A negative photoresist composition and its application

Abstract

This invention belongs to the field of photoresist technology and relates to a negative photoresist composition and its application. The invention provides a negative photoresist composition in which the main film-forming resin comprises bisphenol A type acrylic resin A and bisphenol A type acrylic resin B. The bisphenol A type acrylic resin A is obtained by polymerization of the following monomers: bisphenol A acrylate monomer, epoxy acrylate monomer, and hydroxy acrylate monomer. The bisphenol A type acrylic resin B is obtained by polymerization of the following monomers: bisphenol A acrylate monomer and epoxy acrylate monomer. The negative photoresist composition provided by this invention, through the combination of bisphenol A type acrylic resin A and bisphenol A type acrylic resin B, forms a film with good transmittance and good film thickness uniformity.

Description

Technical Field

[0001] This invention belongs to the field of photoresist technology and relates to a negative photoresist composition and its application. Background Technology

[0002] Overcoat photoresist (OC) is a special type of photoresist used in semiconductor manufacturing, primarily in chip packaging, display panels, and micro / nano fabrication. Its core function is to form a precision protective layer using photolithography. The main functions of the OC layer are protection and planarization. Different alignments or rotational states of liquid crystal molecules result in varying degrees of light retardation for incident polarized light, ultimately affecting the brightness of the emitted light. Sub-pixel and corner differences exist in the three primary colors. Sub-pixel differences cause variations in liquid crystal cell thickness, affecting transmittance, while corner differences cause light leakage due to disordered liquid crystal molecule alignment. To address these issues, a planarization layer (OC) is necessary after the color resist process. Columnar spacers are typically located on the matrix metallization layer (BM). OC planarization also helps to achieve and maintain the uniformity of the columnar spacer height. To achieve the above functions, the OC (Oxide Coating) layer must possess excellent surface coating properties, meaning it can be rapidly coated on uneven surfaces with a certain degree of fluidity and can bond tightly with the organic color resist layer. It also requires the OC layer after heat drying to have good density, completely preventing the penetration of metal ions from the color resist layer. Currently developed OC materials mainly involve epoxy resins using acrylic polymers. Epoxy resins possess excellent adhesion and durability, as well as high-quality insulation and mechanical properties. Therefore, epoxy resins do not produce volatile substances during the curing process. Furthermore, to ensure the strong mechanical properties of the cured resin, it is necessary to introduce supporting groups such as benzene rings. The number and position of these groups are related to resin compatibility. Resins with poor compatibility are prone to causing the leaching of uncured raw material components in the lower layer during the manufacturing process, resulting in poor film quality. Therefore, improving the resin structure and developing OC photoresists that meet process conditions and have good performance are urgent problems that need to be solved by those skilled in the art. Summary of the Invention

[0003] The purpose of this invention is to solve the technical problems in current OC materials, such as the polymer resin being mainly multi-branched with groups such as benzene rings providing support located at the branch positions, resulting in poor compatibility with the underlying uncured RGB material, which easily leads to the precipitation of uncured components in the RGB material and poor film uniformity.

[0004] On one hand, the present invention relates to a negative photoresist composition, wherein the raw materials of the negative photoresist composition include: a main film-forming resin, a crosslinking agent, a photoacid-generating agent, an additive, and an organic solvent;

[0005] The main film-forming resin includes bisphenol A type acrylic resin A and bisphenol A type acrylic resin B;

[0006] The bisphenol A type acrylic resin A is prepared by polymerization of the following monomers: bisphenol A acrylate monomer, epoxy acrylate monomer, and hydroxy acrylate monomer.

[0007] The bisphenol A type acrylic resin B is prepared by polymerization of the following monomers: bisphenol A acrylate monomer and epoxy acrylate monomer.

[0008] The content of bisphenol A type acrylic resin A in the negative photoresist composition is 5-15% by weight.

[0009] The content of bisphenol A type acrylic resin B in the negative photoresist composition is 5-15% by mass percentage.

[0010] Furthermore, in the negative photoresist composition provided by the present invention, any of the bisphenol A acrylate monomers is selected from at least one of bisphenol A glycerol diacrylate and bisphenol A glycerol dimethacrylate;

[0011] Any of the epoxy acrylate monomers described herein is selected from at least one of glycidyl acrylate, oxetane methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and (3,4-epoxycyclohexyl) methyl acrylate.

[0012] The hydroxyacrylate monomer is selected from at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, 5-hydroxypentyl acrylate, and 4-hydroxybutyl acrylate.

[0013] Furthermore, in the negative photoresist composition provided by the present invention, the bisphenol A type acrylic resin A is prepared by polymerization reaction of 1-50 parts of bisphenol A acrylate monomer, 1-50 parts of epoxy acrylate monomer, and 1-40 parts of hydroxy acrylate monomer as reactive monomers.

[0014] By weight, the bisphenol A type acrylic resin B is prepared by polymerization reaction of 1-50 parts of bisphenol A acrylate monomer and 1-50 parts of epoxy acrylate monomer as reactive monomers.

[0015] Specifically, the polymerization reaction is of the type of free radical polymerization.

[0016] Generally, those skilled in the art use reactive monomers, free radical initiators, and organic solvents as raw materials to carry out polymerization reactions to obtain bisphenol A type acrylic resin A or bisphenol A type acrylic resin B.

[0017] Exemplarily, the free radical initiator is an azo initiator, such as 2,2'-azobis(isobutyric acid)dimethyl, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), or methyl azodiisobutyrate; the free radical initiator is a peroxide initiator, such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, tert-butyl peroxide-2-ethylhexanoate, potassium persulfate, or sodium persulfate. A single free radical initiator can be used, or two or more can be used in combination.

[0018] Optionally, a chain transfer agent can be added arbitrarily during the polymerization reaction using the above-mentioned free radical initiator.

[0019] For example, the chain transfer agent is selected from at least one of 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, and α-methylstyrene dimer.

[0020] For example, the organic solvent used in the polymerization reaction is one or a mixture of diethylene glycol alkyl ethers, dipropylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, N,N-dimethylamides, lactates, and ketones.

[0021] For example, diethylene glycol alkyl ether solvents are diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; dipropylene glycol alkyl ether solvents are dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; propylene glycol monoalkyl ether solvents are propylene glycol monomethyl ether and propylene glycol monoethyl ether; propylene glycol monoalkyl ether acetate solvents are propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, etc.; N,N-dimethylamide solvents are N,N-dimethylformamide and N,N-dimethylacetamide; lactate solvents are methyl lactate and ethyl lactate; and ketone compounds are cyclobutanone and cyclopentanone.

[0022] Generally, the molecular weight of bisphenol A type acrylic resin A is Mn = 5000~8000, and PDI = 1.2~2.2;

[0023] The molecular weight of bisphenol A type acrylic resin B is Mn = 3000~5000 and PDI = 1.2~2.0.

[0024] Furthermore, in the negative photoresist composition provided by the present invention, the crosslinking agent is selected from pentaerythritol glycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerol triglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, 4,4'-biphenyl bisphenol diglycidyl ether. At least one of the following: glyceryl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, 3,3''5,5''-tetramethylbiphenyl bisphenol diglycidyl ether, 2,2'-[oxybis(2,1-ethyleneoxymethylene)]bisepoxyethylene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 1,2-cyclohexanedicarboxylate diglycidyl ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, and 4,5-epoxytetrahydrophthalic acid diglycidyl ester.

[0025] Furthermore, in the negative photoresist composition provided by the present invention, the photoacid-generating agent is an iodonium salt and / or a thionium salt;

[0026] The thioonium salt is at least one of triphenylhexafluoroantimony thioonium salt, triphenylhexafluoroarsenic thioonium salt, triphenyltetrafluoroborate thioonium salt, 4-methylphenyldiphenylhexafluorophosphate thioonium salt, triphenylhexafluorophosphate thioonium salt, diphenylthioonium salt, and 4-(phenylthio)phenylhexafluorophosphate thioonium salt;

[0027] The iodonium salt is at least one selected from diphenylhexafluoroantimony iodonium salt, diphenylhexafluorophosphate iodonium salt, diphenylhexafluoroarsenate iodonium salt, diphenyltetrafluoroborate iodonium salt, xylylhexafluoroarsenate iodonium salt, and di-tert-butylphenylhexafluorophosphate iodonium salt.

[0028] Furthermore, in the negative photoresist composition provided by the present invention, the additive is selected from at least one of BYK300, BYK325, BYK330, BYK333, BYK355, KP301, KP331, KP323, KP104, KP112, KF96, F563, and SURFLON S-386;

[0029] The organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, benzene, toluene, butyrolactone, propylene glycol monoalkyl ether, tert-butyl acetate, cyclopentanone, n-butyl acetate, methyl isobutyl ketone, 2-pentanone, 4-methyl-2-pentanone, cyclohexanone, 2-heptanone, γ-butyrolactone, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate and N,N-dimethylformamide.

[0030] Furthermore, in the negative photoresist composition provided by the present invention, the negative photoresist composition comprises, by mass percentage, 5-15% bisphenol A type acrylic resin A, 5-15% bisphenol A type acrylic resin B, 1-5% crosslinking agent, 1-5% photoacid generator, 1-5% additives, and 55-87% organic solvent.

[0031] Furthermore, in the negative photoresist composition provided by the present invention, the negative photoresist composition has a THK of 1.0~2.0 micrometers, good film thickness uniformity, transmittance of 98% or more, adhesion rating of not less than +++, and pencil hardness of 6B.

[0032] On the other hand, the present invention relates to the application of the negative photoresist composition in the preparation of OC materials.

[0033] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages:

[0034] The negative photoresist composition prepared in this invention, as an OC material, can be used to prepare photoresists with different hardness and adhesion by adjusting the different mass ratios of bisphenol A type acrylic resin A and bisphenol A type acrylic resin B. The resulting film layer has good transmittance and good film thickness uniformity. Because the polymer resin in this photoresist composition has fewer branches and the benzene ring is positioned in the main chain, it exhibits good compatibility. Comprehensive testing shows that the cured film layer of the negative photoresist composition maintains good transmittance and film thickness uniformity while ensuring good adhesion. Detailed Implementation

[0035] The technical solution of the present invention will be described below with reference to embodiments. However, the present invention is not limited to the following embodiments. Unless otherwise specified, the experimental and detection methods described in each embodiment are conventional methods; the reagents and materials described are commercially available unless otherwise specified. Unless otherwise specified, all percentages in the following embodiments refer to mass percentages. Unless otherwise specified, all proportions in the following embodiments refer to mass ratios.

[0036] Example 1

[0037] This embodiment provides a method for synthesizing bisphenol A type acrylic resin A.

[0038] Under nitrogen protection, 50.0 g of bisphenol A glycerol diacrylate, 50.0 g of glycidyl methacrylate, 37.0 g of hydroxyethyl acrylate, 8.0 g of azobisisobutyronitrile, 5.0 g of α-methylstyrene dimer, and 300 g of cyclopentanone were added to a 1 L three-necked flask. The mixture was stirred and heated to 80 °C, reacted for 5 h, and then cooled to room temperature to obtain a bisphenol A type acrylic resin solution A1. Mn = 6000, PDI = 1.9.

[0039] Example 2

[0040] This embodiment provides a method for synthesizing bisphenol A type acrylic resin A.

[0041] Under nitrogen protection, 50.0 g of bisphenol A glycerol diacrylate, 50.0 g of glycidyl acrylate, 37.0 g of hydroxyethyl acrylate, 8.0 g of azobisisobutyronitrile, 5.0 g of α-methylstyrene dimer, and 300 g of cyclopentanone were added to a 1 L three-necked flask. The mixture was stirred and heated to 80 °C, reacted for 5 h, and then cooled to room temperature to obtain bisphenol A type acrylic resin solution A2. Mn = 6000, PDI = 1.8.

[0042] Example 3

[0043] This embodiment provides a method for synthesizing bisphenol A type acrylic resin A.

[0044] Under nitrogen protection, 50.0 g of bisphenol A glycerol dimethacrylate, 50.0 g of tetrahydrofurfuryl methacrylate, 37.0 g of 5-hydroxypentyl acrylate, 8.0 g of azobisisobutyronitrile, 5.0 g of α-methylstyrene dimer, and 300 g of cyclopentanone were added to a 1 L three-necked flask. The mixture was stirred and heated to 80 °C, reacted for 5 h, and then cooled to room temperature to obtain bisphenol A type acrylic resin solution A3. Mn = 7000, PDI = 2.1.

[0045] Example 4

[0046] This embodiment provides a method for synthesizing bisphenol A type acrylic resin A.

[0047] Under nitrogen protection, 50.0 g of bisphenol A glycerol dimethacrylate, 50.0 g of glycidyl acrylate, 37.0 g of 5-hydroxypentyl acrylate, 8.0 g of azobisisobutyronitrile, 5.0 g of α-methylstyrene dimer, and 300 g of cyclopentanone were added to a 1 L three-necked flask. The mixture was stirred and heated to 80 °C, reacted for 5 h, and then cooled to room temperature to obtain bisphenol A type acrylic resin solution A4. Mn = 6500, PDI = 2.0.

[0048] Example 5

[0049] This embodiment provides a method for synthesizing bisphenol A type acrylic resin B.

[0050] Under nitrogen protection, 100.0 g of bisphenol A glycerol diacrylate, 83.0 g of glycidyl methacrylate, 12.0 g of azobisisobutyronitrile, 5.0 g of α-methylstyrene dimer, and 300 g of cyclopentanone were added to a 1 L three-necked flask. The mixture was stirred and heated to 80 °C, reacted for 4 h, and then cooled to room temperature to obtain bisphenol A type acrylic resin solution B1. Mn = 3000, PDI = 1.3.

[0051] Example 6

[0052] This embodiment provides a method for synthesizing bisphenol A type acrylic resin B.

[0053] Under nitrogen protection, 100.0 g of bisphenol A glycerol diacrylate, 83.0 g of glycidyl acrylate, 12.0 g of azobisisobutyronitrile, 5.0 g of α-methylstyrene dimer, and 300 g of cyclopentanone were added to a 1 L three-necked flask. The mixture was stirred and heated to 80 °C, reacted for 4 h, and then cooled to room temperature to obtain bisphenol A type acrylic resin solution B2. Mn = 3500, PDI = 1.3.

[0054] Example 7

[0055] This embodiment provides a method for synthesizing bisphenol A type acrylic resin B.

[0056] Under nitrogen protection, 100.0 g of bisphenol A glycerol dimethacrylate, 83.0 g of glycidyl methacrylate, 12.0 g of azobisisobutyronitrile, 5.0 g of α-methylstyrene dimer, and 300 g of cyclopentanone were added to a 1 L three-necked flask. The mixture was stirred and heated to 80 °C, reacted for 4 h, and then cooled to room temperature to obtain bisphenol A type acrylic resin solution B3. Mn = 3800, PDI = 1.5.

[0057] Example 8

[0058] This embodiment provides a method for synthesizing bisphenol A type acrylic resin B.

[0059] Under nitrogen protection, 100.0 g of bisphenol A glycerol dimethacrylate, 83.0 g of glycidyl acrylate, 12.0 g of azobisisobutyronitrile, 5.0 g of α-methylstyrene dimer, and 300 g of cyclopentanone were added to a 1 L three-necked flask. The mixture was stirred and heated to 80 °C, reacted for 4 h, and then cooled to room temperature to obtain bisphenol A type acrylic resin solution B4. Mn = 4000, PDI = 1.5.

[0060] Example 9

[0061] This embodiment provides a method for preparing a negative photoresist composition.

[0062] Under nitrogen protection, 15g of bisphenol A type acrylic resin A1, 15g of bisphenol A type acrylic resin B1, 3g of pentaerythritol glycidyl ether crosslinking agent, 2g of BYK333 auxiliary agent, 5g of triphenylhexafluoroantimony thionium salt photoacid generator, and 60g of cyclopentanone solvent were added to a 250mL three-necked flask. The mixture was stirred and dissolved to obtain a clear negative photoresist composition.

[0063] Examples 10-20, Comparative Examples 1-8

[0064] The preparation methods of Examples 10-20 and Comparative Examples 1-8 are the same as those of Example 9, except that the type and quality of acrylic resin and the type of crosslinking agent are different.

[0065] Table 1: Formulations of photoresist compositions for Examples 9-20 and Comparative Examples 1-8

[0066]

[0067] Example 21

[0068] This embodiment provides a method for photocuring a negative photoresist composition into a film.

[0069] The photoresist composition was spin-coated onto a clean ITO wafer at 390 rpm for 15 s. It was then pre-baked at 80°C for 120 s, followed by exposure for 12 s, and finally dried and cured at 200°C. This yielded the photocured film test sample M1.

[0070] Examples 22-32

[0071] The preparation methods of Examples 22-32 are the same as those of Example 21, and the photolithographically patterned test samples M2-M12 are prepared. The difference is that the negative photoresist composition used is that of Examples 9-20.

[0072] Example 33

[0073] This embodiment provides a test method for a negative photoresist composition and a test sample M of a photocured film.

[0074] (1) GPC instrument: Agilent 1260; Column: Agilent Plege 3μm MIXED-D (300mm×7.5mm)×2; Mobile phase: THF; Flow rate: 1.0mL / min; Detector: RID detector; Acquisition time: 30min; Workstation: Agilent GPC;

[0075] (2) Transmittance instrument: UV-Vis spectrophotometer; wavelength 200~800nm;

[0076] (3) Coating instrument: MycroWS-650MZ-23NPPB; rotation speed 300-1000rpm;

[0077] (4) Hardness instrument: pencil hardness tester;

[0078] (5) Adhesion tester: cross-cut tester (BYK5123 with 11 teeth and 1mm tooth spacing), 3M 610 tape is used; test method and evaluation standard: refer to GB / T9286-2021;

[0079] (6) Film thickness instrument: step meter; model: Bruker Dektak 150;

[0080] Comparative Example 9

[0081] The purchased commercial OC photoresist composition was spin-coated onto a clean ITO wafer at 360 rpm for 15 seconds. Pre-baking was performed at 90°C for 120 seconds, followed by exposure for 20 seconds, and then drying and curing at 230°C. The resulting photocured test sample M13 was obtained.

[0082] Comparative Examples 10-17

[0083] The preparation methods of Comparative Examples 10-17 are the same as those of Example 21, and test samples M14-M21 are prepared after photocuring. The difference is that the negative photoresist composition used is that of Comparative Examples 1-8.

[0084] Table 2 Performance test results of test sample M in Examples 21-32 and Comparative Examples 9-17

[0085]

[0086] Notes: 1) Adhesion grading evaluation standard: ++++ - edges are neat and smooth, one grid is peeled off; +++ - the total peeling area of ​​the cross-cutting area does not exceed 5%; ++ - the total peeling area of ​​the cross-cutting area is greater than 5% and does not exceed 15%; + - the total peeling area of ​​the cross-cutting area is greater than 15% but does not exceed 35%; 2) Hardness evaluation standard: the standard adopted is GB / T6739-2006, each sample is measured three times, and the judgment result standard is from 6B-BH-6H, the hardness gradually increases; 3) Film thickness uniformity evaluation standard: the film thickness is measured by selecting points using the 49-point method, and the 3σ value is calculated by the standard deviation method.

[0087] As shown in Table 2, the film thickness uniformity of Examples 21-32 is good, with THK-3σ all within 0.3 mm and transmittance all above 98%. Furthermore, they exhibit good adhesion and hardness, indicating that the OC photoresist prepared by this invention meets the process requirements. Comparative Example 9 shows poorer film thickness uniformity and transmittance compared to the examples, and its adhesion is reduced. The main resin in the photoresist compositions of Comparative Examples 10-13 is a single bisphenol A type acrylic resin A, resulting in poor film hardness after photocuring. The main resin in the photoresist compositions of Comparative Examples 14-17 is a single bisphenol A type acrylic resin B, leading to decreased film adhesion and hardness after photocuring.

[0088] The embodiments described above are only some, not all, of the embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate preferred embodiments. All other embodiments obtained by those skilled in the art through related deductions and substitutions based on the inventive concept, without inventive effort, are within the scope of protection of the present invention.

Claims

1. A negative photoresist composition, raw materials of which comprise: A main film-forming resin, a crosslinking agent, a photo-acid generator, an additive, and an organic solvent; The main film-forming resin comprises bisphenol A type acrylic resin A and bisphenol A type acrylic resin B; The bisphenol A type acrylic resin A is prepared by polymerization of bisphenol A acrylate monomers, epoxy acrylate monomers, and hydroxyl acrylate monomers; The bisphenol A type acrylic resin B is prepared by polymerization of bisphenol A acrylate monomers and epoxy acrylate monomers. The content of the bisphenol A type acrylic resin A in the negative photoresist composition is 5-15% by mass; The content of the bisphenol A type acrylic resin B in the negative photoresist composition is 5-15% by mass.

2. The negative photoresist composition according to claim 1, wherein Any of the bisphenol A acrylate monomers is at least one selected from bisphenol A glyceryl diacrylate and bisphenol A glyceryl dimethacrylate; Any of the epoxy acrylate monomers is at least one selected from glycidyl acrylate, oxetane methacrylate, glycidyl methacrylate, glycidyl acrylate, tetrahydrofurfuryl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and (3,4-epoxycyclohexyl) methyl acrylate; The hydroxyl acrylate monomer is at least one selected from hydroxyethyl acrylate, hydroxypropyl acrylate, 5-hydroxypentyl acrylate, and 4-hydroxybutyl acrylate.

3. The negative photoresist composition according to claim 1, wherein The bisphenol A type acrylic resin A is prepared by polymerization of 1-50 parts of bisphenol A acrylate monomers, 1-50 parts of epoxy acrylate monomers, and 1-40 parts of hydroxyl acrylate monomers as reaction monomers by mass. The bisphenol A type acrylic resin B is prepared by polymerization of 1-50 parts of bisphenol A acrylate monomers and 1-50 parts of epoxy acrylate monomers as reaction monomers by mass.

4. The negative photoresist composition according to claim 3, wherein The bisphenol A type acrylic resin A has a molecular weight of Mn=5000-8000 and a PDI of 1.2-2.

2. The bisphenol A type acrylic resin B has a molecular weight of Mn=3000-5000 and a PDI of 1.2-2.

0.

5. The negative photoresist composition according to claim 1, wherein The crosslinking agent is at least one selected from pentaerythritol glycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerol tri-glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, 4,4'-diphenyl bisphenol diglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, 3,3''5,5''-tetramethyl diphenyl bisphenol diglycidyl ether, 2,2'-[oxybis(2,1-ethylenglycoloxy methylene)]bisoxirane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, and 4,5-epoxytetrahydrophthalic acid diglycidyl ester.

6. The negative photoresist composition according to claim 1, wherein The photo-acid generator is an iodonium salt and / or a sulfonium salt. The sulfonium salt is at least one of triphenyl hexafluoroantimonate sulfonium salt, triphenyl hexafluoroarsenate sulfonium salt, triphenyl tetrafluoroborate sulfonium salt, 4-methylphenyl diphenyl hexafluorophosphate sulfonium salt, triphenyl hexafluorophosphate sulfonium salt, diphenyl sulfonium salt and 4-(phenylthio)phenyl hexafluorophosphate sulfonium salt; The iodonium salt is at least one of diphenyl hexafluoroantimonate iodonium salt, diphenyl hexafluorophosphate iodonium salt, diphenyl hexafluoroarsenate iodonium salt, diphenyl tetrafluoroborate iodonium salt, dimethylphenyl hexafluoroarsenate iodonium salt and di-t-butylphenyl hexafluorophosphate iodonium salt.

7. The negative photoresist composition according to claim 1, wherein The auxiliary agent is at least one of BYK300, BYK325, BYK330, BYK333, BYK355, KP301, KP331, KP323, KP104, KP112, KF96, F563, SURFLONS-386; The organic solvent is at least one of dichloromethane, chloroform, tetrahydrofuran, benzene, toluene, butyrolactone, propylene glycol monoalkyl ether, t-butyl acetate, cyclopentanone, n-butyl acetate, methyl isobutyl ketone, 2-pentanone, 4-methyl-2-pentanone, cyclohexanone, 2-heptanone, gamma-butyrolactone, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate and N, N-dimethylformamide.

8. The negative photoresist composition according to claim 1, wherein The negative photoresist composition is composed of bisphenol A type acrylic resin A 5~15%, bisphenol A type acrylic resin B 5~15%, crosslinking agent 1~5%, photoacid generator 1~5%, auxiliary agent 1~5% and organic solvent 55~87% in mass percentage.

9. The negative photoresist composition according to claim 8, wherein The negative photoresist composition has THK of 1.0~2.0 microns, good film thickness uniformity, transmittance of above 98%, adhesion rating evaluation of no less than +++, and pencil hardness of 6B.

10. Use of the negative photoresist composition according to any one of claims 1~9 in preparation of OC material.

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