification) of the photosensitive resin composition of Example 1 during 100 s of development.

[0078] Figure 3 It is a SEM image (5000 times magnification) of the photosensitive resin composition of Comparative Example 1 during 100 s of development.

[0079] Figure 4 It is a SEM image (20000 times magnification) of the photosensitive resin composition of Comparative Example 1 during 100 s of development. Detailed Description of the Invention

[0080] To facilitate the understanding of the present invention, the following examples are listed. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0081] Preparation Example 1

[0082] Synthesize an alkali-soluble resin B1 solution:

[0083] (1) In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen is allowed to flow at 0.02 L / min to form a nitrogen atmosphere. Add the solvent toluene, 170.4 g (1.2 mol) of glycidyl methacrylate, 70.4 g (0.4 mol) of benzyl methacrylate and 41.6 g (0.4 mol) of styrene. After complete dissolution, add 1.64 g of azobisisobutyronitrile initiator and slowly heat to 65 °C and react for 5 h for free radical polymerization. Add an excess of n-hexane to obtain a white precipitate. Then filter with a Buchner funnel, and wash the filter cake thoroughly with n-hexane to remove the residual monomers and azobisisobutyronitrile therein, and dry in a vacuum oven at room temperature for later use.

[0084] (2) Weigh 141.2 g of the dried white powdery resin and put it into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer. Add the solvent amount of diethylene glycol dimethyl ether, heat up to 80 °C, start stirring. After the resin is completely dissolved, heat up to 90 °C, add 2.62 g of triphenylphosphine (ring-opening catalyst), and slowly dropwise add 43.2 g (0.6 mol) of acrylic acid to carry out the ring-opening reaction, controlling the dropping time to be 1 h. Add 3.22 g of tetrabutylammonium bromide (esterification catalyst), and then slowly dropwise add 41.6 g (0.4 mol) of malonic acid to carry out the esterification reaction, controlling the dropping time to be 1 h. Distill the reaction mixture under reduced pressure to remove the solvent, wash it thoroughly with n-hexane to remove the residual monomers and catalysts, and dry it in a vacuum oven at room temperature for standby.

[0085] (3) Weigh 178.8 g of the finally obtained white powdery resin, add 600 g of propylene glycol monomethyl ether acetate and stir to dissolve it to obtain an alkali-soluble resin B1 with a solid content of 29.8%. The structure of this resin is as follows:

[0086]

[0087] Among them, p / (p + m + n + o) = 20%, m / (p + m + n + o) = 40%, n / (p + m + n + o) = 20%, o / (p + m + n + o) = 20%, and R is methylene.

[0088] Preparation Example 2

[0089] Synthesize an alkali-soluble resin B2 solution:

[0090] In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, make nitrogen flow at 0.02 L / min to form a nitrogen atmosphere. Add the solvent amount of toluene, 103.2 g (1.2 mol) of methacrylic acid, 70.4 g (0.4 mol) of benzyl methacrylate, and 41.6 g (0.4 mol) of styrene. After complete dissolution, add 1.64 g of azobisisobutyronitrile initiator and slowly heat up to 65 °C and react for 5 h to carry out free radical polymerization. Add an excess of n-hexane to obtain a white precipitate. Then filter it with a Buchner funnel, and wash the filter cake thoroughly with n-hexane to remove the residual monomers and azobisisobutyronitrile, and dry it in a vacuum oven at room temperature for standby.

[0091] (2) Weigh 178.8 g of this white powdery resin and add 600 g of propylene glycol monomethyl ether acetate and stir to dissolve it to obtain an alkali-soluble resin B2 with a solid content of 29.8%. The structure of this resin is as follows:

[0092]

[0093] Among them, p, m, n, and o are the same as those in B1.

[0094] Preparation Example 3

[0095] Synthesize an alkali-soluble resin B3 solution:

[0096] The preparation method of Preparation Example 3 is the same as that of Preparation Example 1 and has a similar structure. The differences are as follows: in (1), 227.2 g (1.6 mol) of glycidyl methacrylate, 35.2 g (0.2 mol) of benzyl methacrylate, and 20.8 g (0.2 mol) of styrene are used. In (2), 141.6 g of the dried white powdery resin is weighed; 57.6 g (0.8 mol) of acrylic acid and 52 g (0.5 mol) of malonic acid are added dropwise. In B3, p / (p + m + n + o) = 30%, m / (p + m + n + o) = 50%, n / (p + m + n + o) = 10%, o / (p + m + n + o) = 10%, and R is a methylene group.

[0097] Preparation Example 4

[0098] Synthesize an alkali-soluble resin B4 solution:

[0099] The preparation method of Preparation Example 4 is the same as that of Preparation Example 1 and has a similar structure. The difference is that in (2), 41.6 g (0.4 mol) of malonic acid is replaced with 83 g (0.5 mol) of phthalic acid. In B4, p / (p + m + n + o) = 10%, m / (p + m + n + o) = 50%, n / (p + m + n + o) = 20%, o / (p + m + n + o) = 20%, and R is a phenylene group.

[0100] Preparation Example 5

[0101] Synthesize an alkali-soluble resin B5 solution:

[0102] The preparation method of Preparation Example 5 is the same as that of Preparation Example 1 and has a similar structure. The differences are as follows: in (1), 198.8 g (1.4 mol) of glycidyl methacrylate, 105.6 g (0.6 mol) of benzyl methacrylate, and 0 g (0 mol) of styrene are used. In (2), 152.2 g of the dried white powdery resin is weighed; 50.4 g (0.7 mol) of acrylic acid and 41.6 g (0.4 mol) of malonic acid are added dropwise. In B5, p / (p + m + n + o) = 30%, m / (p + m + n + o) = 40%, n / (p + m + n + o) = 30%, o / (p + m + n + o) = 0%, and R is a methylene group.

[0103] Examples 1 to 7 and Comparative Example 1 all provide a photosensitive resin composition, and the specific formulation details are shown in Table 1.

[0104] Table 1

[0105]

[0106]

[0107]

[0108] During the experiment, the colorant, alkali-soluble resin, and some additives were added to the system in the form of a solution. Therefore, the parts by weight in Table 1 represent the mass fraction of the added solution. Those skilled in the art can calculate the actual solid content based on the solid content. —— represents not adding the corresponding substance.

[0109] A: C.I. Pigment Blue 15:6, solid content 20.2%, pigment content 12%.

[0110] C: Dipentaerythritol hexaacrylate (DPHA, KAYARAD);

[0111] D: OXE-01 (BASF);

[0112] E1: FTX-218 (Donghua New Materials), solid content 20%;

[0113] E2: 2-Vinyl-triethoxysilane (Beijing Reagent Company);

[0114] G1: PGMEA (Propylene glycol monomethyl ether acetate);

[0115] G2: PGME (Propylene glycol ethyl ether);

[0116] G3: MBA (3-Methoxybutyl acetate).

[0117] Performance testing

[0118] The following tests were conducted on the photosensitive resin compositions obtained in the above examples and comparative examples:

[0119] 1) Heat resistance evaluation

[0120] The heat resistance of the photosensitive resin composition was verified by the film thickness reduction rate and color difference after coating. The film thickness reduction rate was less than 5%, and the color difference ΔEab was less than 3%.

[0121] Film thickness reduction rate = (film thickness after the sixth post-baking / film thickness after the first post-baking) * 100%, required to be less than 5%; the test instrument was a Bruker profilometer Dektak-XT.

[0122] The color difference was the color difference value ΔEab between the sample after the sixth post-baking and the sample after the first post-baking, required to be less than 3%; the test instrument was a Konica Minolta CM-5.

[0123] 2) Development latitude evaluation

[0124] Seven coatings were fabricated and developed for 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, and 100 s respectively. After post-baking each coating, the line width (CD) was measured, and the development latitude (ΔCD-um / 10 secs) was calculated. It is required that ΔCD-um / 10 secs be greater than -0.8.

[0125] 3) Evaluation of edge straightness

[0126] The surface morphology of the pixel was observed at 5000 times magnification by Hitachi SU8010 cold field emission scanning electron microscope.

[0127] 〇: The linear deviation of the pattern edge is less than 0.5 μm.

[0128] △: The linear deviation of the pattern edge is greater than 0.5 μm and less than 1 μm.

[0129] ×: The linear deviation of the pattern edge is greater than 1 μm.

[0130] 4) Evaluation of film residue

[0131] The film residue situation was evaluated by observing the pixels in the same area at 1000 times magnification through an optical microscope.

[0132] 〇: No film residue.

[0133] △: Slight film residue.

[0134] ×: Serious film residue.

[0135] 5) Evaluation of undercut (for Example 1 and Comparative Example 1)

[0136] After developing the coating for 100 s, post-baking was carried out. After post-baking, cross-sectional observations were made at 5000 times and 20000 times magnification by Hitachi SU8010 cold field emission scanning electron microscope (SEM).

[0137] The results of performance tests 1) to 4) are shown in Table 2.

[0138] Table 2

[0139]

[0140]

[0141] From the data in Table 2, it can be seen that compared with the comparative example, the example of the present invention has good heat resistance (the film reduction rate is 3.09 - 3.35%, and ΔEab is 0.48 - 0.67), has good development latitude (-0.69 - -0.29), and the test results of edge straightness and film residue are excellent. Especially when developed for 100 s, there is no undercut problem.

[0142] The results of Performance Test 5) are as Figures 1 to 4 shown, where Figure 1 and Figure 2 are the SEM scanning test results of the photosensitive resin composition of Example 1 during development for 100 s, with magnification factors of 5000 times and 20000 times respectively; Figure 3 and Figure 4 are the SEM scanning test results of the photosensitive resin composition of Comparative Example 1 during development for 100 s, with magnification factors of 5000 times and 20000 times respectively; Figure 1 and Figure 2 show a gentle slope and no undercut phenomenon, Figure 3 and Figure 4 show a higher slope and an undercut phenomenon at the bottom. This proves that using an alkali-soluble resin containing an unsaturated vinyl structure can effectively inhibit the undercut phenomenon and improve the development margin.

[0143] The applicant declares that the present invention uses the above embodiments to illustrate the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition includes an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator; The alkali-soluble resin has a structure shown in Formula I; In Formula I, R1 and R2 are each independently selected from -OH or an acrylate group, and at least one of R1 and R2 is an acrylate group; In Formula I, R3 is selected from any one of C1-C12 alkyl, C6-C30 aryl, or a carboxyl group; In Formula I, R4 is selected from any one of -H, C1-C12 alkyl, or C6-C30 aryl, or a group formed by connecting at least two of them; In Formula I, R5 and R6 are each independently selected from -H or -CORCOOH, and at least one of R5 and R6 is -CORCOOH, and R is selected from C1-C12 alkylene; In Formula I, R7, R8, and R9 are each independently selected from -H or methyl; In Formula I, (p + m) / (p + m + n + o) = 10-80%, n / (p + m + n + o) = 0-30%, o / (p + m + n + o) = 0-20%.

2. The photosensitive resin composition according to claim 1, wherein The alkali-soluble resin has a structure shown in Formula II; R1, R2, R3, R4, R7, R8, R9, p, m, n, and o all have the same defined range as in claim 1.

3. The photosensitive resin composition according to claim 1, wherein The alkali-soluble resin has a structure shown in Formula III; R1, R2, p, m, n, and o all have the same defined range as in claim 1.

4. The photosensitive resin composition according to claim 2 or 3, characterized in that, p < m.

5. The photosensitive resin composition according to claim 4, wherein p / (p + m + n + o) = 10-30%, m / (p + m + n + o) = 20-50%.

6. The photosensitive resin composition according to claim 1, wherein n / (p + m + n + o) = 10-20%, o / (p + m + n + o) = 10-20%.

7. The photosensitive resin composition according to any one of claims 1 to 3, wherein Both R1 and R2 are selected from acrylate groups.

8. The photosensitive resin composition according to claim 1, characterized in that, The photosensitive resin composition includes the following components by solid weight parts:

9. The photosensitive resin composition according to claim 8, wherein, The solid content of the photosensitive resin composition is 10-30%.

10. The photosensitive resin composition according to claim 9, characterized in that, The solid content of the photosensitive resin composition is 15-20%.

11. The photosensitive resin composition according to claim 8, wherein The total solid amount of the colorant, alkali-soluble resin, photopolymerizable compound, photoinitiator, and additive is 100 parts by weight.

12. The photosensitive resin composition according to claim 8, wherein The photosensitive resin composition includes the following components by solid weight parts:

13. Use of the photosensitive resin composition according to any one of claims 1 to 12, characterized in that, The photosensitive resin composition is applied to a color filter.

14. A color filter, characterized in that, The color filter contains the photosensitive resin composition according to any one of claims 1-12.

15. A liquid crystal panel, characterized in that, The liquid crystal panel contains the color filter according to claim 14.

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