Black photoresist composition and use method thereof

Abstract

The invention relates to a black photoresist composition and a use method thereof. The black photoresist composition comprises the following components: resin containing vinyl and carboxyl, a curing agent containing amino, a flatting agent and an initiator, the initiator includes a combination of a photoinitiator and a thermal initiator. According to the black photoresist composition provided by the invention, the photoinitiator and the thermal initiator are used as initiators together, so that the production cost of the black photoresist composition can be reduced, the curing efficiency of the black photoresist composition near a base material can be improved, the curing uniformity degree is improved, the adhesive force of the black photoresist composition is stronger, and the service life of the black photoresist composition is prolonged. The water boiling resistance and the UV aging resistance are higher; besides, the curing agent containing amino can improve the curing degree of the resin containing vinyl and carboxyl, and can block the carboxyl, so that the alkali-resistant cleaning agent cleaning capability of the black photoresist composition is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of liquid crystal display, and in particular relates to a black photoresist composition and a use method thereof. Background Art

[0002] General black photoresist (BM photoresist) contains UV system resin, and uses photoinitiator to initiate free radical resin reaction. General photoinitiators are divided into free radical photoinitiators and cationic photoinitiators. Free radical photoinitiators react quickly and easily cause internal stress after film formation. In addition, since BM photoresist is generally initiated by LDI, the light source gradually decays during the penetration process. The curing degree of the BM photoresist surface is higher than that of the bottom layer. The reaction degree of the bottom BM photoresist is insufficient and the curing degree is insufficient, resulting in poor adhesion and insufficient water boiling resistance at the position closer to the substrate. Cationic photoinitiators are expensive and require unique cationic resins for reaction, which limits their application in many occasions.

[0003] After the final baking of BM photoresist, it is generally necessary to be cleaned with an alkaline cleaning agent, and then a second layer of BM photoresist is sprayed. Since acrylic resin contains carboxyl groups, its ability to resist cleaning with alkaline cleaning agents is poor; and since the exposure energy of LDI machines at many construction sites is very low, the energy is fixed and gradually decays with the use time, it is easy to cause insufficient initiation efficiency. If the curing efficiency is improved by increasing the content of photoinitiator, the cost of BM photoresist will increase due to the high cost of photoinitiator (ranging from 1,000 yuan to 10,000 yuan).

[0004] CN114755890A discloses a low-temperature negative black photoresist composition and a black matrix thereof, comprising an organic solvent and a solute dissolved in the organic solvent, wherein the solute comprises a photocurable resin containing double bonds and hydroxyl groups, an alkali-soluble acrylate photopolymerizable monomer, a photoinitiator, a colorant and a low-temperature blocked isocyanate crosslinking agent; CN117486769A discloses a high-adhesion acidic monomer, a black photoresist and a preparation method thereof, wherein the black photoresist comprises, by weight, 30 to 50 parts of a black color paste, 5 to 20 parts of an alkali-soluble resin, 8 to 12 parts of a high-adhesion acidic monomer, 3 to 5 parts of an initiator, 0.2 to 1 part of a silane coupling agent, 0.2 to 1 part of a leveling agent and 20 to 50 parts of an organic solvent. However, existing black photoresist compositions generally have poor adhesion, water boiling resistance, and aging resistance, as well as uneven curing and poor resistance to cleaning with alkaline cleaning agents. Therefore, it is necessary to design a black photoresist composition with strong adhesion, good water boiling resistance, good resistance to cleaning with alkaline cleaning agents, and good aging resistance, and uniform curing. Summary of the invention

[0005] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a black photoresist composition and a method for using the same. By designing and screening the various components of the black photoresist composition, the black photoresist composition is cured more evenly, the boiling water resistance and anti-aging properties are improved, the adhesion to the substrate is enhanced, and the ability to resist cleaning with alkaline cleaning agents is improved.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a black photoresist composition, the components of which include a resin containing vinyl and carboxyl groups, a curing agent containing amino groups, a leveling agent and an initiator; the initiator includes a combination of a photoinitiator and a thermal initiator.

[0008] The black photoresist composition provided by the present invention uses a photoinitiator and a thermal initiator as initiators. Since the thermal initiator is cheap (less than one hundred yuan), the production cost of the black photoresist composition can be greatly reduced. Compared with the free radical type photoinitiator, the black photoresist composition has a small shrinkage during the curing film formation process, and the initiation rate and polymerization degree are easy to adjust. Free radicals are released when heated, and the initiation reaction is not restricted by the shape of the object. The curing is uniform, and the problems of too low exposure energy, higher surface curing rate than the bottom layer, insufficient reaction degree at the position close to the substrate, and insufficient adhesion of the black photoresist composition are avoided. The adhesion of the black photoresist composition on the substrate is improved, and then the water boiling resistance, high temperature and high humidity resistance and UV aging resistance of the black photoresist composition are improved. In addition, the thermal initiator can further improve the water boiling resistance of the black photoresist composition by increasing the curing rate of the vinyl.

[0009] In the black photoresist composition provided by the present invention, the curing agent containing amino groups can block the carboxyl groups while further improving the curing degree of the black photoresist composition, thereby improving the ability of the black photoresist composition to resist cleaning by alkaline cleaning agents. Since the thermal initiator promotes the curing of double bonds in the resin containing vinyl and carboxyl groups, and the curing agent containing amino groups promotes the curing of carboxyl groups in the resin containing vinyl and carboxyl groups, the two play a synergistic role and jointly enhance the water boiling resistance of the black photoresist composition.

[0010] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0011] As a preferred technical solution, the resin containing vinyl and carboxyl groups includes any one of acid-modified novolac epoxy acrylate resin, acid-modified o-cresol epoxy acrylate resin, acid-modified epoxy acrylate resin or bisphenol fluorene modified acrylate resin or a combination of at least two thereof.

[0012] In the present invention, the acid-modified phenolic epoxy acrylate resin can be purchased, exemplarily from but not limited to Showa YSR-01; the acid-modified o-cresol epoxy acrylate resin can be purchased, exemplarily from but not limited to Showa PR300CP; the acid-modified epoxy acrylate resin can be purchased, exemplarily from but not limited to Nippon Kayaku CCR-1173HW; the bisphenol fluorene-modified acrylate resin can be purchased, exemplarily from but not limited to Showa YSR-06.

[0013] Preferably, the weight average molecular weight of the resin containing vinyl and carboxyl groups is 3000-30000, for example, it can be 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 22000, 24000, 26000, 27000, 28000, 29000, etc.

[0014] Preferably, the acid value of the resin containing vinyl and carboxyl groups is 40-150 mgKOH / g, for example, it can be 50 mgKOH / g, 60 mgKOH / g, 70 mgKOH / g, 80 mgKOH / g, 90 mgKOH / g, 100 mgKOH / g, 110 mgKOH / g, 120 mgKOH / g, 130 mgKOH / g, 140 mgKOH / g, etc.

[0015] Preferably, the curing agent containing amino groups includes any one of amino resin, polyurethane, polyaniline, 3,3',5,5'-tetramethylbenzidine or 4,4'-diaminodiphenylmethane, or a combination of at least two thereof, and amino resin is more preferred.

[0016] Preferably, the amino resin comprises melamine formaldehyde resin.

[0017] In the present invention, the melamine formaldehyde resin can be purchased, and can be exemplarily purchased from, but not limited to, CYMEL 325 and CYMEL 303LF of allnex (Cytec).

[0018] Preferably, the weight average molecular weight of the amino resin, polyaniline and polyurethane is independently 200-5000, for example, 400, 600, 800, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, etc.

[0019] Preferably, the mass ratio of the resin containing vinyl and carboxyl groups to the curing agent containing amino groups is (1-4):1, for example, it can be 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, etc.

[0020] Preferably, the leveling agent includes any one of a fluorine leveling agent, a silicone leveling agent or an acrylic leveling agent, or a combination of at least two of them.

[0021] Preferably, the mass percentage of the leveling agent in the black photoresist composition is 0.05-1%, for example, it can be 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, etc.

[0022] In the present invention, the photoinitiator is a highly photosensitizing photoinitiator. Preferably, the photoinitiator includes any one of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime) or OXE-03, or a combination of at least two thereof.

[0023] Preferably, the mass ratio of the photoinitiator to the resin containing vinyl and carboxyl groups is (0.1-0.4):1, for example, it can be 0.12:1, 0.14:1, 0.16:1, 0.18:1, 0.2:1, 0.22:1, 0.24:1, 0.26:1, 0.28:1, 0.3:1, 0.32:1, 0.34:1, 0.36:1, 0.38:1, etc.

[0024] Preferably, the decomposition temperature of the thermal initiator is 60-200°C, for example, it can be 62°C, 64°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 90°C, 100°C, 120°C, 140°C, 160°C, 180°C, etc.

[0025] In the present invention, the decomposition temperature of the thermal initiator itself is a range value rather than a point value. The humidity of the environment and other factors will affect the decomposition temperature of the thermal initiator, so there is a minimum decomposition temperature and a maximum decomposition temperature.

[0026] Preferably, the boiling point of the thermal initiator is 236-350°C, for example, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, etc.

[0027] Preferably, the thermal initiator comprises azobisisobutyronitrile and / or dibenzoyl peroxide.

[0028] Preferably, the mass ratio of the thermal initiator to the photoinitiator is (0.5-2):1, for example, it can be 0.52:1, 0.54:1, 0.56:1, 0.58:1, 0.6:1, 0.62:1, 0.64:1, 0.66:1, 0.68:1, 0.7:1, 0.72:1, 0.74:1, 0.76:1, 0.78:1, 0.8:1, 0.82:1, 0.84:1, 0.86:1, 0.88:1, 0.9:1, 0.92:1, 0.95:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, etc.

[0029] Preferably, the components of the black photoresist composition further include a silane coupling agent.

[0030] In the present invention, the silane coupling agent needs to contain a group that can react with the resin containing vinyl and carboxyl groups, such as an amino group, an epoxy group, a vinyl group, etc. Preferably, the silane coupling agent includes any one of aminosilane, epoxysilane, vinylsilane or isocyanate silane, or a combination of at least two thereof.

[0031] Preferably, the mass ratio of the silane coupling agent to the resin containing vinyl and carboxyl groups is (0.05-0.4):1, for example, it can be 0.06:1, 0.08:1, 0.1:1, 0.12:1, 0.14:1, 0.16:1, 0.18:1, 0.2:1, 0.22:1, 0.24:1, 0.26:1, 0.28:1, 0.3:1, 0.32:1, 0.34:1, 0.36:1, 0.38:1, etc.

[0032] Preferably, the components of the black photoresist composition further include a black color paste.

[0033] Preferably, the L value of the black color paste is 25-29, the a value is -2 to 2, and the b value is -2 to 2.

[0034] In the present invention, the black color paste can be purchased, and can be purchased from, for example, but not limited to, Shandong Kairuier SBK-789.

[0035] Preferably, the mass ratio of the black color paste to the resin containing vinyl and carboxyl groups is (1-10):1, for example, it can be 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, etc.

[0036] Preferably, the components of the black photoresist composition further include a solvent.

[0037] Preferably, the solvent includes any one of propylene glycol methyl ether acetate, ethyl acetate, dibasic acid ester, isopropanol or isobutanol, or a combination of at least two thereof.

[0038] Preferably, the mass percentage of the solvent in the black photoresist composition is 50-70%, for example, it can be 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, etc.

[0039] The present invention does not impose any special restrictions on the preparation method of the provided black photoresist composition, as long as a uniformly mixed black photoresist composition can be obtained.

[0040] In a second aspect, the present invention provides a method for using the black photoresist composition according to the first aspect, the method comprising:

[0041] The black photoresist composition as described in the first aspect is coated on a substrate, and surface drying, exposure, development and final baking are performed in sequence to obtain a photoresist pattern.

[0042] Preferably, the coating method includes spray coating or spin coating.

[0043] Preferably, the coating has a thickness of 2-6 μm, for example, 2.2 μm, 2.5 μm, 2.8 μm, 3 μm, 3.2 μm, 3.5 μm, 3.8 μm, 4 μm, 4.2 μm, 4.5 μm, 4.8 μm, 5 μm, 5.2 μm, 5.5 μm, 5.8 μm, etc.

[0044] Preferably, the surface drying temperature is 60-80°C, for example, it may be 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 74°C, 76°C, 78°C, etc.

[0045] Preferably, the surface drying time is 2-5 min, for example, it can be 2.2 min, 2.4 min, 2.6 min, 2.8 min, 3 min, 3.2 min, 3.4 min, 3.6 min, 3.8 min, 4 min, 4.2 min, 4.4 min, 4.6 min, 4.8 min, etc.

[0046] The surface drying temperature should not be too high and the time should not be too long, otherwise the black photoresist composition may cause excessive solvent volatilization during the surface drying process, or the thermal initiator may overreact, resulting in difficulty in development.

[0047] Preferably, the exposure light energy is 70-400 mJ / cm 2 , for example, 100 mJ / cm 2 、150mJ / cm 2 、200mJ / cm 2 、250mJ / cm 2 、300mJ / cm 2 、350mJ / cm 2 wait.

[0048] Preferably, the wavelength of the exposure light is 350-400 nm, for example, it can be 355 nm, 360 nm, 365 nm, 370 nm, 375 nm, 380 nm, 385 nm, 390 nm, 395 nm, etc.

[0049] Preferably, the developer used for the development comprises Na 2 CO 3 Any one of aqueous solution, NaOH aqueous solution or YS-992 aqueous solution or a combination of at least two thereof.

[0050] In the present invention, YS-992 was purchased from Guangzhou Yisheng Environmental Protection Technology Co., Ltd.

[0051] Preferably, the mass percentage of the solute in the developer is 0.5-2%, for example, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, etc.

[0052] Preferably, the final baking temperature is 160-200°C, for example, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, etc.

[0053] Preferably, the final baking time is 30-60 min, for example, it can be 32 min, 35 min, 38 min, 40 min, 42 min, 45 min, 48 min, 50 min, 52 min, 55 min, 58 min, etc.

[0054] Preferably, the minimum decomposition temperature of the thermal initiator in the black photoresist composition is ≤ the surface drying temperature ≤ the minimum decomposition temperature of the thermal initiator + 20°C; the minimum decomposition temperature of the thermal initiator + 100°C ≤ the final baking temperature ≤ the boiling point of the thermal initiator - 30°C.

[0055] In the present invention, the "minimum decomposition temperature of the thermal initiator + 20°C" means the temperature value obtained by adding 20°C to the minimum decomposition temperature of the thermal initiator. For example, when the decomposition temperature of the thermal initiator is 60-80°C, 60°C is the minimum decomposition temperature of the thermal initiator, so 60 plus 20 equals 80, that is, the surface drying temperature is ≤80°C. The meanings of "minimum decomposition temperature of the thermal initiator + 100°C" and "boiling point of the thermal initiator - 30°C" are the same as above.

[0056] In the method for using the black photoresist composition provided by the present invention, it is necessary to ensure that the thermal initiator in the black photoresist composition does not initiate a reaction or initiates a small amount during the surface drying process, so as not to affect the development of the black photoresist composition to obtain a pattern, and then thermally initiate it during the final baking; therefore, it is necessary to control the surface drying temperature not to be too high, otherwise the thermal initiator will start to initiate a reaction during the surface drying process, affecting the development.

[0057] For example, the decomposition temperature of azobisisobutyronitrile (AIBN) is 65-85°C (the minimum decomposition temperature is 65°C), the half-life of AIBN is 1 hour at 82°C, and the half-life of AIBN is 0.1 hour at a higher temperature such as 101°C. For another example, the decomposition temperature of benzoyl peroxide (BPO) is 60-80°C (the minimum decomposition temperature is 60°C). Although it begins to decompose and generate free radicals at 60°C, the decomposition rate is relatively slow, with a half-life of 10 hours at 72°C, 1 hour at 90°C, 8 minutes at 110°C, and 1 minute at 131°C. Setting the surface drying temperature according to the condition that the minimum decomposition temperature of the thermal initiator ≤ the surface drying temperature ≤ the minimum decomposition temperature of the thermal initiator + 20°C will not affect the development.

[0058] During the final baking, it is hoped that the thermal initiator can initiate the reaction. Generally, the final baking temperature is set to be ≥160°C. Since the boiling point of AIBN is 236°C, if the final baking temperature is too high, the thermal initiator will volatilize and lose the initiation effect. In addition, the volatilized thermal initiator will produce holes on the surface of the film layer, which will deteriorate the performance. The appropriate final baking temperature can ensure that the thermal initiator will not volatilize and can initiate the reaction well. The boiling point of BPO is 349.7°C. If the final baking temperature is set to 160-200°C, it will not affect its reaction performance.

[0059] In a third aspect, the present invention provides a use of the black photoresist composition as described in the first aspect in a display device.

[0060] Compared with the prior art, the present invention has the following beneficial effects:

[0061] The black photoresist composition provided by the present invention uses a photoinitiator and a thermal initiator as initiators, which can reduce production costs and improve the curing efficiency of the black photoresist composition near a substrate, so that the black photoresist composition has stronger adhesion, more uniform curing, and complete development within 30 minutes. The surface is flat after final baking, and the water boiling resistance and UV aging resistance of the black photoresist composition can be improved. The water boiling time can reach 40-120 hours, and the hardness is 3-5B after ultraviolet light irradiation for 300 hours. In addition, the amino-containing curing agent used can improve the curing degree of the black photoresist composition and improve the ability of the black photoresist composition to be cleaned by an alkaline cleaning agent. The hardness is 3-5B after being treated with an alkaline cleaning agent for 30 minutes. DETAILED DESCRIPTION

[0062] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0063] The sources of some components in the embodiments and comparative examples are as follows:

[0064] (1) Acid-modified o-cresol epoxy acrylate resin: purchased from Showa PR300CP, with a weight average molecular weight of 7000-10000 and an acid value of 75-85 mgKOH / g;

[0065] (2) Acid-modified epoxy acrylate resin: purchased from Nippon Kayaku CCR-1173HW, with a viscosity of 50 Pa·s (25°C) and an acid value of 70 mgKOH / g;

[0066] (3) Acid-modified phenolic epoxy acrylate resin: purchased from Showa YSR-01, with a weight average molecular weight of 9000-15000 and an acid value of 60-110 mgKOH / g;

[0067] (4) Bisphenol fluorene modified acrylic resin: purchased from Showa YSR-06, with a weight average molecular weight of 4500-5500 and an acid value of 100-110 mgKOH / g;

[0068] (5) Melamine formaldehyde resin: purchased from Allnex (Cytec) CYMEL 303LF;

[0069] (6) Leveling agent: purchased from BYK-330;

[0070] (7) 3,3',5,5'-Tetramethylbenzidine TMB: purchased from Rebo, CAS No. 54827-17-7;

[0071] (8) Azobisisobutyronitrile: purchased from Shuangqi, decomposition temperature is 65-85°C;

[0072] (9) Dibenzoyl peroxide: purchased from Haijing Chemical, decomposition temperature is 60-80°C;

[0073] (10) Epoxy silane: purchased from Xinyue KBM-403;

[0074] (11) Black color paste: purchased from Shandong Kairuier SBK-789, with an L value of 27.72, a value of -0.07, and b value of 0.52.

[0075] Example 1

[0076] A black photoresist composition, the components of which are shown in the following table:

[0077] Components Mass / g Acid modified o-cresol epoxy acrylate resin 15 Melamine formaldehyde resin 5 OXE-02 3 Thermal initiator AIBN 1.5 Epoxy silane KBM-403 1 Leveling agent BYK-330 0.1 Propylene glycol methyl ether acetate 50 Black color paste 20

[0078] The preparation method of the black photoresist composition comprises:

[0079] Acid-modified o-cresol epoxy acrylate resin, melamine formaldehyde resin, OXE-02, AIBN, epoxy silane KBM-403, leveling agent BYK-330, propylene glycol methyl ether acetate and black color paste were added in sequence, stirred for 1 hour, and then filtered using a 1 μm filter membrane to obtain the black photoresist composition.

[0080] Example 2

[0081] A black photoresist composition, the components of which are shown in the following table:

[0082] Components Mass / g Acid modified epoxy acrylate resin 10 4,4'-Diaminodiphenylmethane 5 OXE-02 3 Thermal initiator BPO 1.5 Epoxy silane KBM-403 1 Leveling agent BYK-330 0.1 Isopropyl alcohol 50 Black color paste 20

[0083] The preparation method of the black photoresist composition is the same as that of Example 1.

[0084] Example 3

[0085] A black photoresist composition, the components of which are shown in the following table:

[0086]

[0087]

[0088] The preparation method of the black photoresist composition is the same as that of Example 1.

[0089] Example 4

[0090] A black photoresist composition, the components of which are shown in the following table:

[0091] Components Mass / g Acid modified o-cresol epoxy acrylate resin 10 3,3',5,5'-Tetramethylbenzidine TMB 6 OXE-02 3 Thermal initiator BPO 1.5 Epoxy silane KBM-403 1 Leveling agent BYK-330 0.1 Ethyl acetate 50 Black color paste 20

[0092] The preparation method of the black photoresist composition is the same as that of Example 1.

[0093] Example 5

[0094] A black photoresist composition, the components of which are shown in the following table:

[0095]

[0096]

[0097] The preparation method of the black photoresist composition is the same as that of Example 1.

[0098] Example 6

[0099] A black photoresist composition, the components of which are shown in the following table:

[0100] Components Mass / g Acid modified o-cresol epoxy acrylate resin 10 3,3',5,5'-Tetramethylbenzidine TMB 6 OXE-02 3.5 Thermal initiator BPO 1 Epoxy silane KBM-403 1 Leveling agent BYK-330 0.1 Ethyl acetate 50 Black color paste 20

[0101] The preparation method of the black photoresist composition is the same as that of Example 1.

[0102] Example 7

[0103] A black photoresist composition and a preparation method thereof, which differs from Example 4 only in that the amount of 3,3',5,5'-tetramethylbenzidine TMB used is 2 g, and the other raw materials, process parameters and steps are the same as those of Example 4.

[0104] Example 8

[0105] A black photoresist composition and a preparation method thereof, which differs from Example 4 only in that the amount of 3,3',5,5'-tetramethylbenzidine TMB used is 15 g, and the other raw materials, process parameters and steps are the same as those of Example 4.

[0106] Comparative Example 1

[0107] A black photoresist composition and a preparation method thereof, which differs from Example 1 only in that the amount of thermal initiator AIBN in the black photoresist composition is 0, and the remaining raw materials, amounts and process parameters are the same as those in Example 1.

[0108] Comparative Example 2

[0109] A black photoresist composition and a preparation method thereof, which differs from Example 1 only in that the thermal initiator AIBN is replaced by a photoinitiator TPO, and the remaining raw materials, dosages and process parameters are the same as those in Example 1.

[0110] Comparative Example 3

[0111] A black photoresist composition and a preparation method thereof, which differs from Example 1 only in that the amount of thermal initiator AIBN in the black photoresist composition is 0 g, the amount of OXE-02 is 4.5 g, and the remaining raw materials, amounts and process parameters are the same as those in Example 1.

[0112] Comparative Example 4

[0113] A black photoresist composition and a preparation method thereof, which differs from Example 1 only in that an equal amount of melamine formaldehyde resin is replaced by pentaerythritol, and the remaining raw materials, process parameters and steps are the same as those in Example 1.

[0114] Application Example 1

[0115] A method for using a black photoresist composition, the method comprising:

[0116] The black photoresist composition provided in Example 1 was sprayed on a glass substrate with a thickness of 10 μm to a coating thickness of 4 μm, and then the surface was dried at 60° C. for 5 min and exposed using an ultraviolet photolithography machine with an exposure energy of 100 mJ / cm 2 , wavelength is 365nm, the exposed glass substrate is treated with 1% Na 2 CO 3 After aqueous solution development, final baking was performed at 180° C. for 40 min to obtain a photoresist pattern.

[0117] Application Example 2

[0118] A method for using a black photoresist composition, the method comprising:

[0119] The black photoresist composition provided in Example 2 was spin-coated on a glass substrate with a thickness of 5 μm, and then the surface was dried at 70°C for 3 min, and exposed using an LDI photolithography machine with an exposure energy of 150 mJ / cm 2 , wavelength is 370nm, the exposed glass substrate is developed with 0.5% NaOH aqueous solution, and then final baked at 190°C for 30 minutes to obtain a photoresist pattern.

[0120] Application Example 3

[0121] A method for using a black photoresist composition, the method comprising:

[0122] The black photoresist composition provided in Example 3 was spin-coated on a glass substrate with a thickness of 20 μm to a coating thickness of 6 μm, and then the surface was dried at 80°C for 2 min and exposed using an i-line photolithography machine with an exposure energy of 70 mJ / cm 2, wavelength is 365nm; the developer YS-992 of Guangzhou Yisheng Environmental Protection Technology Co., Ltd. is diluted into a 1% aqueous solution, the exposed glass substrate is developed with a 1% YS-992 aqueous solution, and then finally baked at 190°C for 40 minutes to obtain a photoresist pattern.

[0123] Application Examples 4-8, Comparative Application Examples 1-4

[0124] A method for using a black photoresist composition, which differs from Application Example 1 only in that the black photoresist composition provided in Example 1 is replaced by the black photoresist compositions provided in Examples 4-8 and Comparative Examples 1-4, respectively, and the remaining reagents, process parameters and steps are the same as those in Application Example 1.

[0125] Comparative Application Example 5

[0126] A method for using a black photoresist composition, which differs from Application Example 1 only in that the surface drying temperature is set to 120° C., and the remaining reagents, process parameters and steps are the same as those in Application Example 1.

[0127] Performance Testing

[0128] (1) Observe whether the photoresist patterns of the above application examples and comparative application examples are fully developed within 30 minutes when preparing the photoresist patterns;

[0129] (2) Morphology after final baking: Observe with naked eyes whether the surface of the black photoresist composition in the above application examples and comparative application examples after final baking is flat;

[0130] (3) Boiling ability test: immerse the workpiece in boiling water at 100°C and perform a 100-grid test according to GBT-9286-1998 every 20 hours until the 100-grid value is ≤ 3B. Record the total boiling time.

[0131] (4) Alkaline cleaning agent cleaning ability test: The alkaline cleaning agent YS-121 produced by Guangzhou Yisheng Environmental Protection Technology Co., Ltd. was diluted into a 3% aqueous solution, wherein the alkali content of YS-121 was 20%, and ultrasonically treated in a 3% YS-121 aqueous solution at 55°C for 30 minutes, and then a hundred-grid test was performed in accordance with GBT-9286-1998;

[0132] (5) Anti-aging performance: Use 1.6W / cm 2 The UV aging test chamber uses UVA-340 as the light source. After 300 hours of irradiation, a 100-grid test is performed in accordance with GBT-9286-1998.

[0133] Table 1

[0134]

[0135]

[0136] As can be seen from Table 1, the black photoresist composition provided by the present invention has no cracks on the surface after final baking, the glass substrate does not deform, and can be fully developed within 30 minutes, and has good resistance to water boiling and cleaning with alkaline cleaning agents. The present invention can significantly improve the resistance to water boiling and cleaning with alkaline cleaning agents of the black photoresist composition by using a photoinitiator and a thermal initiator as initiators and a curing agent containing an amino group.

[0137] As can be seen from Application Example 6, the amount of thermal initiator used is too little, the initiation efficiency is insufficient, and the effect is slightly worse than that of Application Example 4; as can be seen from Application Example 7, the amount of amino-containing curing agent used is too little, the curing degree is low, and the content of unreacted carboxyl groups at the tail end of the resin containing vinyl and carboxyl groups is high, and the cleaning ability of alkaline cleaning agents is slightly poor. As can be seen from Application Example 8, the amount of amino-containing curing agent used is too much, the proportion of resin containing vinyl and carboxyl groups in the black photoresist composition is small, the UV curing degree is low, and the performance of the black photoresist composition deteriorates.

[0138] As can be seen from Comparative Application Example 1, without using a thermal initiator, the bottom layer of the black photoresist composition has a low curing degree, uneven curing, poor water boiling resistance, alkaline cleaning agent cleaning resistance and anti-aging performance. The black photoresist composition provided in Comparative Application Example 2 has cracks on the surface and the glass substrate is deformed. This is because Comparative Example 2 uses other cheap photoinitiators instead of thermal initiators. Since the light penetration in the dark photoresist composition is low, the surface curing degree is high and the bottom layer reaction degree is low, so a large amount of internal stress is generated in the thicker black photoresist composition, resulting in surface shrinkage and cracks. At the same time, the internal stress will also cause the glass substrate to bend and deform. The black photoresist composition provided by the present invention uses a thermal initiator, so it reacts uniformly in the final baking, cures uniformly, and has low internal stress, which effectively prevents this defect.

[0139] Although comparative application example 3 has a strong ability to resist water boiling, it uses a large amount of photoinitiators with high photosensitivity. The price of photoinitiators is too expensive, which is 20 to 30 times more expensive than that of thermal initiators. Using thermal initiators to replace part of the photoinitiators can effectively reduce the production cost of the black photoresist composition. As can be seen from comparative application example 4, the curing agent containing amino groups is replaced with an alcohol curing agent, whose curing temperature is higher than that of the curing agent containing amino groups. Under the condition of less than 200°C, it usually does not react. Generally, a catalyst must be added to promote the reaction. Adding a catalyst is equivalent to adding impurities to the final film-forming product, which will affect the performance of the black photoresist composition. Comparative application example 5 increases the surface drying temperature, and it cannot be developed cleanly after exposure, indicating that the surface drying temperature is increased, the thermal initiator begins to initiate the reaction during the surface drying process, and the solvent in the black photoresist composition evaporates too much, resulting in the phenomenon of difficulty in development.

[0140] The applicant declares that the present invention illustrates the black photoresist composition and the use method thereof through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A black photoresist composition, characterized in that: The components of the black photoresist composition include a resin containing vinyl and carboxyl groups, a curing agent containing amino groups, a leveling agent and an initiator; The initiator includes a combination of a photoinitiator and a thermal initiator.

2. The black photoresist composition according to claim 1, characterized in that: The resin containing vinyl and carboxyl groups includes any one of acid-modified novolac epoxy acrylate resin, acid-modified o-cresol epoxy acrylate resin, acid-modified epoxy acrylate resin or bisphenol fluorene modified acrylate resin or a combination of at least two thereof; Preferably, the weight average molecular weight of the resin containing vinyl and carboxyl groups is 3000-30000; Preferably, the acid value of the resin containing vinyl groups and carboxyl groups is 40-150 mgKOH / g.

3. The black photoresist composition according to claim 1 or 2, characterized in that: The amino-containing curing agent includes any one of amino resin, polyurethane, polyaniline, 3,3',5,5'-tetramethylbenzidine or 4,4'-diaminodiphenylmethane, or a combination of at least two thereof, and amino resin is more preferred; Preferably, the amino resin comprises melamine formaldehyde resin; Preferably, the weight average molecular weight of the amino resin, polyaniline and polyurethane is independently 200-5000; Preferably, the mass ratio of the resin containing vinyl and carboxyl groups to the curing agent containing amino groups is (1-4):

1.

4. The black photoresist composition according to any one of claims 1 to 3, characterized in that: The leveling agent includes any one of a fluorine leveling agent, a silicone leveling agent or an acrylic leveling agent, or a combination of at least two thereof; Preferably, the mass percentage of the leveling agent in the black photoresist composition is 0.05-1%; Preferably, the photoinitiator comprises any one of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime) or OXE-03, or a combination of at least two thereof; Preferably, the mass ratio of the photoinitiator to the resin containing vinyl and carboxyl groups is (0.1-0.4):1; Preferably, the decomposition temperature of the thermal initiator is 60-200°C; Preferably, the boiling point of the thermal initiator is 236-350°C; Preferably, the thermal initiator comprises azobisisobutyronitrile and / or dibenzoyl peroxide; Preferably, the mass ratio of the thermal initiator to the photoinitiator is (0.5-2):

1.

5. The black photoresist composition according to any one of claims 1 to 4, characterized in that: The components of the black photoresist composition also include a silane coupling agent; Preferably, the silane coupling agent includes any one or a combination of at least two of aminosilane, epoxysilane, vinylsilane or isocyanate silane; Preferably, the mass ratio of the silane coupling agent to the resin containing vinyl groups and carboxyl groups is (0.05-0.4):

1.

6. The black photoresist composition according to any one of claims 1 to 5, characterized in that: The components of the black photoresist composition also include a black color paste; Preferably, the mass ratio of the black color paste to the resin containing vinyl and carboxyl groups is (1-10):1; Preferably, the components of the black photoresist composition further include a solvent; Preferably, the solvent includes any one or a combination of at least two of propylene glycol methyl ether acetate, ethyl acetate, a dibasic acid ester, isopropanol or isobutanol; Preferably, the mass percentage of the solvent in the black photoresist composition is 50-70%.

7. A method for using the black photoresist composition according to any one of claims 1 to 6, characterized in that: The method of use includes: The black photoresist composition according to any one of claims 1 to 6 is coated on a substrate, and surface drying, exposure, development and final baking are performed in sequence to obtain a photoresist pattern.

8. The method of use according to claim 7, characterized in that: The coating method includes spray coating or spin coating; Preferably, the coating has a thickness of 2-6 μm; Preferably, the surface drying temperature is 60-80°C; Preferably, the surface drying time is 2-5 minutes; Preferably, the exposure light energy is 70-400 mJ / cm 2 ; Preferably, the wavelength of the exposure light is 350-400 nm.

9. The method of use according to claim 7 or 8, characterized in that: The developer used for the development includes any one of a Na2CO3 aqueous solution, a NaOH aqueous solution or a YS-992 aqueous solution or a combination of at least two thereof; Preferably, the final baking temperature is 160-200°C; Preferably, the final baking time is 30-60 minutes; Preferably, the minimum decomposition temperature of the thermal initiator in the black photoresist composition is ≤ the surface drying temperature ≤ the minimum decomposition temperature of the thermal initiator + 20°C; The minimum decomposition temperature of the thermal initiator + 100°C ≤ the final baking temperature ≤ the boiling point of the thermal initiator - 30°C.

10. Use of the black photoresist composition according to any one of claims 1 to 6 in a display device.

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