Interpenetrating network structure BM photoresist and preparation method thereof

Abstract

The application discloses an interpenetrating crosslinking network structure BM photoresist and a preparation method thereof, and belongs to the technical field of photoresist materials. In the application, the surface of untreated carbon black is subjected to hydroxymethylation by an oxidant and a catalyst, active oxidation-reduction sites are introduced, then (methyl) acrylic acid, a vinyl (acyl) amide compound and an initiator are added, and surface graft copolymerization is initiated on the carbon black for further treatment; after the reaction is successful, epoxy resin with a specific structure is introduced, and finally the carbon black with a surface graft crosslinking copolymer is obtained. The BM photoresist provided by the application contains the carbon black with the surface graft crosslinking copolymer, in the curing process, the resin in the matrix can construct a relatively dense interpenetrating crosslinking network with the carbon black with the graft crosslinking copolymer after crosslinking, so that the structural stability and application performance are further enhanced, and a high-impedance BM photoresist with high light shielding property, strong chemical resistance, high impedance, strong adhesion and high-precision patterns is obtained.

Description

Technical Field

[0001] This invention belongs to the field of photoresist material technology, specifically relating to an interpenetrating cross-linked network structure BM photoresist and its preparation method. Background Technology

[0002] Liquid crystal displays (LCDs) are the most common medium for ultra-high-definition displays, widely used in LCD monitors, LCD TVs, LCD mobile phones, and many other fields. Color filters are one of the core components of LCD imaging and are key to improving visibility and achieving high-definition display. To obtain a clearer image, the BM (Black Matrix) photoresist needs to be further enhanced in terms of light-blocking properties, thus requiring the photoresist mixture to contain more pigments such as carbon black.

[0003] However, higher pigment content places higher demands on the materials. When forming color filters, especially in high-pigment-content photoresists, UV (ultraviolet) light struggles to reach the deep layers of the coating, leading to poor curing of the materials in the UV etching composition. This can result in issues such as dissolution in RGB dispersions and poor resistance to the acid and alkali effects of developers. Consequently, the photoresist may exhibit rough edges, undercutting, or even complete detachment, ultimately causing light leakage and reduced clarity. Furthermore, carbon black, a common pigment in photoresists, has tiny carbon particles that easily aggregate to form a continuous network. These particles are electrically conductive due to their free electron movement. Increasing the carbon black concentration to improve opacity can significantly reduce the resistance of the resulting black matrix. Short circuits between the electrodes and the black matrix, or between opposing electrodes, can easily trigger various display defects.

[0004] Therefore, it is essential to propose a new interpenetrating cross-linked network structure BM photoresist and its preparation method. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a BM photoresist with strong adhesion, chemical resistance, and high resolution interpenetrating cross-linked network structure and its preparation method.

[0006] The first aspect of the present invention is to provide an interpenetrating cross-linked network structure BM photoresist, which, by weight, comprises the following raw materials: 25 parts of carboxyl-containing photosensitive resin, 20-30 parts of surface-modified carbon black, 0.1-3 parts of photoinitiator, 1-20 parts of multifunctional monomer, and 150-400 parts of fourth solvent. The surface-modified carbon black is a grafted crosslinked copolymer carbon black, prepared by the following steps: (1) Under the protection of inert gas, carbon black, oxidant, first solvent and catalyst are mixed, heated, stirred and refluxed. After the reaction is completed, the mixture is filtered, washed until neutral and then vacuum dried to obtain hydroxymethylated carbon black. (2) Under inert gas protection, hydroxymethylated carbon black, second solvent, initiator and reactant monomer are mixed and heated, stirred and refluxed to obtain a first dispersion slurry containing acrylic acid-co-amine copolymer surface modified carbon black or methacrylic acid-co-amide copolymer surface modified carbon black; (3) The third solvent is added to the first dispersion slurry containing acrylic acid-co-amine copolymer surface modified carbon black or methacrylic acid-co-amide copolymer surface modified carbon black. After stirring, the second solvent is separated, so that the acrylic acid-co-amine copolymer surface modified carbon black or methacrylic acid-co-amide copolymer surface modified carbon black is transferred to the third solvent to form the second dispersion slurry. (4) Add epoxy resin to the second dispersion slurry, and after heating, stirring and reflux reaction, filter to obtain the second dispersion slurry, and vacuum dry to obtain the carbon black of the grafted crosslinked copolymer.

[0007] In some embodiments, the carbon black has a DBP value of 30-100 ml / 100 g and a specific surface area of ​​30-150 m². 2 / g; the oxidant is selected from at least one of formaldehyde, nitric acid, hydrogen peroxide solution, sulfuric acid, acidic potassium permanganate solution, potassium dichromate solution, and saturated potassium persulfate solution; the first solvent is formaldehyde; the catalyst is selected from at least one of sodium hydroxide, calcium oxide, and sodium bicarbonate.

[0008] In some embodiments, the second solvent is selected from at least one of deionized water, dimethyl sulfoxide, and N,N-dimethylacetamide; the initiator is selected from at least one of cerium ammonium nitrate, cerium nitrate, cerium ammonium sulfate, cerium sulfate, cerium carbonate, and cerium isooctanoate.

[0009] In some embodiments, the reactive monomers include a first comonomer and a second comonomer. The first comonomer is acrylic acid or methacrylic acid, the structure of which is shown in general chemical formula [1]. The second comonomer is an enamide compound or an enamine compound. The structure of the enamide compound is shown in general chemical formula [2], and the structure of the enamine compound is shown in general chemical formula [3]. [1] In formula [1], R1 represents a hydrogen atom or a methyl group; [2] In formula [2], R1 represents one of hydrogen atom, phenyl, phenoxy, 2,3-catechol, 4-chlorophenyl and 3-bromophenyl; R2 represents one of hydrogen atom, isopropyl and phenyl. [3] In formula [3], R3 represents one of hydrogen atom, phenyl, phenoxy, 2,3-catechol, 4-chlorophenyl and 3-bromophenyl; R4 represents one of ethyl and phenyl; R5 represents one of hydrogen atom, isopropyl and phenyl.

[0013] In some embodiments, the third solvent is selected from at least one of toluene, xylene, acetone, butyl acetate, methanol, and dichloromethane.

[0014] In some embodiments, the epoxy resin is selected from one of the following: bisphenol F type epoxy resin, bisphenol A type epoxy resin, dicyclopentadiene epoxy resin, phenolic varnish type epoxy resin, cresolic varnish type epoxy resin, triphenol methane type epoxy resin, epoxy resin with naphthalene skeleton, and epoxy resin with biphenyl skeleton; the structure of the bisphenol F type epoxy resin is shown in general chemical formula [4], the structure of the bisphenol A type epoxy resin is shown in general chemical formula [5], the structure of the dicyclopentadiene epoxy resin is shown in general chemical formula [6], and the structure of the epoxy resin with biphenyl skeleton is shown in general chemical formula [7] or [8]. [4] In equation [4], n is any integer value from 1 to 50; [5] In equation [5], n is any integer value from 1 to 40; [6] In equation [6], n is any integer value from 1 to 30; [7] In equation [7], n is any integer value from 1 to 50; [8] In Equation [8], n is any integer value between 0 and 10.

[0020] In some implementations, in step (1), the reflux reaction time is 5-8 hours; in step (2), the reflux reaction time is 5-7 hours; and in step (4), the reflux reaction time is 4-6 hours.

[0021] The second aspect of this invention is to provide a method for preparing an interpenetrating cross-linked network structure BM photoresist, comprising the following steps; S1: Mix the carboxyl-containing photosensitive resin, surface-modified carbon black, photoinitiator, multifunctional monomer and fourth solvent in parts by weight to obtain a mixture; S2: Grinding the mixture yields the interpenetrating cross-linked network structure BM photoresist.

[0022] In some embodiments, the carboxyl-containing photosensitive resin is selected from one of acrylic resin, epoxy-modified acrylic resin, polyester-modified acrylic resin, bisphenol fluorene-modified acrylic resin, polyurethane acrylic resin, silicone-modified acrylic resin, and polyamide-modified acrylic resin; the photoinitiator is selected from one of triazine compound, biimidazole compound, acetophenone compound, oxime ester compound, benzophenone compound, thioxanthone compound, and phosphine oxide compound; the multifunctional monomer is selected from 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, and triethylene glycol. The fourth solvent is selected from one of the following: diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate; the fourth solvent is selected from at least one of the following: propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, and N-methylpyrrolidone.

[0023] In some embodiments, the mixture is ground until the particle size is 50-80 nm.

[0024] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention creatively provides a surface-modified carbon black. First, carbon black is hydroxymethylated using an oxidant to increase its surface oxygen content, making it rich in active hydrogen. Then, an initiator generates active free radicals on the carbon black surface, initiating a (meth)acrylic acid-co-(amide) copolymer layer. The carbon black surface possesses active carboxyl and amine groups, achieving strong electrostatic and steric stabilization, thus improving the dispersibility of carbon black in resin. Finally, epoxy resin is introduced, reacting with nitrogen atoms on the side chains of the grafted copolymer to ultimately construct an interpenetrating cross-linked network structure on the carbon black surface. Epoxy resin possesses excellent electrical insulation, chemical resistance, and adhesion. By forming a stable, cured interpenetrating network structure with carbon black, it can further enhance the surface-modified carbon black's performance in chemical resistance, electrical insulation, and adhesion.

[0025] 2. The present invention also provides a high-impedance BM photoresist prepared using the above-mentioned surface-modified carbon black. The high-impedance BM photoresist further includes a carboxyl-containing photosensitive resin, a photoinitiator, a multifunctional monomer, and a fourth solvent, ultimately obtaining a high-impedance BM photoresist with high light-blocking properties, strong chemical resistance, high impedance, strong adhesion, and high-precision patterns. Detailed Implementation

[0026] The present invention will now be described in further detail with reference to specific embodiments.

[0027] In the following examples and comparative examples, the carbon black may be selected from PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, PRINTEX-BLACK-550, PRINTEX-BLACK-350, SPECIALBLACK-250, SPECIALBLACK-250, SPECIALBLACK-100, and LAMP BLACK-101 from Orion GmbH, Germany; and diagram black Ⅱ, diagram black N339, diagram black SH, diagram black H, diagram black LH, and diagram black from Mitsubishi Heavy Industries, Ltd., Japan. LA, diagram black SF, diagram black N550M, diagram black M, diagram black E, diagram black G, diagram black R, diagram black N760M, diagram black LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, #3030, #3050, MA7, MA77, MA8;RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RA from Columbia Chemical Co., Ltd. VEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RA VEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170; the photoinitiator may be selected from triazine compounds: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-S-triazine, and 2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Bisimidazole compounds: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole; Acetophenone compounds: 2-hydroxy-2-methyl-1-phenylprop-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylprop-1-one, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2 2-Dimethoxy-2-phenylacetophenone, 2-methyl-(4-methylthiophenyl)-2-morpholinone and 2-benzyl-2-dimethylamino-1-(4-morpholinphenyl)-but-1-one; oxime esters: 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]acetophenone-1-(O-acetyl oxime); benzophenone compounds: 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone; thioxanthone compounds: 2 4-Diethylthioxanthanone, 2-chlorothioxanthanone, isopropylthioxanthanone, and 2-isopropylthioxanthanone; phosphine oxide compounds: one of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,6-xylyl)phosphoyl chloride.

[0028] Modified Example 1 Take 300g of PRINTEX-V carbon black, 2L of oxidant (formaldehyde, also used as the first solvent), and 150mL of 20% sodium hydroxide solution into a three-necked flask equipped with a reflux condenser. Start the stirrer and heat to 50°C for at least 5 hours. Filter the reaction slurry and wash the carbon black with deionized water until neutral. After vacuum drying at 50°C, modified hydroxymethylated carbon black of Example 1 is obtained.

[0029] Synthesis example 2-9 First, 30 parts of the hydroxymethylated carbon black prepared in Modified Example 1, 0.97 parts of the first comonomer (acrylic acid, hereinafter referred to as AA), a specified amount of the second comonomer (3,4-dihydroxycinnamoamide or 2-isopropenylphenylaniline, hereinafter referred to as X-1 or X-2 respectively), and 150 parts of the second solvent (deionized water) were added to a 250 mL three-necked flask. Then, 0.64 parts of a 30.0% cerium ammonium nitrate aqueous solution (hereinafter referred to as Ce-1) were added to the dropping funnel. The entire reaction system was then evacuated, and nitrogen gas was continuously purged for 30 min, repeated 5-6 times. After adjusting the system temperature to 30-35℃, the cerium ammonium nitrate aqueous solution was added dropwise at a certain rate to initiate the reaction. The system temperature was maintained at 30-35℃ under reflux for at least 5 h. After the reaction was completed, a first dispersion slurry containing surface-modified carbon black of acrylic acid-co-amine copolymer or surface-modified carbon black of methacrylic acid-co-amide copolymer was obtained. The types and amounts of materials used are shown in Table 1.

[0030] The third solvent (xylene, hereinafter referred to as B-1) is added to the first dispersion slurry from the previous step. After thorough stirring, all the surface-modified carbon black of the acrylic acid-co-amine copolymer or the surface-modified carbon black of the methacrylic acid-co-amide copolymer is transferred to the xylene. Deionized water is separated by ordinary filtration, and the carbon black is uniformly dispersed in xylene to form the second dispersion slurry. Then, epoxy resin (selected from bisphenol F epoxy resin WXDIC®830 from China National Chemical Corporation, bisphenol A epoxy resin DER330 from Dow Chemical Company, dicyclopentadiene phenolic epoxy resin DNE260 from Chang Chun Group in Taiwan, or bisphenol fluorene epoxy resin from Zhengzhou Alpha Chemical Co., Ltd., hereinafter referred to as H-1, H-2, H-3, or H-4 respectively) is added and heated, stirred, and refluxed for 4-6 hours. After the reaction is completed, the second dispersion slurry is filtered, and finally vacuum dried to obtain the grafted crosslinked copolymer carbon black. The types and amounts of materials used are shown in Table 1.

[0031] Table 1

[0032] Comparative Example 10 20 parts of unmodified carbon black PRINTEX-V, 25 parts of bisphenol fluorene modified acrylic resin (KBR-101, purchased from KISCO, South Korea), 0.37 parts of photoinitiator 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(0-acetyl-oxime) (hereinafter referred to as DPHA), 6.25 parts of polyfunctional monomer (dipentaerythritol hexaacrylate, hereinafter referred to as DPHA) and 212.5 parts of fourth solvent (propylene glycol monomethyl ether acetate, hereinafter referred to as PGMEA) were mixed and dispersed evenly to obtain a uniform black mixture, which is the BM photoresist of Comparative Example 10.

[0033] Comparative Example 11 20 parts of hydroxymethylated carbon black prepared in Modified Example 1, 25 parts of bisphenol fluorene modified acrylic resin (KBR-101, purchased from KISCO, South Korea), 0.37 parts of photoinitiator 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(0-acetyl-oxime) (hereinafter referred to as DPHA), 6.25 parts of polyfunctional monomer (dipentaerythritol hexaacrylate, hereinafter referred to as DPHA) and 212.5 parts of fourth solvent (propylene glycol monomethyl ether acetate, hereinafter referred to as PGMEA) were mixed and dispersed evenly to obtain a uniform black mixture, which is the BM photoresist of Comparative Example 11.

[0034] Examples 12-19 20 parts of carbon black modified with graft copolymers from the above synthetic examples 2-9, 25 parts of bisphenol fluorene modified acrylic resin (KBR-101, purchased from KISCO, South Korea), 0.37 parts of photoinitiator 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(0-acetyl-oxime) (hereinafter referred to as DPHA), 6.25 parts of polyfunctional monomer (dipentaerythritol hexaacrylate, hereinafter referred to as DPHA) and 212.5 parts of fourth solvent (propylene glycol monomethyl ether acetate, hereinafter referred to as PGMEA) were mixed and dispersed evenly to obtain a uniform black mixture, which were the BM photoresists of Examples 12-19.

[0035] The photoresist dispersibility of Examples 12-19 and Comparative Examples 10 and 11 was determined using a particle size analyzer (Zetasize pro, manufactured by Malvern). The types and amounts of materials used in Examples 12-19 and Comparative Examples 10 and 11, as well as the average particle size of the dispersions, are shown in Table 2.

[0036] Table 2

[0037] Performance Evaluation First, the BM photoresists prepared in Examples 12-19 and Comparative Examples 10 and 11 were characterized by solution particle size analysis using a particle size analyzer. Then, they were uniformly coated onto ITO-coated glass substrates using spin coating. After drying at 90°C for 5 minutes, the coatings were exposed through a patterned photomask using an exposure machine with a 365nm LED light source. Next, they were developed with a 0.5 wt% Na₂CO₃ aqueous solution, and finally thermosetting at 230°C, 250°C, and 270°C for 30 minutes each. This yielded 3-5 sets of coatings for Examples 12-19 and Comparative Examples 10 and 11 for the following evaluation.

[0038] (1) Surface resistivity Using a high-resistance meter (6517B, manufactured by Keithley) with an 8009 fixture, the surface resistance values ​​of the BM photoresist of Examples 12-19 and Comparative Examples 10 and 11 were measured after curing at 230°C, 250°C, and 270°C under a voltage of 1000V (the results are shown in Table 3).

[0039] (2) OD value Use a spectrophotometer (UV) 2700 (manufactured by Shimadzu Corporation) was used to measure the transmittance of each substrate at 550 nm. The OD values ​​of the coatings of Examples 12-19 and Comparative Examples 10 and 11 after curing at 230°C, 250°C and 270°C were obtained (the results are shown in Table 3).

[0040] (3) Adhesion Examples 12-19 and Comparative Examples 10 and 11, cured and developed at 230℃, were placed under a stable diffused light source to observe their integrity (100-grid pattern). They were then placed in deionized water at 100℃ and boiled for 3 hours, after which the integrity of the 100-grid pattern was observed again (results are shown in Table 4).

[0041] (4) Chemical resistance The BM photoresists of Examples 12-19 and Comparative Examples 10 and 11, which were cured and developed at 230°C, were placed under a stable diffused light source, and their integrity was observed [the results are the same as those obtained in (3) regarding adhesion]. They were then placed in three specific chemical environments at 25°C: aqua regia (concentration 1N), sodium oxide solution (concentration 0.2N), and tetramethylammonium hydroxide (concentration 2.38N). After continuous immersion for 2 hours, the integrity of the 100-cell structure was observed again (the results are shown in Table 5).

[0042] Table 3

[0043] Table 4

[0044] Table 5

[0045] As shown in Tables 3, 4, and 5, the developed layers of BM photoresists in Examples 12-19, formed by copolymer grafting modification of carbon black, exhibit high resistivity and high OD values, as well as strong adhesion. In contrast, the BM photoresists in Comparative Examples 10 and 11, formed with unmodified carbon black and hydroxymethylated carbon black, have lower resistivity and OD values, and their performance indicators significantly decrease with increasing curing temperature. After boiling in water, all cells exhibited peeling abnormalities. Specifically, after immersion in 1N aqua regia, 0.2N sodium hydroxide solution, and 2.38N tetramethylammonium hydroxide solution, the cell density of BM photoresists in Examples 12-19 remained stable at 5B, indicating strong chemical resistance. However, the BM photoresists formed using unmodified carbon black in Comparative Example 10 and hydroxymethylated carbon black in Comparative Example 11 exhibited peeling abnormalities after immersion in the aforementioned three specific chemical environments. The results show that the surface impedance, light-blocking properties, adhesion, and chemical resistance of the BM photoresist formed by copolymer grafting modification of carbon black can be significantly improved.

[0046] The above descriptions are merely some embodiments of the present invention. Those skilled in the art can make various modifications and improvements without departing from the inventive concept of the present invention, and these all fall within the scope of protection of the present invention.

Claims

1. A BM photoresist with an interpenetrating cross-linked network structure, characterized in that, By weight, it includes the following ingredients: The composition includes 25 parts of a carboxyl-containing photosensitive resin, 20-30 parts of surface-modified carbon black, 0.1-3 parts of a photoinitiator, 1-20 parts of a multifunctional monomer, and 150-400 parts of a fourth solvent; wherein the fourth solvent is selected from at least one of propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, and N-methylpyrrolidone. The surface-modified carbon black is a grafted crosslinked copolymer carbon black, prepared by the following steps: (1) Under the protection of an inert gas, carbon black, oxidant, first solvent and catalyst are mixed, heated, stirred and refluxed, and after the reaction is completed, filtered and washed until neutral and then vacuum dried to obtain hydroxymethylated carbon black; wherein, the first solvent is formaldehyde; (2) Under inert gas protection, the hydroxymethylated carbon black, the second solvent, the initiator and the reactant are mixed and heated, stirred and refluxed to obtain a first dispersion slurry containing acrylic acid-co-amine copolymer surface-modified carbon black or methacrylic acid-co-amide copolymer surface-modified carbon black; wherein, the second solvent is selected from at least one of deionized water, dimethyl sulfoxide and N,N-dimethylacetamide; (3) The third solvent is added to the first dispersion slurry containing acrylic acid-co-amine copolymer surface-modified carbon black or methacrylic acid-co-amide copolymer surface-modified carbon black, and the second solvent is separated after stirring, so that the acrylic acid-co-amine copolymer surface-modified carbon black or methacrylic acid-co-amide copolymer surface-modified carbon black is transferred to the third solvent to form a second dispersion slurry; wherein, the third solvent is selected from at least one of toluene, xylene, acetone, butyl acetate, methanol, and dichloromethane; (4) Add epoxy resin to the second dispersion slurry, and after heating, stirring and reflux reaction, filter to obtain the second dispersion slurry, and vacuum dry to obtain the carbon black of the graft crosslinked copolymer.

2. The interpenetrating cross-linked network structure BM photoresist according to claim 1, characterized in that, said carbon black has a DBP value of 30-100 ml / 100 g, a specific surface area of 30-150 m 2 / g; said oxidizing agent is selected from at least one of formaldehyde, nitric acid, hydrogen peroxide solution, sulfuric acid, acidic potassium permanganate solution, potassium dichromate solution, saturated potassium persulfate solution; said catalyst is selected from at least one of sodium hydroxide, calcium oxide, sodium bicarbonate.

3. The interpenetrating cross-linked network structure BM photoresist according to claim 1, characterized in that, The initiator is selected from at least one of cerium ammonium nitrate, cerium nitrate, cerium ammonium sulfate, cerium sulfate, cerium carbonate, and cerium isooctanoate.

4. The interpenetrating cross-linked network structure BM photoresist according to claim 1, characterized in that, The reactive monomers include a first comonomer and a second comonomer. The first comonomer is acrylic acid or methacrylic acid, and its structure is shown in general chemical formula [1]. The second comonomer is an enamide compound or an enamine compound. The structure of the enamide compound is shown in general chemical formula [2], and the structure of the enamine compound is shown in general chemical formula [3]. [1] In formula [1], R1 represents a hydrogen atom or a methyl group; [2] In formula [2], R1 represents one of hydrogen atom, phenyl, phenoxy, 2,3-catechol, 4-chlorophenyl and 3-bromophenyl; R2 represents one of hydrogen atom, isopropyl and phenyl. [3] In formula [3], R3 represents one of hydrogen atom, phenyl, phenoxy, 2,3-catechol, 4-chlorophenyl and 3-bromophenyl; R4 represents one of ethyl and phenyl; R5 represents one of hydrogen atom, isopropyl and phenyl.

5. The interpenetrating cross-linked network structure BM photoresist according to claim 1, characterized in that, The epoxy resin is selected from one of the following: bisphenol F type epoxy resin, bisphenol A type epoxy resin, dicyclopentadiene epoxy resin, phenolic varnish type epoxy resin, cresolic varnish type epoxy resin, triphenol methane type epoxy resin, epoxy resin with naphthalene skeleton, and epoxy resin with biphenyl skeleton; the structure of the bisphenol F type epoxy resin is shown in chemical formula [4], the structure of the bisphenol A type epoxy resin is shown in chemical formula [5], the structure of the dicyclopentadiene epoxy resin is shown in chemical formula [6], and the structure of the epoxy resin with biphenyl skeleton is shown in chemical formula [7] or [8]. [4] In equation [4], n is any integer value from 1 to 50; [5] In equation [5], n is any integer value from 1 to 40; [6] In equation [6], n is any integer value from 1 to 30; [7] In equation [7], n is any integer value from 1 to 50; [8] In Equation [8], n is any integer value between 0 and 10.

6. The interpenetrating cross-linked network structure BM photoresist according to claim 1, characterized in that, In step (1), the reflux reaction time is 5-8 hours; in step (2), the reflux reaction time is 5-7 hours; in step (4), the reflux reaction time is 4-6 hours.

7. A method for preparing a BM photoresist with an interpenetrating cross-linked network structure as described in any one of claims 1-6, characterized in that, Includes the following steps; S1: The carboxyl-containing photosensitive resin, the surface-modified carbon black, the photoinitiator, the multifunctional monomer and the fourth solvent are mixed in parts by weight to obtain a mixture; S2: Grinding the mixture yields the interpenetrating cross-linked network structure BM photoresist.

8. The method for preparing the interpenetrating cross-linked network structure BM photoresist according to claim 7, characterized in that, The carboxyl-containing photosensitive resin is selected from one of acrylic resin, epoxy-modified acrylic resin, polyester-modified acrylic resin, bisphenol fluorene-modified acrylic resin, polyurethane acrylic resin, organosilicon-modified acrylic resin, and polyamide-modified acrylic resin; the photoinitiator is selected from one of triazine compound, biimidazole compound, acetophenone compound, oxime ester compound, benzophenone compound, thioxanthone compound, and phosphine oxide compound; the polyfunctional monomer is selected from one of 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

9. The method for preparing the interpenetrating cross-linked network structure BM photoresist according to claim 7, characterized in that, The mixture is ground until the particle size is 50-80 nm.

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