Black photoresist composition and preparation method therefor, and black bezel manufacturing process

Abstract

The present application belongs to the technical field of photoresists. Disclosed are a black photoresist composition and a preparation method therefor, and a black bezel manufacturing process. The black photoresist composition comprises the following components in parts by weight: 2-20 parts of a bisphenol fluorene acrylic resin, 1-10 parts of a tertiary amine resin containing β-H atoms, 0.1-2 parts of an auxiliary A, 0.2-5 parts of an auxiliary B, 0.5-2 parts of a photoinitiator, 5-10 parts of a light-cured resin monomer, 10-50 parts of a black coloring agent, and 50-500 parts of a polar organic solvent.

Description

Black photoresist composition and preparation method thereof and black frame manufacturing process

[0001] Related applications

[0002] This application claims priority to Chinese patent application No. 202410464312.1 filed on April 17, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present application relates to the field of photoresist technology, and in particular to a black photoresist composition, a preparation method thereof, and a black frame manufacturing process. Background Art

[0004] Existing smart car display cover panels often feature a patterned light-shielding film layer, such as a black matrix and black columnar spacers, along their edges. This light-shielding film layer serves as the black border of the smart car display cover panel. This black border prevents light leakage from the cover panel's edges and blocks light.

[0005] Currently, pad printing, UV curing ink, and LDI photolithography processes can all form specific shapes on flat cover panels. The LDI photolithography process uses black photoresist sprayed on the curved cover panel, and then forms a black border through direct laser imaging.

[0006] However, the application of flat-surface sprayed black photoresist on curved cover plates has certain limitations. Shrinkage holes will appear during film formation, and a good film surface cannot be formed. The uneven film surface causes the shading rate at the weak points of the film surface to fail to meet the requirements.

[0007] Therefore, improvements are needed in the black photoresist used in the spray coating of curved cover plates. Summary of the Invention

[0008] The main purpose of this application is to provide a black photoresist composition, which aims to solve the technical problem that when a flat-surface sprayed black photoresist is applied on a curved cover plate, shrinkage holes will appear during film formation, and a good film surface cannot be formed. The film surface is uneven, resulting in the shading rate at the weak parts of the film surface failing to meet the requirements.

[0009] To achieve the above-mentioned object, the present application provides a black photoresist composition, which comprises an alkali-soluble photopolymer resin, a photocurable resin monomer, an auxiliary agent A, an auxiliary agent B, a photoinitiator, a thermal initiator, a black colorant, and a polar organic solvent;

[0010] Among them, the photopolymer resin includes two types of resins: bisphenol fluorene acrylic resin and tertiary amine resin containing β-H atoms;

[0011] In parts by weight, the black photoresist composition includes 2 to 20 parts of the bisphenol fluorene acrylic resin, 1 to 10 parts of the tertiary amine resin containing β-H atoms, 0.1 to 2 parts of auxiliary agent A, 0.2 to 5 parts of auxiliary agent B, 0.5 to 2 parts of the photoinitiator, 5 to 10 parts of the photocurable resin monomer, 10 to 50 parts of the black colorant and 50 to 500 parts of the polar organic solvent.

[0012] In one embodiment, the bisphenol fluorene acrylic resin is selected from one or more compounds shown in formula (I);

[0013] wherein n is an integer from 10 to 180; R1 and R3 are CH2; R2 and R4 are OH; X and W are A is selected from H or C1-2 alkyl.

[0014] A method for preparing a bisphenol fluorene acrylic resin, comprising the following steps:

[0015] (a) Synthetic intermediate: A compound represented by structural formula (I-2) is produced by ring-opening polymerization of a monomer represented by structural formula (I-1) and an acrylic compound;

[0016] (b) Synthesis of the product: Continue to dropwise add the acrylic acid compound to the intermediate of the above structural formula (I-2) under nitrogen to react to produce the structural formula (I);

[0017] (c) Product post-treatment: When the reaction of the intermediate of formula (I-2) is complete, the product is transferred to a round-bottom flask while hot for purification to obtain a milky white powder resin, which is then dried.

[0018] Specifically, in the above scheme, the acrylic compound is one of methacrylic acid, ethylacrylic acid, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, butyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, tricyclo[5.2.1.02,6]dec-8-yl methacrylate, hydroxyethyl methacrylate, and hydroxybutyl acrylate.

[0019] Further, in the preparation method, the step (a) for preparing the intermediate is as follows: the monomer represented by the structural formula (I-1) and the acrylic compound are mixed in a molar ratio of 1: (2-4), the acrylic compound is added into the monomer represented by the structural formula (I-1), then 1% of tetramethylammonium chloride and 0.5% of phenol based on the total mass of the monomer represented by the structural formula (I-1) and the acrylic compound are added in sequence, the solution is dissolved completely under nitrogen protection at 90°C for 30 min, then the solution is heated to 130°C for continuous reaction, the acid value is determined during the reaction, the reaction is stopped after the solution acid value is less than 2.0 mg, and the intermediate compound is obtained by distillation under reduced pressure.

[0020] In one embodiment, the tertiary amine resin containing a β-H atom is selected from one or more of the compounds represented by the general formula (II):

[0021] wherein R is A is selected from H or C1-2 alkyl; R1 is selected from -CH3, R2 is selected from phenyl (II-1), benzyl (II-2), and phenol group (II-3)

[0022] In one embodiment, the mass ratio of the bisphenol fluorene acrylic resin to the tertiary amine resin containing a β-H atom is in the range of 1:1 to 5:1.

[0023] In one embodiment, the photoinitiator is a carbazyl oxime ester compound, and the photoinitiator is selected from one or more of the compounds represented by the general formula (III):

[0024] wherein R1 is selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, R2 is selected from R3 is selected from -H, -CH3,

[0025] R4 is selected from -CH3, -CH2CH3, In one embodiment, the photoinitiator is:

[0026] In one embodiment, the photoinitiating resin monomer is an acrylic resin, and the photoinitiating resin monomer is selected from one or more of the compounds represented by the general formula (IV) (V):

[0027] R1 is selected from R2 is selected from -H, The mass ratio of the photoinitiator to the photocuring resin monomer ranges from 1:100 to 2:5.

[0028] In an embodiment, the photocuring resin monomer is an oligomer crosslinking agent containing double bonds, and the mass fraction of the photocuring resin monomer is 5-30 parts. The photocuring resin monomer is one or a mixture of several of pentaerythritol triacrylate, pentaerythritol tetraacrylate, 3-hydroxymethyl pentaerythritol triacrylate, 3-hydroxyethyl pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. The photocuring resin monomer opens the double bond into a network crosslinking in the presence of free radicals. If the mass fraction of the photocuring resin monomer is less than 5 parts, the crosslinking density of the photoresist is insufficient, affecting the transition of the material from thermoplastic resin to thermosetting. In this application, if the mass fraction of the photocuring resin monomer is greater than 30 parts, the photoresist is crosslinked too much, the CD value is too high, and the CD Loss precision cannot be controlled. The specific structure of the photocuring resin monomer is shown in IV-1, IV-2, IV-3, V-1, and V-2.

[0029] In an embodiment, the polar organic solvent is a medium-polar and strong-polar organic aprotic polar solvent, which is generally one or more of ethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, triethoxy methacrylate, acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, and butyl butyrate, and the mass ratio to the photocuring resin monomer is between 5:1 and 100:1, preferably between 10:1 and 80:1, and more preferably between 20:1 and 70:1.

[0030] In an embodiment, the black colorant is selected from one or more of cyanine black, aniline black, carbon black, titanium black, and graphite black. In this application, the black colorant can also be a mixed color organic pigment obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, and magenta, so as to be approximately black.

[0031] The black colorant is preferably carbon black particles, the size of the carbon black particles is 100-200 nm, and the mass ratio of the carbon black particles to the photocuring resin monomer ranges from 10:1 to 1:1.

[0032] In the present application, the carbon black particles can be, for example, Printex L6, Printex L, Printex 55, Printex 45, Printex 60, Special Black 550, Special Black 350, Printex 35, Special Black 250, Printex 25, Special Black 100, Printex 200, Hiblack 30, Hiblack 30L from DEGUSSA, Raven 1255, Raven 1200, Raven 1170, Raven 1100 Ultra, Raven 1060 Ultra, Raven 1040, Raven 1035, Raven 1020, Raven 1000, Raven 890, Raven 860 Ultra, Raven 850, Raven 820, Raven 760 Ultra, Raven 460, Raven 450, Raven 410, Raven H.20, Raven 8250B, Raven 6800B from Columbian, R99R, R250R, R330R, R400R, R660R, ML, DL430, etc. from CABOT.

[0033] In one embodiment, the auxiliary agent A contains a perfluorinated substituted vinylic monomer selected from the compounds shown in general formula (VI);

[0034] wherein R1, R2, R3, R4 are selected from -CF3, wherein one of.

[0035] The specific structure of the perfluorinated substituted vinylic monomer is as follows:

[0036] In one embodiment, the auxiliary agent B contains at least one aromatic peroxide, which can participate in the Cope elimination reaction with the β-H atom tertiary amine resin during the post-lithography curing and participate in the photopolymerization curing, and the aromatic peroxide is selected from the compounds shown in general formula (VII);

[0037] wherein R5 is selected from -Cl, -Br, one of. The specific structure of the aromatic peroxide is as follows

[0038] In one embodiment, the thermal initiator contains a bis-imidazole compound selected from the compounds shown in general formula (VIII);

[0039] Wherein, R1, R2 are independently selected from one of -H, methyl, ethyl, bromine or chlorine. The specific structure of the bis-imidazole compound is as follows:

[0040] In an embodiment, the preparation method comprises the following steps:

[0041] (1) Preparation of black color paste: wet grinding the black colorant in a sand mill with 0.05mm to 0.1mm size zirconium balls, and adding the bis-phenyl fluorene acrylic resin composition as a stabilizing resin during the grinding process to obtain a black color paste;

[0042] (2) Preparation of photosensitive liquid: mixing and dispersing the tertiary amine resin containing β-H atom, the photocurable resin, the photoinitiator, the auxiliary A, the auxiliary B, and the polar organic solvent according to the formula amount to form a solution, and then filtering to obtain a photosensitive liquid;

[0043] (3) Preparation of black photoresist composition: mixing the black color paste in step (1) and the photosensitive liquid in step (2), and finally adding an organic solvent to adjust the viscosity, and then dispersing in a dispersion machine to form a uniform solution, and then filtering to obtain.

[0044] The application also provides an application of any of the above black photoresist in the field of intelligent automobile display arc cover plate.

[0045] The application also provides a black frame manufacturing process of an arc display glass-based cover plate, comprising the following steps:

[0046] S11: Spraying the first layer of black photoresist as described above on the hot-bent arc glass substrate in the x direction by inkjet process, and pre-baking to form a layer of 1-3μm thick black glue film;

[0047] S12: Exposing the frame pattern part by LDI laser direct writing photoetching, and then washing away the black photoresist inside the frame by developing process, and then hardening after post-baking to form the first layer of black frame;

[0048] S13: Spraying the second layer of black photoresist as described above on the arc substrate with the first layer of black frame in the y direction by inkjet process, and pre-baking to form a second layer of 1-3μm thick black glue film;

[0049] S14: Exposing the frame pattern part by LDI laser direct writing photoetching again, and then washing away the black photoresist inside the frame by developing process, and then hardening after post-baking to form the second layer of black frame;

[0050] The post-baking temperature in S12 and S14 is 200-250℃.

[0051] The application can achieve the following beneficial effects:

[0052] The black photoresist of the present application has the advantages of resistance to acid, alkali, solvent and stripping liquid, and copper etching liquid after film curing; resistance to 25-280℃ metal plating film; the square resistance is stable at 5.0*10 12 The black photoresist of the present application has the advantages of resistance to acid, alkali, solvent and stripping liquid, and copper etching liquid after film curing; resistance to 25-280℃ metal plating film; the square resistance is stable at 5.0*10 BRIEF DESCRIPTION OF DRAWINGS

[0053] Fig. 1 is a process flow diagram for manufacturing a black frame of a curved display glass substrate according to the present application;

[0054] Fig. 2 is a process flow diagram for black UV curing ink;

[0055] Fig. 3 is a process flow diagram for pad printing ink;

[0056] Fig. 4 is a developed appearance diagram of a black frame prepared according to Example 1 of the present application;

[0057] Fig. 5 is a developed appearance diagram of a black frame prepared according to Example 2 of the present application;

[0058] Fig. 6 is a film thickness diagram of a black frame prepared according to the black UV curing ink process;

[0059] Fig. 7 is an appearance diagram of a black film surface prepared according to Example 2 of the present application;

[0060] Fig. 8 is an appearance diagram of a black film surface prepared according to Example 3 of the present application subjected to weather resistance test;

[0061] Fig. 9 is an appearance diagram of a black film surface prepared according to Example 1 of the present application subjected to development.

[0062] The implementation, functional features and advantages of the present application will be further described with reference to the accompanying drawings. DETAILED DESCRIPTION

[0063] It should be understood that the specific embodiments described herein are merely illustrative of the present application and should not be used in a limiting sense.

[0064] In order for those skilled in the art to better understand the present application, the present application will be described more fully below.

[0065] A black photoresist composition, the photoresist composition comprising an alkali-soluble photopolymerizable resin, a photo-curing resin monomer, an additive A, an additive B, a photoinitiator, a thermal initiator, a black colorant, a polar organic solvent.

[0066] In one embodiment, the black photoresist composition includes 2-20 parts by weight of the bisphenol fluorene acrylic resin, 1-10 parts by weight of the tertiary amine resin containing β-H atom, 0.5-2 parts by weight of the photoinitiator, 5-10 parts by weight of the photocurable resin monomer, 10-50 parts by weight of the black colorant, and 50-500 parts by weight of the polar organic solvent.

[0067] The photopolymerizable resin is a component that imparts photopolymerizability and film-forming ability to the black photoresist. In consideration of photopolymerizability, alkali developability, and adhesion, the photopolymerizable resin is an alkali-soluble epoxy acrylate containing an unsaturated double bond. Further, in consideration of the properties of the black photoresist, the photopolymerizable resin is an alkali-soluble epoxy acrylate including a bisphenol fluorene group and a tertiary amine resin containing a β-H atom.

[0068] In one embodiment, the mass ratio of the bisphenol fluorene acrylic resin to the tertiary amine resin containing a β-H atom ranges from 1:1 to 5:1.

[0069] The present application also provides a preparation method of a bisphenol fluorene acrylic resin, which includes the following steps:

[0070] (a) synthesis of an intermediate: a compound represented by structural formula (I-2) is generated by ring-opening polymerization reaction of a monomer represented by structural formula (I-1) and an acrylic compound;

[0071] (b) synthesis of a product: the acrylic compound is continuously added dropwise to the intermediate of structural formula (I-2) under nitrogen, and a reaction generates structural formula (I);

[0072] (c) post-treatment of the product: when the reaction of the intermediate of structural formula (I-2) is completed, the product is transferred into a round-bottom flask for purification while hot, monitored by a spot chromatography plate, to obtain a milky white powder resin, which is dried, and the process is completed.

[0073] Specifically, in the above scheme, the acrylic compound is one or more of methyl methacrylate, ethyl acrylate, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, butyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, tricyclo[5.2.1.02,6]dec-8-yl methacrylate, hydroxyethyl methacrylate, and hydroxybutyl acrylate.

[0074] Further, in the preparation method, the step (a) for preparing the intermediate is as follows: the monomer represented by the structural formula (I-1) and the acrylic compound are mixed in a molar ratio of 1: (2-4), the acrylic compound is added into the monomer represented by the structural formula (I-1), then 1% of tetramethylammonium chloride and 0.5% of phenol based on the total mass of the monomer represented by the structural formula (I-1) and the acrylic compound are sequentially added, the solution is dissolved completely under nitrogen protection at 90°C for 30 min, then the solution is heated to 130°C for continuous reaction, the acid value is determined during the reaction, the reaction is stopped after the solution acid value is less than 2.0 mg, and the intermediate compound is obtained by distillation under reduced pressure.

[0075] Of course, the epoxy resin with a fluorene group can be purchased from a commercial product or prepared by referring to the method disclosed in the patent with the publication number CN110066382A.

[0076] In an embodiment, the fluorene-based acrylic resin is selected from one or more of the compounds represented by the general formula (I).

[0077] wherein n is an integer of 10-180; R1 and R3 are CH2; R2 and R4 are OH; X and W are A is selected from H or C 1～2 alkyl.

[0078] The tertiary amine resin containing a β-H atom is selected from one or more of the compounds represented by the general formula (II).

[0079] wherein R is A is selected from H or C 1～2 R1 is selected from -H, -CH3, R2 is selected from phenyl, benzyl, and phenol group. The CAS number of the tertiary amine resin containing a β-H atom is 13206-64-9. The specific structure of the tertiary amine resin containing a β-H atom is as follows:

[0080] In an embodiment, the mass ratio of the fluorene-based acrylic resin to the tertiary amine resin containing a β-H atom is in the range of 1:1 to 5:1.

[0081] In an embodiment, the photoinitiator comprises a carbazyl oxime ester compound, and the photoinitiator is selected from one or more of the compounds represented by the general formula (III).

[0082] wherein R1 is selected from -H, -CH3, R2 is selected from R3 is selected from

[0083] R4 is selected from

[0084] In an embodiment, the photo-curable resin monomer is selected from one or more of the compounds shown in general formula (IV) (V);

[0085] R1 is selected from R2 is selected from -H, The mass ratio of the photo-initiator to the photo-curable resin monomer is in the range of 1:100 to 2:5.

[0086] Specifically, the photo-initiator containing carbazolyl oxime ester compound can be OXE-2, which can be obtained by purchasing commercially available products.

[0087] In an embodiment, the photo-curable resin monomer is one or a mixture of several of pentaerythritol triacrylate, pentaerythritol tetraacrylate, 3-hydroxymethyl pentaerythritol triacrylate, 3-hydroxyethyl pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate, which opens the double bond into a network crosslinking in the presence of free radicals. In the present application, if the mass fraction of the photo-curable resin monomer is higher than 30 parts, it will cause the photoresist to be crosslinked too much, the CD value to be too high, and the CD Loss precision to be uncontrollable. The specific structure of the photo-curable resin monomer is shown in IV-1, IV-2, IV-3, V-1, and V-2.

[0088] In the present application, the photo-curable resin monomer undergoes a photo-polymerization reaction under the action of the photo-initiator carbazolyl oxime ester compound to generate an organic polymer structure with a three-dimensional crosslinking structure, which can improve the crosslinking degree of the photoresist, thereby improving the stability, corrosion resistance, and heat resistance of the black frame.

[0089] In the present application, the black colorant is required to have better heat resistance, light resistance and solvent resistance. In an embodiment, the black colorant can be selected from black organic pigments such as perylene black, cyanine black, aniline black and the like. The black colorant can also be a mixed color organic pigment obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like to make it approximately black. The black colorant can also be selected from one or more of carbon black, titanium black, graphite black. The black colorant in the present application can also be dispersed using a dispersant to obtain better coloring effect. The dispersant can be an anionic, cationic, nonionic, amphoteric, fluorine-based surfactant and the like.

[0090] In an embodiment, the black colorant is carbon black particles, the size of the carbon black particles is 100 nm to 200 nm, and the mass ratio of the carbon black particles to the photocurable resin monomer is in the range of 10: 1 to 1: 1.

[0091] In the present application, the carbon black particles can be, for example, Printex L6, Printex L, Printex 55, Printex 45, Printex 60, Special Black 550, Special Black 350, Printex 35, Special Black 250, Printex 25, Special Black 100, Printex 200, Hiblack 30, Hiblack 30L from DEGUSSA, Raven 1255, Raven 1200, Raven 1170, Raven 1100 Ultra, Raven 1060 Ultra, Raven 1040, Raven 1035, Raven 1020, Raven 1000, Raven 890, Raven 860 Ultra, Raven 850, Raven 820, Raven 760 Ultra, Raven 460, Raven 450, Raven 410, Raven H.20, Raven 8250B, Raven 6800B from Columbian, R99R, R250R, R330R, R400R, R660R, ML, DL430 from CABOT and the like.

[0092] In an embodiment, the auxiliary agent A contains a perfluorinated substituted vinyl monomer selected from the compounds shown in general formula (VI);

[0093] wherein R1, R2, R3, R4 are selected from, One of them. The perfluorosubstituted ethylene monomer is specifically structured as follows:

[0094] In this application, the auxiliary agent A can significantly change the surface tension, viscosity, and leveling property of the photoresist solvent system, and improve the spray application performance. Moreover, under the action of the photoinitiator, fluorine groups are introduced during polymerization, similar to the structure as follows, and a small amount of fluorine-containing polymer structure can improve the weather resistance of the light shielding film layer formed after curing of the black photoresist.

[0095] In an embodiment, the auxiliary agent B comprises at least one aromatic peroxide selected from the compounds shown in general formula (VII);

[0096] wherein R5 is selected from one of -F, -Cl, and -Br. The aromatic peroxide is specifically structured as follows:

[0097] In this application, during the curing process after lithography, the auxiliary agent B can undergo Cope elimination reaction with the β-H atom tertiary amine resin to participate in photopolymerization and curing. The β-H atom tertiary amine resin that undergoes Cope elimination reaction to obtain a resin containing unsaturated bonds can also polymerize with the remaining unreacted photo-cured resin monomer, thereby improving the crosslinking density. When R1 in the structure shown in (II) is a C2 alkane carbon chain, if it occurs on the right side, ethylene monomer will be generated to participate in the photo-activated monomer, thereby providing a smaller molecular weight for the copolymer, as shown in the following reaction:

[0098] When R2 is C1 and H, there is no group that can undergo COPE elimination on the right side, so the reaction will occur on the left side, generating an unsaturated olefin with a molecular weight greater than 3, thereby providing a longer carbon chain, as shown in the following reaction:

[0099] In an embodiment, the thermal initiator comprises a bis-imidazole compound selected from the compounds shown in general formula (VIII);

[0100] wherein R1 and R2 are independently selected from one of -H, -Cl, and -Br. The bis-imidazole compound is specifically structured as follows:

[0101] The double bond of the photo-cured resin monomer is opened under the action of the bis-imidazole initiator to perform thermal polymerization reaction:

[0102] The left side of the right side of the reaction formula is the thermal polymerization of the short carbon chain ethylene generated after the COPE elimination reaction. The right side of the right side of the reaction formula is a long carbon chain that can be distinguished according to the COPE elimination above.

[0103] Specifically, the thermal initiator containing the bis-imidazole compound can be B-CIM, which can be obtained by purchasing a commercially available product.

[0104] In the present application, the combination of oxime ester photoinitiator and bis-imidazole thermal initiator improves the crosslinking density of the resin during polymerization.

[0105] Moreover, the use of bis-imidazole thermal initiator in the present application enables the residual unsaturated bond of the black photoresist composition to continue to polymerize at the temperature of the post-baking process in the black frame manufacturing process, thereby improving the crosslinking degree and optimizing the weather resistance of the cured film.

[0106] In an embodiment, the polar organic solvent is a ketone solvent or an ester solvent in an aprotic polar solvent, which has low viscosity and the advantage of complete removal after post-baking. In an embodiment, the polar organic solvent is an organic aprotic polar solvent with medium and strong polarity, which is generally one or more of ethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, triethoxymethyl acrylate, acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, and the mass ratio of the photo-curable resin monomer is between 5:1 and 100:1, preferably between 10:1 and 80:1, and more preferably between 20:1 and 70:1. The use of the aprotic polar solvent has a significant solvent effect on the Cope elimination reaction, and the Cope elimination reaction rate can be improved by millions of times, thereby improving the double bond formation rate of the Cope elimination reaction. Furthermore, the viscosity of the black photoresist can be adjusted to improve its sprayability.

[0107] The present application also provides a preparation method of the above-mentioned photoresist composition, which comprises the following steps:

[0108] (1) Preparation of black paste: wet grinding of the black colorant is carried out in a sand mill with 0.05mm-0.1mm size zirconium balls, and the bisphenol fluorene acrylate resin composition is added as a stabilizing resin during the grinding process to obtain the black paste;

[0109] (2) Preparation of photosensitive liquid: the tertiary amine resin containing β-H atoms, the photo-curable resin, the photoinitiator, the auxiliary A, the auxiliary B, and the polar organic solvent are mixed and dispersed into a solution according to the formula amount, and then filtered to obtain the photosensitive liquid;

[0110] (3) Preparation of black photoresist composition: mix the black color paste in step (1) and the photosensitive solution in step (2), and finally supplement organic solvent to adjust the viscosity, disperse into a uniform solution in a dispersing machine, and obtain after filtration.

[0111] The application also provides an application of the above-mentioned black photoresist in the field of intelligent automobile display curved cover plates. It can be understood that the black photoresist composition of the application can also be applied to other processes requiring a black frame, such as a tablet computer.

[0112] Referring to FIG. 1, the application further provides a manufacturing process of a black frame of a curved display glass-based cover plate, comprising the following steps:

[0113] S11: Spraying a first layer of the black photoresist described above on the hot-bent curved glass substrate in the x direction by an inkjet process, and pre-baking to form a 1-3 μm thick black glue film of the first layer;

[0114] S12: Exposing the frame pattern part by LDI laser direct writing lithography, and after the black photoresist in the frame is washed away by a developing process, post-baking to harden to form the first layer of black frame;

[0115] S13: Spraying a second layer of the black photoresist described above on the curved substrate with the first layer of black frame in the y direction by an inkjet process, and pre-baking to form a 1-3 μm thick black glue film of the second layer;

[0116] S14: Exposing the frame pattern part by LDI laser direct writing lithography again, and after the black photoresist in the frame is washed away by a developing process, post-baking to harden to form the second layer of black frame;

[0117] The post-baking temperature in S12 and S14 is 200-250°C.

[0118] Laser direct writing lithography (LDI) is a technology that directly acts on photoresist with a computer-controlled laser beam to form a fine pattern. Unlike traditional lithography technology, it does not need to use a physical mask, thereby saving cost and shortening the production cycle. The working principle of the technology is that the laser beam generated by a laser is controlled by a scanning system to perform accurate scanning exposure on the surface of the photoresist, so that the molecular chains on the photoresist undergo polymerization reaction under laser irradiation to form the required pattern. Laser direct writing lithography can realize high-precision pattern transfer, and is suitable for special lithography application scenarios with substrate warping or substrate deformation.

[0119] In the black frame manufacturing process of the present application, the resin in the black photoresin composition cannot be completely polymerized and cured due to the use of LDI laser direct writing process with lower energy than the black UV curing ink process. However, the use of the bis-imidazole thermal initiator in the present application allows the remaining unsaturated bonds in the black photoresin composition to continue to polymerize and secondarily cure at the temperature of the post-baking process in the black frame manufacturing process, thereby improving the crosslinking degree and optimizing the weather resistance of the cured film. Moreover, the combination of the oxime ester photoinitiator and the bis-imidazole thermal initiator improves the crosslinking density of the resin during polymerization.

[0120] In summary, in the present application, the bisphenol fluorene acrylic resin, the tertiary amine resin containing β-H atoms, and the photocured resin monomer undergo polymerization reaction in the LDI laser direct writing process under the action of the additive A and the additive B, the photoinitiator, and the thermal initiator, and finally obtain a black frame. The aromatic peroxide in the additive B can undergo Cope elimination reaction with the tertiary amine resin containing β-H atoms and participate in photopolymerization and curing. At the same time, in the post-baking process, thermal polymerization reaction occurs under the action of the bis-imidazole thermal initiator, the tertiary amine resin containing β-H atoms undergoes crosslinking polymerization with the additive A, introduces fluorine groups, improves the weather resistance of the light shielding film formed after curing, improves the crosslinking density of the resin, and optimizes the performance after curing. Moreover, the Cope elimination reaction of the tertiary amine resin containing β-H atoms produces a resin containing unsaturated bonds, which can also undergo polymerization with the remaining unreacted photocured resin monomer, thereby improving the crosslinking density. The polar solvent is an aprotic polar solvent, and the use of the aprotic polar solvent can improve the Cope elimination reaction rate by millions of times.

[0121] Finally, the black photoresin of the present application has the advantages of resistance to acid and alkali, solvents, and stripping solution and copper etching solution; resistance to 25-280°C metal plating film; and stable square resistance of 5.0 x 10 12 The sprayed arc glass cover plate has good uniformity, and the minimum precision of the developed film after the photoetching process can reach 3 μm. The black frame produced has no burr "sawtooth", has high light shielding rate, and has low film thickness, which can reduce the amount used in the production process.

[0122] Example 1

[0123] The present embodiment provides a black photoresist composition, which comprises 100 parts of the bisphenol fluorene acrylic resin, 50 parts of the β-H atom tertiary amine resin, 5 parts of the photoinitiator b-1, 5 parts of the thermal initiator b-2, 50 parts of the photocuring resin monomer, 180 parts of the carbon black colorant, 50 parts of the solvent e-1, 50 parts of the solvent e-2, 100 parts of the solvent e-3, 0.2 parts of the auxiliary agent A, and 2 parts of the auxiliary agent B, by weight.

[0124] The black colorant is wet ground in a sand mill with 0.05mm-0.1mm size zirconium balls and organic solvent, and the bisphenol fluorene acrylic resin composition is added as a stabilizing resin during the grinding process to obtain a black color paste.

[0125] The β-H atom containing tertiary amine resin, the photocuring resin, the photoinitiator, the auxiliary agent A, the auxiliary agent B, and the polar organic solvent are mixed and dispersed into a solution according to the formulation amounts, and then filtered to obtain a photosensitive liquid.

[0126] The black color paste and the photosensitive liquid are mixed, and finally organic solvent is added to adjust the viscosity, and then dispersed into a uniform solution in a dispersing machine, and filtered to obtain a black photoresist composition.

[0127] Examples 2-12

[0128] The black photoresist is prepared in the same manner as in Example 1, except that the composition ratio is as shown in Table 1.

[0129] Table 1:

[0130] The black photoresist compositions obtained in Examples 1-12 are spin-coated onto a glass substrate, baked at 100°C for 2min to form a gel film with a film thickness of less than 5 microns on the glass substrate, and then exposed to light using a photomask at an energy of 60mJ / cm 2 , and then developed in a 0.045% KOH solution for 90s, and then baked at 200°C for 30min to obtain black photoresist coating layers 1-12.

[0131] Comparative Example 1

[0132] Black UV curing ink process

[0133] S21, a first layer of black photoresist is coated on a planar glass substrate using a coating process to form a layer of black gel film with a film thickness of 1-3 microns, wherein the black photoresist is a commercially available product.

[0134] S22, mask the non-exposed area with Masker, and expose the area outside the Masker.

[0135] S23, after the black photoresist in the frame is washed away by the developing process, the first layer of black frame is formed after post-baking (Post-bake) hardening.

[0136] Referring to FIGS. 2 and 6, the film thickness of the black frame prepared by the black UV-cured ink process reaches 11.7 um.

[0137] Comparative Example 2

[0138] Pad printing ink process

[0139] S31, after the arc surface display glass base cover plate is cleaned and dried.

[0140] S32, pad printing ink is applied to the black light-shielding area where film is needed using a pad printing gun head, and then post-baking (Post-bake) is performed for curing. The details of the pad printing ink process can be referred to FIG. 3 and Chinese Patent CN 114537005 A, which will not be described in detail here.

[0141] The appearance, OD density, film thickness, surface resistance, and tensile strength of the prepared black photoresist composition coatings 1-12 were tested. The test results are shown in Table 2.

[0142] The test method is as follows:

[0143] The appearance of the black photoresist coating was determined by visual inspection.

[0144] OD density: The OD density of the black photoresist composition coatings 1-12 obtained in Examples 1-12 was tested using a densitometer LS117 at 5 points per sample under normal temperature and pressure conditions, with ink thickness <15 um.

[0145] Film thickness: Step film thickness meter (Japan small plate ET200A-3D step meter) or probe film thickness meter was used.

[0146] Surface resistance: The resistivity of the ink of the black photoresist composition coatings 1-12 obtained in Examples 1-12 was tested using an impedance meter ACL-800 at 5 points under normal temperature and pressure conditions.

[0147] Tensile strength: The test was performed using a European spectrum OU4080 tensile adhesion tester.

[0148] Table 2:

[0149] The resistivity, dyne value, OD, grid test, surface hardness, water boiling test, alcohol resistance test, alkali resistance test, acid resistance test, high temperature and humidity test, high temperature test, and low temperature test were performed on the black photoresist composition coatings 1 to 12. The test results are shown in Table 3. The test methods are as follows:

[0150] Surface resistance: The resistivity of the black photoresist composition coatings 1 to 12 obtained in Examples 1 to 12 was tested using an impedance meter ACL-800 at room temperature and pressure.

[0151] Dyne value: The dyne value of the black photoresist composition coatings 1 to 12 obtained in Examples 1 to 12 was tested using a dyne pen at room temperature and pressure. The pen cap was removed, the pen face was parallelly contacted with the silk screen face, and a 5 cm long line was drawn on the ink face. After 2 seconds, the observation was performed.

[0152] OD density: The OD density of the black photoresist composition coatings 1 to 12 obtained in Examples 1 to 12 was tested using a densitometer LS117 at room temperature and pressure. The ink thickness was < 15 μm.

[0153] Grid test: The grid test was performed on the black photoresist composition coatings 1 to 12 obtained in Examples 1 to 12 at room temperature and pressure. The grid knife was formed at an angle of 15° to 30° with the glass film layer, and the knife tip was contacted with the glass film layer with sufficient force. The grid knife was moved on the glass film layer to cross the lines, and the surface of the glass film layer was cleaned with a brush and rubbed with fingers to remove the bubbles and wrinkles between the adhesive tape and the film layer. However, the force should not be too large. After 90 ± 30 seconds, the adhesive tape was slowly peeled off at an angle of 180°, and then the peeling was observed.

[0154] Surface hardness: The pencil method was used to test the surface hardness of the black photoresist composition coatings 1 to 12 obtained in Examples 1 to 12. A pencil with a hardness of 3H and a load of 500 g was used to draw 5 lines at different positions at a test angle of 45°. The scratches were observed.

[0155] Water boiling test: The water boiling test was performed on the black photoresist composition coatings 1 to 12 obtained in Examples 1 to 12 using a water bath. The samples were placed in a constant temperature water bath at 100°C for 1 h. After the test was completed, the grid test was performed, and the peeling was observed.

[0156] Alcohol resistance test: The alcohol resistance test was performed on the black photoresist composition coatings 1 to 12 obtained in Examples 1 to 12 using a dust-free cloth dipped in alcohol. The abrasion tester was loaded with 1000 g, and the test was performed for 50 times. The peeling was observed.

[0157] Alkali resistance test: 5% NaOH solution was dropped on the surface of the black photoresist composition coating 1 to 12 obtained from Examples 1 to 12, and the appearance was observed after standing for 24 hrs, and the cross test was performed, and then the peeling was observed.

[0158] Acid resistance test: 5% H2SO4 solution was dropped on the surface of the black photoresist composition coating 1 to 12 obtained from Examples 1 to 12, and the appearance was observed after standing for 24 hrs, and the cross test was performed, and then the peeling was observed.

[0159] High temperature and high humidity test: the black photoresist composition coating 1 to 12 obtained from Examples 1 to 12 was subjected to structure adhesive and partial structure parts, and then was placed in a constant temperature and humidity test chamber at 85°C / 85% RH for 1000 hrs, and after taking out and recovering at room temperature for 2 hrs, the test was performed.

[0160] High temperature test: the black photoresist composition coating 1 to 12 obtained from Examples 1 to 12 was subjected to structure adhesive and partial structure parts, and then was placed in a constant temperature test chamber at 90°C for 1000 hrs, and after taking out and recovering at room temperature for 2 hrs, the test was performed.

[0161] Low temperature test: the black photoresist composition coating 1 to 12 obtained from Examples 1 to 12 was subjected to structure adhesive and partial structure parts, and then was placed in a constant temperature test chamber at -40°C for 1000 hrs, and after taking out and recovering at room temperature for 2 hrs, the test was performed.

[0162] Table 3:

[0163] Referring to FIG. 4 and FIG. 5, FIG. 4 and FIG. 5 are appearance diagrams of the black photoresist composition coating prepared from Example 1 and Example 2, respectively, and developed in 0.045% KOH solution, and it can be seen that the black frame prepared by using the black photoresist composition of the present application is developed clearly without residue.

[0164] Referring to FIG. 7, the black film layer in FIG. 7 is the finished product prepared by lacking the additive A in Example 2, and the white part in the upper right corner in FIG. 7 is the part of the black film layer lacking the additive A, which is not smooth. Since the additive A is lacking in Example 2, the black photoresist prepared in Example A has poor leveling, which causes the black film layer to have the phenomenon that part of the black film layer is not smooth.

[0165] Referring to FIG. 8, the black film layer in FIG. 8 is the finished product prepared by lacking the additive B in Example 3, and the white part in FIG. 8 is the area where the film surface is peeled off after the weather resistance test is performed on the black film surface prepared in Example 3. Since the additive B is lacking in Example 3, the adhesion of the black film surface prepared in Example 3 is weakened, which performs poorly in the weather resistance test.

[0166] Referring to FIG. 9, the black film layer in FIG. 9 is the finished product prepared by adding the auxiliary agent A and the auxiliary agent B in Example 1. The white area in FIG. 9 is the blank area after development, and it can be seen that there is no burr "sawtooth" phenomenon in the vertical direction of the developed area after the photoetch process, and the surface of the photoresist film after curing is black and bright, the leveling is normal, and there is no back edge phenomenon on the surrounding frame.

[0167] This is because the auxiliary agent A can significantly change the surface tension, viscosity, leveling of the photoresist solvent system, and improve the spraying workability during the curing process after photoetching. Moreover, under the action of the photo initiator, fluorine groups are introduced during polymerization, similar to the structure as follows, and a small amount of fluorine-containing polymer structure can improve the weather resistance of the light shielding film layer formed after curing of the black photoresist.

[0168] The auxiliary agent B can undergo Cope elimination reaction with the β-H atom tertiary amine resin and participate in photo-polymerization and curing. The β-H atom tertiary amine resin that undergoes Cope elimination reaction also contains unsaturated bonds and can polymerize with the remaining unreacted photo-curing resin monomer to improve the crosslinking density. The use of the auxiliary agent B can improve the adhesion of the black photoresist film surface and enhance the weather resistance of the black photoresist.

[0169] It can be seen from the results of the above table that the black photoresist has the advantages of acid and alkali resistance, solvent and stripping liquid, copper etching liquid erosion; resistance to 25-280°C metal plating film; under the high temperature and humidity environment of 85°C / 85%, the square resistance is stable at 5.0*10 12 ohms / □. Moreover, the surface of the photoresist film after curing is black and bright, the OD density, film thickness, surface impedance and anti-pulling force performance are far superior to the black frame obtained by UV inkjet process and pad printing process, and the amount used can be reduced in production process application. For example, in Example 1 and Comparative Example 2, the film thickness of the black frame obtained by the present application is one fourth of that of the UV inkjet process under the condition of achieving the same light shielding effect. After the photoetch process, the minimum development accuracy can reach 3μm, and the black frame has no burr "sawtooth".

[0170] The above is only an example of the present application, and does not limit the patent scope of the present application, and any equivalent structure or equivalent process transformation using the contents of the specification and drawings, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A black photoresist composition, wherein, The photoresist composition comprises alkali-soluble photopolymer resin, photo-curing resin monomer, additive A, additive B, photo-initiator, thermal initiator, black colorant, polar organic solvent; The photopolymer resin comprises two types of resins: bisphenol fluorene acrylic resin and tertiary amine resin containing β-H atom; The black photoresist composition comprises 2-20 parts of the bisphenol fluorene acrylic resin, 1-10 parts of the tertiary amine resin containing β-H atom, 0.1-2 parts of additive A, 0.2-5 parts of additive B, 0.5-2 parts of the photo-initiator, 5-10 parts of the photo-curing resin monomer, 10-50 parts of the black colorant and 50-500 parts of the polar organic solvent, by weight.

2. The black photoresist composition of claim 1, wherein, The bisphenol fluorene acrylate resin is selected from one or more of the compounds shown in general formula (I); wherein n is an integer from 10 to 180; R1and R3are CH2; R2and R4are OH; X and W are A is selected from H or C1-2 alkyl.

3. The black photoresist composition of claim 1, wherein, The mass ratio of the bisphenol fluorene-based acrylic resin to the tertiary amine resin containing a β-H atom selected from one or more of the compounds represented by general formula (II) is in the range of 1:1 to 5:

1. wherein R is A is selected from H or C1-2alkyl; R1is selected from -H, -CH3, R2 is selected from phenyl, benzyl and phenol group.

4. The black photoresist composition of claim 1, wherein, The photoinitiator is a carbazyl oxime ester compound, and the photoinitiator is selected from one or more of the compounds shown in general formula (III); wherein R1is selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, R2is selected from R3is selected from -H, -CH3, R4is selected from -CH3, -CH2CH3, 5. The black photoresist composition of claim 1, wherein, The photocurable resin monomer is an acrylic resin, and the photocurable resin monomer is selected from one or more of the compounds shown in general formulas (IV) and (V); R1is selected from R2is selected from -H and The mass ratio of the photo-initiator to the photo-curing resin monomer ranges from 1:100 to 2:

5.

6. The black photoresist composition of claim 1, wherein, The polar organic solvent is a medium-polar and strong-polar organic aprotic polar solvent selected from one or more of ethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, triethoxymethyl acrylate, acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, and the mass ratio of the polar organic solvent to the photo-curing resin monomer ranges from 5:1 to 100:1, preferably from 10:1 to 80:1, and more preferably from 20:1 to 70:

1.

7. The black photoresist composition of claim 1, wherein, The black colorant is selected from one or more of cyanine black, aniline black, carbon black, titanium black and graphite black, and the black colorant is preferably carbon black particles with a size of 100-200 nm, and the mass ratio of the carbon black particles to the photo-curing resin monomer ranges from 10:1 to 1:

1.

8. The black photoresist composition of claim 1, wherein, The co-agent A contains a perfluorinated vinylic monomer selected from the group consisting of compounds represented by the general formula (VI); wherein R1, R2, R3, R4are selected from -CF3, One of them.

9. The black photoresist composition of claim 1, wherein, The auxiliary agent B comprises at least one aromatic peroxide, and can participate in photopolymerization curing by Cope elimination reaction with β-H atom tertiary amine resin during post-lithography curing, the aromatic peroxide is selected from compounds shown in general formula (VII); R5 is selected from -F, -Cl and -Br.

10. The black photoresist composition of claim 1, wherein, The thermal initiator comprises a bis-imidazole compound selected from the group consisting of compounds shown in general formula (VIII); R1 and R2 are independently selected from -H, methyl and ethyl.

11. A method for producing the black photoresist composition according to any one of claims 1 to 10, wherein The preparation method comprises the following steps: (1) preparing black color paste: wet grinding the black colorant in a sand mill with 0.05-0.1 mm zirconium balls, and adding the bisphenol fluorene acrylic resin composition as a stabilizing resin during the grinding process to obtain the black color paste; (2) preparing photosensitive liquid: mixing and dispersing the tertiary amine resin containing β-H atom, the photo-curing resin, the photo-initiator, the additive A, the additive B and the polar organic solvent according to the formula amount to form a solution, and filtering to obtain the photosensitive liquid; (3) preparing black photoresist composition: mixing the black color paste in step (1) and the photosensitive liquid in step (2), and finally adding organic solvent to adjust the viscosity, and dispersing in a disperser to form a uniform solution, and filtering to obtain the black photoresist composition.

12. A process for making a black border for a curved display glass-based cover panel, wherein, The manufacturing process comprises the following steps: S11: spraying the black photoresist of any one of claims 1-12 on the hot-bent curved glass substrate in the x direction by the inkjet process to form a first layer of black photoresist, and pre-baking to form a black photoresist film with a thickness of 1-3 μm; S12: exposing the frame pattern part by LDI laser direct writing lithography, washing away the black photoresist in the frame by developing process, and forming the first layer of black frame after hardening by post-baking; S13: spraying the second layer of black photoresist according to any one of claims 1 to 12 in y direction on the arc surface substrate with the first layer of black frame by inkjet process, and forming the second layer of black photoresist film with a thickness of 1-3 μm after pre-baking; S14: exposing the frame pattern part by LDI laser direct writing lithography again, washing away the black photoresist in the frame by developing process, and forming the second layer of black frame after hardening by post-baking; The temperature of post-baking in S12 and S14 is 200-250 ℃.

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