Positive photoresist composition as well as preparation method and application thereof

Abstract

The invention provides a positive photoresist composition as well as a preparation method and application thereof. The positive photoresist composition comprises acrylic copolymer resin and a photosensitizer, the acrylic copolymer resin comprises a first structural unit, a second structural unit and a third structural unit. The positive photoresist composition has the advantages of favorable aging resistance, high refractive index, high transmittance, high adhesive force and high hardness.

Description

Technical Field

[0001] The invention relates to the field of optical materials, and in particular to a positive photoresist composition and a preparation method and application thereof. Background Art

[0002] In the field of optical material technology, microlens is an important optical element widely used in display devices and image sensors. The main function of microlens is to converge or diverge light to achieve precise control of light and improve the transmittance of light. The performance of microlens, such as refractive index, transmittance and anti-aging performance, directly affects the performance of display devices and image sensors. Therefore, the development of microlens materials with high refractive index, high transmittance and excellent anti-aging performance is of great significance to improve the performance of display devices and image sensors.

[0003] Positive photoresist compositions have higher resolution than negative photoresist compositions, and are often used as high-resolution microlens materials. Acrylic resins in positive photoresist compositions have good transparency, weather resistance and ease of processing, but have relatively low refractive index. Existing technology mainly improves the refractive index of acrylic resins by introducing heteroatoms such as sulfur and halogens, thereby improving the refractive index of positive photoresist compositions. However, these methods can cause the anti-aging properties of acrylic resins and the positive photoresist compositions composed thereof to decrease, particularly after high-temperature thermal aging, their transmittance and anti-yellowing properties can significantly decrease. In addition, the adhesion and hardness of the positive photoresist compositions also need to be further strengthened.

[0004] Therefore, how to make the positive photoresist composition have high refractive index, high transmittance, high adhesion and high hardness without sacrificing its anti-aging performance is an important challenge facing current technology. Summary of the invention

[0005] The present invention provides a positive photoresist composition and a preparation method and application thereof. The positive photoresist composition has good anti-aging performance, high refractive index, high transmittance, high adhesion and high hardness, and effectively overcomes the defects of the prior art.

[0006] The present invention provides a positive photoresist composition, comprising an acrylic copolymer resin and a photosensitizer, wherein the acrylic copolymer resin comprises a first structural unit, a second structural unit, and a third structural unit; the first structural unit is as shown in Formula 1:

[0007] Formula 1,

[0008] Among them, R 1 Any one selected from a hydrogen atom and a methyl group, R 2 , R 3Each independently selected from any one of the groups represented by Formula 1-1 and Formula 1-2, n 1 Any integer between 0 and 10.

[0009] Formula 1-1, Formula 1-2;

[0010] The second structural unit is shown in Formula 2:

[0011] Formula 2,

[0012] Among them, R 1 Any one selected from a hydrogen atom, a methyl group, R 2 Any one selected from the groups shown in Formula 1-1 and Formula 1-2, R 4 Any one selected from carboxyl and hydroxyl groups, n 2 Any integer between 0 and 10.

[0013] Formula 1-1, Formula 1-2;

[0014] The structure of the third structural unit is shown in Formula 3:

[0015] Formula 3,

[0016] Among them, R 1 Any one selected from a hydrogen atom, a methyl group, R 2 Any one selected from the groups shown in Formula 1-1 and Formula 1-2, R 5 Any one selected from the groups shown in Formula 3-1, Formula 3-2, and Formula 3-3, n 3 Any integer between 0 and 10.

[0017] Formula 1-1, Formula 1-2, Formula 3-1,

[0018] Formula 3-2, Formula 3-3.

[0019] According to one embodiment of the present invention, the first structural unit includes one or more of the structural units shown in Formula 4-1, Formula 4-2, and Formula 4-3; and / or, the second structural unit includes one or more of the structural units shown in Formula 5-1, Formula 5-2, and Formula 5-3; and / or, the third structural unit includes one or more of the structural units shown in Formula 6-1, Formula 6-2, and Formula 6-3; and / or, the weight average molecular weight of the acrylic copolymer resin is 500 g / mol to 100000 g / mol; and / or, the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 5%-95%.

[0020] According to one embodiment of the present invention, the acrylic copolymer resin is copolymerized by a monomer raw material including a first acrylate monomer, a second acrylate monomer, and a third acrylate monomer; preferably, the structure of the first acrylate monomer is as shown in Formula 7; preferably, the structure of the second acrylate monomer is as shown in Formula 8; preferably, the structure of the third acrylate monomer is as shown in Formula 9; preferably, the mass percentage of the first acrylate monomer in the monomer raw material is 5% to 95%; preferably, the mass percentage of the second acrylate monomer in the monomer raw material is 5% to 95%; preferably, the mass percentage of the third acrylate monomer in the monomer raw material is 5% to 95%.

[0021] According to one embodiment of the present invention, the first acrylate monomer includes one or more of the compounds shown in Formula 10-1, Formula 10-2, and Formula 10-3; and / or, the second acrylate monomer includes one or more of the compounds shown in Formula 11-1, Formula 11-2, and Formula 11-3; and / or, the third acrylate monomer includes one or more of the compounds shown in Formula 12-1, Formula 12-2, and Formula 12-3.

[0022] According to one embodiment of the present invention, the positive photoresist composition satisfies: 0<a≤0.3, preferably 0.1≤a≤0.2, wherein a is the mass ratio of the photosensitive agent to the acrylic copolymer resin; and / or, the positive photoresist composition further includes one or more of a sensitizer, an additive and a solvent, and the additive includes one or more of a silane coupling agent and a leveling agent.

[0023] According to one embodiment of the present invention, the degree of esterification of the diazonaphthoquinone compound is 50% to 85%; and / or the sensitizer contains a hydroxyphenyl group; and / or the mass ratio of the sensitizer to the acrylic copolymer resin is 0 to 0.3; and / or the mass ratio of the additive to the acrylic copolymer resin is 0 to 0.1; and / or the solvent includes propylene glycol monomethyl ether acetate and / or diethylene glycol methyl ethyl ether.

[0024] Another aspect of the present invention provides a method for preparing the above-mentioned positive photoresist composition, comprising the following steps: mixing a photosensitive agent and an acrylic copolymer resin to obtain the positive photoresist composition; preferably, the process of mixing the photosensitive agent and the acrylic copolymer resin comprises: mixing the photosensitive agent, a sensitizer, an additive and the acrylic copolymer resin, and then adding a solvent thereto to obtain the positive photoresist composition.

[0025] Another aspect of the present invention provides a structural member, comprising the positive photoresist composition or a cured product formed by curing the positive photoresist composition prepared according to the preparation method of the positive photoresist composition.

[0026] According to one embodiment of the present invention, the refractive index of the cured product is 1.55-1.65; and / or the transmittance of the cured product after heat aging at 150±5° C. for 240±2 hours is greater than or equal to 90%.

[0027] Another aspect of the present invention provides a method for preparing the above-mentioned structural part, comprising the following steps: subjecting a positive photoresist composition to a molding process to obtain a molding product; sequentially exposing and developing the molding product to obtain the structural part; wherein the developer comprises an alkali solution.

[0028] The implementation of the present invention has at least the following beneficial effects: the positive photoresist composition of the present invention comprises an acrylic copolymer resin and a photosensitizer; the acrylic copolymer resin comprises a first structural unit represented by Formula 1, a second structural unit represented by Formula 2, and a third structural unit represented by Formula 3. The positive photoresist composition has good anti-aging performance, high refractive index, high transmittance, high adhesion and high hardness, which is beneficial to prolonging the service life of display devices and image sensors, and is suitable for the fields of optical device manufacturing, display device manufacturing, image sensor manufacturing, and polymer material science research. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] The embodiment of the present invention provides a positive photoresist composition, including an acrylic copolymer resin and a photosensitizer, wherein the acrylic copolymer resin includes a first structural unit, a second structural unit, and a third structural unit; the first structural unit is shown in Formula 1:

[0031] Formula 1,

[0032] Among them, R 1 Any one selected from a hydrogen atom and a methyl group, R 2 , R 3 Each independently selected from any one of the groups represented by Formula 1-1 and Formula 1-2, n 1 is any integer between 0 and 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,

[0033] Formula 1-1, Formula 1-2;

[0034] The second structural unit is shown in Formula 2:

[0035] Formula 2,

[0036] Among them, R 1 Any one selected from a hydrogen atom and a methyl group, R 2 Any one selected from the groups shown in Formula 1-1 and Formula 1-2, R 4 Any one selected from carboxyl and hydroxyl groups, n 2 is any integer between 0 and 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,

[0037] Formula 1-1, Formula 1-2;

[0038] The structure of the third structural unit is shown in Formula 3:

[0039] Formula 3,

[0040] Among them, R 1 Any one selected from a hydrogen atom and a methyl group, R 2 Any one selected from the groups shown in Formula 1-1 and Formula 1-2, R 5 Any one selected from the groups shown in Formula 3-1, Formula 3-2, and Formula 3-3, n 3 is any integer between 0 and 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,

[0041] Formula 1-1, Formula 1-2, Formula 3-1,

[0042] Formula 3-2, Formula 3-3.

[0043] Exemplarily, the acrylic copolymer resin may include a compound represented by Formula 13:

[0044] Formula 13,

[0045] Among them, R 1 Any one selected from a hydrogen atom and a methyl group, R 2 , R 3 Each independently selected from any one of the groups shown in Formula 1-1 and Formula 1-2, R 4 Any one selected from carboxyl and hydroxyl, R 5 Any one selected from the groups shown in Formula 3-1, Formula 3-2, and Formula 3-3, n 1 is any integer between 0 and 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, n 2 is any integer between 0 and 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, n 3 is any integer between 0 and 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,

[0046] Formula 1-1, Formula 1-2, Formula 3-1,

[0047] Formula 3-2, Formula 3-3.

[0048] According to the inventor's research, the acrylic copolymer resin containing the first structural unit, the second structural unit, and the third structural unit can increase the refractive index of the positive photoresist composition, thereby improving the performance of the display device and the image sensor, enabling it to more accurately control the convergence and divergence of light, thereby improving the quality of the image and the display effect. Secondly, the acrylic copolymer resin containing the first structural unit, the second structural unit, and the third structural unit can make the anti-aging performance of the positive photoresist composition still have a high transmittance even after high-temperature thermal aging, which is beneficial to prolonging the service life of the display device and the image sensor.

[0049] Among them, the first structural unit, the second structural unit, and the third structural unit are repeating units of the acrylic copolymer resin, all of which contain aromatic groups such as benzene rings. Among them, the first structural unit mainly plays a role in adjusting the refractive index, which is beneficial to improving the refractive index of the positive photoresist composition, the second structural unit mainly plays a role in developing adjustment, which is beneficial to improving the performance of display devices and image sensors, and the third structural unit mainly plays a role in curing and cross-linking, increasing the hardness and chemical solvent resistance of the acrylic copolymer resin, thereby improving the anti-aging performance and hardness of the positive photoresist composition.

[0050] The positive photoresist composition in the embodiment of the present invention includes a photosensitizer and an acrylic copolymer resin containing a first structural unit, a second structural unit, and a third structural unit. The positive photoresist composition has good anti-aging performance, high refractive index, high adhesion and high hardness performance. Specifically, the cured product of the positive photoresist composition has good anti-aging performance, high refractive index, high adhesion and high hardness performance.

[0051] In some embodiments, the first structural unit includes one or more of the structural units shown in Formula 4-1, Formula 4-2, and Formula 4-3:

[0052] Formula 4-1,

[0053] Formula 4-2,

[0054] Formula 4-3.

[0055] In addition, the second structural unit includes one or more of the structural units shown in Formula 5-1, Formula 5-2, and Formula 5-3:

[0056] Formula 5-1, Formula 5-2

[0057] Formula 5-3.

[0058] In addition, the third structural unit includes one or more of the structural units shown in Formula 6-1, Formula 6-2, and Formula 6-3:

[0059] Formula 6-1, Formula 6-2

[0060] Formula 6-3.

[0061] In a specific implementation, the weight average molecular weight of the acrylic copolymer resin is 500 g / mol to 100,000 g / mol, for example, 500 g / mol, 1,000 g / mol, 5,000 g / mol, 10,000 g / mol, 20,000 g / mol, 50,000 g / mol, 80,000 g / mol, 100,000 g / mol or a range consisting of any two of them, which is beneficial to the curing of the positive photoresist composition.

[0062] In some embodiments, the mass percentage of acrylic copolymer resin in the positive photoresist composition is 5%-95%, for example, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or a range composed of any two thereof, which is beneficial for the positive photoresist composition to have both good anti-aging properties and a higher refractive index.

[0063] In some embodiments, the acrylic copolymer resin is obtained by copolymerizing a monomer raw material including a first acrylic ester monomer, a second acrylic ester monomer, and a third acrylic ester monomer.

[0064] Among them, the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer all contain unsaturated bonds, specifically carbon-carbon double bonds. In the copolymerization reaction, the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are copolymerized through the carbon-carbon double bonds to form an acrylic copolymer resin. The first acrylate monomer, the second acrylate monomer, and the third acrylate monomer correspondingly form the first structural unit, the second structural unit, and the third structural unit in the acrylic copolymer resin.

[0065] In some embodiments, the structure of the first acrylate monomer is shown in Formula 7, which is used to form the first structural unit:

[0066] Formula 7,

[0067] Among them, R 1 Any one selected from a hydrogen atom and a methyl group, R 2 , R 3 Each independently selected from any one of the groups represented by Formula 1-1 and Formula 1-2, n 1 is any integer between 0 and 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,

[0068] Formula 1-1, Formula 1-2.

[0069] In addition, the structure of the second acrylate monomer is shown in Formula 8, which is used to form the second structural unit:

[0070] Formula 8,

[0071] Among them, R 1 Any one selected from a hydrogen atom and a methyl group, R 2 Any one selected from the groups shown in Formula 1-1 and Formula 1-2, R 4 Any one selected from carboxyl and hydroxyl groups, n 2is any integer between 0 and 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,

[0072] Formula 1-1, Formula 1-2;

[0073] In addition, the structure of the third acrylate monomer is shown in Formula 9:

[0074] Formula 9,

[0075] Among them, R 1 Any one selected from a hydrogen atom and a methyl group, R 2 Any one selected from the groups shown in Formula 1-1 and Formula 1-2, R 5 Any one selected from the groups shown in Formula 3-1, Formula 3-2, and Formula 3-3, n 3 is any integer between 0 and 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,

[0076] Formula 1-1, Formula 1-2, Formula 3-1,

[0077] Formula 3-2, Formula 3-3.

[0078] In some embodiments, the mass percentage of the first acrylate monomer to the monomer raw material is 5% to 95%, for example 5%, 6%, 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 86%, 88%, 90%, 92%, 95% or a range consisting of any two thereof.

[0079] In addition, the mass percentage of the second acrylate monomer in the monomer raw material is 5% to 95%, for example, 5%, 6%, 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 86%, 88%, 90%, 92%, 95% or a range consisting of any two thereof.

[0080] In addition, the mass percentage of the third acrylate monomer in the monomer raw material is 5% to 95%, for example, 5%, 6%, 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 86%, 88%, 90%, 92%, 95% or a range consisting of any two thereof.

[0081] In some embodiments, the first acrylate monomer includes one or more of the compounds shown in Formula 10-1, Formula 10-2, and Formula 10-3:

[0082] Formula 10-1,

[0083] Formula 10-2,

[0084] Formula 10-3.

[0085] In addition, the second acrylate monomer includes one or more compounds represented by Formula 11-1, Formula 11-2, and Formula 11-3:

[0086] Formula 11-1, Formula 11-2,

[0087] Formula 11-3.

[0088] In addition, the third acrylate monomer includes one or more compounds represented by Formula 12-1, Formula 12-2, and Formula 12-3:

[0089] Formula 12-1, Formula 12-2,

[0090] Formula 12-3.

[0091] In some embodiments, the positive photoresist composition satisfies: 0<a≤0.3, wherein a is the mass ratio of the photosensitive agent to the acrylic copolymer resin, for example 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.25, 0.30 or a range consisting of any two of them, preferably 0.1≤a≤0.2, which is conducive to the formation and development of the pattern after exposure of the positive photoresist composition.

[0092] In a specific implementation, the photosensitizer includes a diazonaphthoquinone compound.

[0093] In some embodiments, the positive photoresist composition further includes one or more of a sensitizer, an additive, and a solvent.

[0094] In a specific implementation, the additive includes one or more of a silane coupling agent and a leveling agent.

[0095] In a specific implementation, the diazonaphthoquinone compound specifically includes one or more compounds represented by Formula 14-1 to Formula 14-5:

[0096] Formula 14-1, Formula 14-2,

[0097] Formula 14-3, Formula 14-4,

[0098] Formula 14-5,

[0099] Wherein, for any one of 14-1 to 14-5, the groups D therein may be the same or different, and D is selected from a hydrogen atom, one or more of the compounds represented by formula 14-6 to formula 14-7, and at least one D is not a hydrogen atom:

[0100] Formula 14-6 Formula 14-7.

[0101] Generally, naphthoquinone diazide compounds are obtained by esterification of naphthoquinone diazide sulfonic acid halides and phenolic compounds in a weakly alkaline environment.

[0102] Specifically, the phenolic compounds include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2' or 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy 4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy 3'-methoxybenzophenone, 2,3,4,2' or 2,3,4,6'-pentahydroxybenzophenone, 2,4,6,3', 2,4,6,4' or 2,4,6,5'-hexahydroxybenzophenone, 3,4,5,3', 3,4,6,6'-tetrahydroxybenzophenone. One or more of 5,4' or 3,4,5,5'-hexahydroxybenzophenone, bis(2,4-dihydroxybenzene)methane, bis(p-hydroxybenzene)methane, tris(p-hydroxybenzene)methane, 1,1,1-tris(p-hydroxybenzene)ethane, bis(2,3,4-trihydroxybenzene)methane, 2,2-bis(2,3,4-trihydroxybenzene)propane, 1,1,3-tris(2,5-dimethyl 4-hydroxybenzene)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxybenzene]-1-methylethyl]phenyl]ethylidene]bisphenol, and bis(2,5-dimethyl 4-hydroxybenzene)-2-hydroxybenzene methane.

[0103] In a specific implementation, the diazonaphthoquinone compound includes one or more of 1,2-diazonaphthoquinone-4-sulfonate, 1,2-diazonaphthoquinone-5-sulfonate, and 1,2-diazonaphthoquinone-6-sulfonate.

[0104] Illustratively, 1,2-diazonaphthoquinone-5-sulfonate includes one or more of 2,3,4'-trihydroxybenzophenone-1,2-diazonaphthoquinone-5-sulfonate prepared by esterification reaction of trihydroxybenzophenone and 2-diazo-1-naphthol-5-sulfonic acid, 2,3,4,4'tetrahydroxybenzophenone-1,2-diazonaphthoquinone-5-sulfonate prepared by esterification reaction of tetrahydroxybenzophenone and 2-diazo-1-naphthol-5-sulfonic acid, a compound prepared by esterification reaction of polyhydroxybenzophenone and 1,2-diazonaphthoquinone, and a compound prepared by esterification reaction of polyhydroxybenzophenone and 1,2-diazonaphthoquinone, 2-diazo-1-naphthol-5-sulfonic acid.

[0105] Generally, naphthoquinone diazide compounds are obtained by the esterification reaction of naphthoquinone diazide sulfonic acid halides and phenolic compounds in a weak alkaline environment. The degree of esterification of naphthoquinone diazide compounds refers to the ratio of the number of hydroxyl groups of the phenolic compounds used to prepare naphthoquinone diazide compounds participating in the esterification reaction to the total number of hydroxyl groups before participating in the esterification reaction, that is, the ratio of the number of ester groups of the naphthoquinone diazide compound to the total number of its ester groups and hydroxyl groups.

[0106] In some embodiments, the degree of esterification of the diazonaphthoquinone compound is 50% to 85%, for example, 50%, 60%, 65%, 70%, 75%, 80%, 85% or a range composed of any two thereof, which is beneficial to improving the residual film rate and storage stability of the positive photoresist composition.

[0107] In some embodiments, the sensitizer contains a hydroxyphenyl group, specifically including compounds represented by Formula 15-1 to Formula 15-5, which is beneficial for increasing the photosensitivity of the positive photoresist composition:

[0108] Formula 15-1, Formula 15-2,

[0109] Formula 15-3, Formula 15-4,

[0110] Formula 15-5.

[0111] In a specific implementation, the mass ratio of the sensitizer to the acrylic copolymer resin is 0-0.3, for example, 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3 or the range of any two thereof.

[0112] In addition, the mass ratio of the additive to the acrylic copolymer resin is 0-0.1; for example, 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 or a range consisting of any two thereof.

[0113] Specifically, the silane coupling agent includes one or more of a silane coupling agent having a carboxyl group, a silane coupling agent having a methyl propyl group, a silane coupling agent having an isocyanate group, and a silane coupling agent having an epoxy group, and specifically includes one or more of trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 2-(3',4'-epoxycyclohexyl)ethyltrimethoxysilane.

[0114] The mass ratio of the silane coupling agent to the acrylic copolymer resin is 0-0.1, preferably 0.001-0.05, for example, 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05 or a range consisting of any two of them, which is beneficial to improving the adhesion between the positive photoresist composition and the substrate.

[0115] Specifically, the leveling agent includes one or more of a fluorine-based surfactant and a silicone-based surfactant, and specifically includes BYK-333 (manufactured by BYK CHEMIE Co., Ltd.), R-08 (manufactured by DIC Corporation), R-475 (manufactured by DIC Corporation), R-30 (manufactured by DIC Corporation), BM-1000 (manufactured by BM CHEMIE Co., Ltd.), BM-1100 (manufactured by BM CHEMIE Co., Ltd.), FLUORADE FC-135 (manufactured by Sumitomo 3M Co., Ltd.), FLUORADE FC-170C (manufactured by Sumitomo 3M Co., Ltd.), FLUORADE FC-430 (manufactured by Sumitomo 3M Co., Ltd.), FLUORADE FC-431 (manufactured by Sumitomo 3M Co., Ltd.), SAFLON S-112 (manufactured by Asahi Glass Co., Ltd.), SAFLON S-113 (manufactured by Asahi Glass Co., Ltd.), SAFLON S-131 (manufactured by Asahi Glass Co., Ltd.), SAFLON S-141 (manufactured by Asahi Glass Co., Ltd.), Saflon S-145 (manufactured by Asahi Glass Co., Ltd.), Saflon S-382 (manufactured by Asahi Glass Co., Ltd.), Saflon SC-101 (manufactured by Asahi Glass Co., Ltd.), Saflon SC-102 (manufactured by Asahi Glass Co., Ltd.), Saflon SC-103 (manufactured by Asahi Glass Co., Ltd.), Saflon SC-104 (manufactured by Asahi Glass Co., Ltd.), Saflon SC-105 (manufactured by Asahi Glass Co., Ltd.), Saflon One or more of SC-106 (manufactured by Asahi Glass Co., Ltd.), SH-28PA (manufactured by Toray Silicone Co., Ltd.), SH-190 (manufactured by Toray Silicone Co., Ltd.), SH-193 (manufactured by Toray Silicone Co., Ltd.), SZ-6032 (manufactured by Toray Silicone Co., Ltd.), SF-8428 (manufactured by Toray Silicone Co., Ltd.), DC-57 (manufactured by Toray Silicone Co., Ltd.), and DC190 (manufactured by Toray Silicone Co., Ltd.).

[0116] In addition, the mass ratio of the leveling agent to the acrylic copolymer resin is 0.001-0.05, preferably 0.001-0.02, for example, 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02 or a range consisting of any two of them, which is beneficial for coating the positive photoresist composition on the substrate.

[0117] In some embodiments, the solvent includes propylene glycol monomethyl ether acetate and / or diethylene glycol methyl ethyl ether.

[0118] The embodiment of the present invention further provides a method for preparing the positive photoresist composition, which comprises the following steps: mixing a photosensitizer and an acrylic copolymer resin to obtain a positive photoresist composition.

[0119] In some embodiments, the process of mixing the photosensitive agent and the acrylic copolymer resin includes: mixing the photosensitive agent, the sensitizer, the additive, and the acrylic copolymer resin, and then adding a solvent thereto to obtain a positive photoresist composition.

[0120] In a specific implementation, firstly synthesize a first acrylate monomer, a second acrylate monomer and a third acrylate monomer; then copolymerize the monomer raw materials including the first acrylate monomer, the second acrylate monomer and the third acrylate monomer under the action of an initiator to obtain an acrylic copolymer resin; after mixing a photosensitizer, a sensitizer, an additive and the acrylic copolymer resin, a solvent is added thereto to obtain a mixture, and the viscosity of the mixture is controlled to be 3 cPs-20 cPs, for example, 3 cPs, 5 cPs, 8 cPs, 10 cPs, 13 cPs, 15 cPs, 18 cPs, 20 cPs or a range consisting of any two thereof, to obtain a positive photoresist composition.

[0121] Wherein, the initiator includes azo compounds, and the azo compounds specifically include azobisisobutylcyanide.

[0122] An embodiment of the present invention further provides a structural component, comprising the positive photoresist composition or a cured product formed by curing the positive photoresist composition prepared according to the preparation method of the positive photoresist composition.

[0123] In some embodiments, the refractive index of the cured product is 1.55-1.65, for example, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, or a range consisting of any two thereof.

[0124] In addition, the transmittance of the cured product after heat aging at 150±5°C for 240±2 hours is greater than or equal to 90%, for example, greater than or equal to 90%, greater than or equal to 91%, greater than or equal to 92%, greater than or equal to 93%, greater than or equal to 94%, greater than or equal to 95%, greater than or equal to 96%, greater than or equal to 97%, greater than or equal to 98%, greater than or equal to 99%, greater than or equal to 99.5%, or a range consisting of any two thereof.

[0125] An embodiment of the present invention also provides a method for preparing the above-mentioned structural part, comprising the following steps: subjecting a positive photoresist composition to a molding process to obtain a molding product; sequentially exposing and developing the molding product to obtain a structural part; wherein the developer comprises an alkaline solution.

[0126] In specific implementation, the positive photoresist composition is subjected to molding treatment and exposure, and then developed with an alkaline developer. The exposed part of the positive photoresist composition and the alkaline developer are dissolved and removed after an acid-base reaction, leaving a positive image of the unexposed part.

[0127] The present invention is further described below through specific embodiments.

[0128] Example 1

[0129] 1. Synthesis of the first acrylate monomer

[0130] After preparing a flask with a mechanical stirrer, a thermometer, and a cooling jacket, add 240 g of tetrahydrofuran, 26.5 g of 1,3,5-tribenzoyl chloride, and 30.0 g of triethylamine under a nitrogen stream, and after passing 5°C cooling water through the flask jacket, gradually drop 13.0 g of hydroxyethyl methacrylate into the flask, and then keep it at room temperature for 2 hours. Then add 34.0 g of p-hydroxybiphenyl into the flask, continue to react for 12 hours, filter, and obtain a clear solution. Then put the clear solution into water, obtain a precipitate with water, and dry it in a vacuum drying oven to obtain the compound shown in formula 10-1.

[0131] 2. Synthesis of the second acrylate monomer

[0132] After preparing a flask equipped with a mechanical stirrer, a thermometer, and a cooling jacket, add 240 g of tetrahydrofuran, 26.5 g of 1,3,5-tribenzoyl chloride, and 10.0 g of triethylamine under a nitrogen stream, and after passing 5 °C cooling water through the flask jacket, gradually drop 13.0 g of hydroxyethyl methacrylate into the flask, keep the carbon black at room temperature for 2 hours, and filter to obtain a clear solution. Then put the clear solution into water, obtain a precipitate with water, and dry it in a vacuum drying oven to obtain the compound shown in Formula 11-1.

[0133] 3. Synthesis of the third acrylate monomer

[0134] After preparing a flask equipped with a mechanical stirrer, a thermometer, and a cooling jacket, 240 g of tetrahydrofuran, 12.6 g of phloroglucinol, and 30.0 g of triethylamine were added under a nitrogen stream, and 5 °C cooling water was passed through the flask jacket, and 10.4 g of methacryloyl chloride was gradually added dropwise to the flask, and then kept at room temperature for 2 hours, and then 18.4 g of epichlorohydrin was added to the flask and heated to 100 °C and stirred for 1 hour, and filtered to obtain a clear solution. The clear solution was then put into water, and after obtaining a precipitate with water, it was dried in a vacuum drying oven to obtain the compound shown in Formula 12-1.

[0135] 4. Synthesis of acrylic copolymer resin

[0136] 10.0 g of the compound represented by formula 10-1, 5.0 g of the compound represented by formula 11-1, 5.0 g of the compound represented by formula 12-1, 0.2 g of azobisisobutyl cyanide, and 80.0 g of solvent propylene glycol monomethyl ether acetate (PGMEA) were placed in a sandwich reactor, nitrogen was introduced to exclude oxygen, the temperature was raised to 65°C, and the reaction was carried out under stirring for 24 hours to obtain an acrylic copolymer resin solution.

[0137] 5. Preparation of positive photoresist composition

[0138] 100 parts by mass of the acrylic copolymer resin obtained in step 4 (the mass parts are calculated based on the mass of the acrylic copolymer resin in the acrylic copolymer resin solution), 25 parts by mass of a photosensitive agent (TPA520, Miwon), 10 parts by mass of a sensitizer shown in formula 15-1, 1 part by mass of γ-glycidoxypropyltrimethoxysilane (XIAMETER™ OFS-6040 Silane, DOW), and 0.5 parts by mass of BYK-333 are added to a mixing tank equipped with an ultraviolet blocking film and a stirrer, and a solvent of propylene glycol monomethyl ether acetate is added while stirring to obtain a mixture. The amount of solvent is adjusted so that the viscosity of the mixture is 20 cPs. After the above components are mixed evenly, they are filtered through a microporous filter with a pore size of 0.45 μm to prepare a positive photoresist composition, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0139] Example 2

[0140] The difference from Example 1 is that in step 4, the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 5.0 g of the compound represented by Formula 10-1, 10.0 g of the compound represented by Formula 11-1, and 5.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0141] Example 3

[0142] 1. Synthesis of the first acrylate monomer

[0143] After preparing a flask with a mechanical stirrer, a thermometer, and a cooling jacket, 240 g of tetrahydrofuran, 26.1 g of 1,3,5-isocyanatotriphenylene oxide, and 0.1 g of dibutyltin dilaurate were added under a nitrogen stream, and the temperature of the flask was raised to 65°C. Then, 13.0 g of hydroxyethyl methacrylate was gradually added dropwise to the flask, and then the temperature was kept at 65°C for 2 hours. Then, 34.0 g of p-hydroxybiphenyl was added to the flask, and the reaction was continued at 65°C for 12 hours to obtain a reaction solution. The reaction solution was then put into water, and after obtaining a precipitate with water, it was dried in a vacuum drying oven to obtain a compound shown in Formula 10-2.

[0144] 2. Synthesis of the second acrylate monomer

[0145] After preparing a flask equipped with a mechanical stirrer, a thermometer, and a cooling jacket, add 240 g of tetrahydrofuran, 12.6 g of phloroglucinol, and 10.0 g of triethylamine under a nitrogen stream, pass 5 °C cooling water through the flask jacket, and then gradually drop 10.4 g of methacryloyl chloride into the reactor, then keep the mixture at room temperature for 2 hours, filter, and obtain a clear solution. Then, put the clear solution into water, obtain a precipitate with water, and dry it in a vacuum drying oven to obtain the compound shown in Formula 11-2.

[0146] 3. Synthesis of the third acrylate monomer

[0147] After preparing a flask with a mechanical stirrer, a thermometer, and a cooling jacket, 240 g of tetrahydrofuran, 12.6 g of phloroglucinol, and 0.1 g of dibutyltin dilaurate were added under a nitrogen stream, the temperature of the reactor was raised to 65 ° C, and 15.5 g of isocyanoethyl methacrylate was gradually added dropwise to the reactor, and then maintained at 65 ° C for 2 hours. 18.4 g of epichlorohydrin was added to the flask, heated to 100 ° C and stirred for 1 hour to obtain a reaction solution. The reaction solution was then put into water, precipitated with water, and dried in a vacuum drying oven to obtain a compound shown in Formula 12-2.

[0148] 4. Synthesis of acrylic copolymer resin

[0149] 10.0 g of the compound represented by formula 10-2, 5.0 g of the compound represented by formula 11-2, 5.0 g of the compound represented by formula 12-2, 0.2 g of azobisisobutyl cyanide, and 80.0 g of solvent PGMEA were placed in a sandwich reactor, nitrogen was introduced to exclude oxygen, the temperature was raised to 65°C, and the reaction was carried out for 24 hours under stirring to obtain an acrylic copolymer resin solution.

[0150] 5. Preparation of positive photoresist composition

[0151] 100 parts by mass of the acrylic copolymer resin obtained in step 4 (the mass parts are calculated based on the mass of the acrylic copolymer resin in the acrylic copolymer resin solution), 25 parts by mass of a photosensitive agent (TPA520, Miwon), 10 parts by mass of a sensitizer shown in formula 15-1, 1 part by mass of γ-glycidoxypropyltrimethoxysilane (XIAMETER™ OFS-6040 Silane, DOW), and 0.5 parts by mass of BYK-333 are added to a mixing tank equipped with an ultraviolet blocking film and a stirrer, and a solvent of propylene glycol monomethyl ether acetate is added while stirring to obtain a mixture. The amount of solvent is adjusted so that the viscosity of the mixture is 20 cPs. After the above components are mixed evenly, they are filtered through a microporous filter with a pore size of 0.45 μm to prepare a positive photoresist composition, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0152] Example 4

[0153] The difference from Example 3 is that in step 4, the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 5.0 g of the compound represented by Formula 10-2, 10.0 g of the compound represented by Formula 11-2, and 5.0 g of the compound represented by Formula 12-2, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0154] Example 5

[0155] 1. Synthesis of the first acrylate monomer

[0156] After preparing a flask with a mechanical stirrer, a thermometer, and a cooling jacket, 240 g of tetrahydrofuran, 12.6 g of phloroglucinol, and 0.1 g of dibutyltin dilaurate were added under a nitrogen stream, and the temperature of the flask was raised to 65 ° C. Then 15.5 g of isocyanoethyl methacrylate was gradually added dropwise to the flask, and then the temperature was kept at 65 ° C for 2 hours. Then 39.0 g of 4-biphenyl isocyanate was added to the flask, and the reaction was continued at 65 ° C for 12 hours to obtain a reaction solution. The reaction solution was then put into water, and after obtaining a precipitate with water, it was dried in a vacuum drying oven to obtain the compound shown in Formula 10-3.

[0157] 2. Synthesis of the second acrylate monomer

[0158] After preparing a flask equipped with a mechanical stirrer, a thermometer, and a cooling jacket, 240 g of tetrahydrofuran, 12.6 g of phloroglucinol, and 0.1 g of dibutyltin dilaurate were added under a nitrogen stream, the temperature of the flask was raised to 65°C, 15.5 g of isocyanoethyl methacrylate was gradually added dropwise to the flask, and then the temperature was maintained at 65°C for 2 hours to obtain a reaction solution. The reaction solution was then put into water, precipitated with water, and dried in a vacuum drying oven to obtain a compound represented by formula 11-3.

[0159] 3. Synthesis of the third acrylate monomer

[0160] After preparing a flask with a mechanical stirrer, a thermometer, and a cooling jacket, add 240 g of tetrahydrofuran, 26.5 g of 1,3,5-tribenzoyl chloride, and 30.0 g of triethylamine under a nitrogen stream, and after passing 5°C cooling water through the flask jacket, gradually drop 13.0 g of hydroxyethyl methacrylate into the flask, and then keep it at room temperature for 2 hours. Then add 14.8 g of glycidol to the flask and stir the reaction at room temperature for 12 hours. Filter to obtain a clear solution. Then put the clear solution into water, obtain a precipitate with water, and dry it in a vacuum drying oven to obtain the compound shown in formula 12-3.

[0161] 4. Synthesis of acrylic copolymer resin

[0162] 10.0 g of the compound represented by formula 10-3, 5.0 g of the compound represented by formula 11-3, 5.0 g of the compound represented by formula 12-3, 0.2 g of azobisisobutyl cyanide, and 80.0 g of solvent PGMEA were placed in a sandwich reactor, nitrogen was introduced to exclude oxygen, the temperature was raised to 65°C, and the reaction was carried out with stirring for 24 hours to obtain an acrylic copolymer resin solution.

[0163] 5. Preparation of positive photoresist composition

[0164] 100 parts by mass of the acrylic copolymer resin obtained in step 4 (the mass parts are calculated based on the mass of the acrylic copolymer resin in the acrylic copolymer resin solution), 25 parts by mass of a photosensitive agent (TPA520, Miwon), 10 parts by mass of a sensitizer shown in formula 15-1, 1 part by mass of γ-glycidoxypropyltrimethoxysilane (XIAMETER™ OFS-6040 Silane, DOW), and 0.5 parts by mass of BYK-333 are added to a mixing tank equipped with an ultraviolet blocking film and a stirrer, and a solvent propylene glycol monomethyl ether acetate is added while stirring to form a mixture. The amount of solvent is adjusted so that the viscosity of the mixture is 20 cPs. After the above components are mixed evenly, they are filtered through a microporous filter with a pore size of 0.45 μm to prepare a positive photoresist composition, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0165] Example 6

[0166] The difference from Example 5 is that in step 4, the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 5.0 g of the compound shown in Formula 10-3, 10.0 g of the compound shown in Formula 11-3, and 5.0 g of the compound shown in Formula 12-3, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0167] Example 7

[0168] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 30.0 g of the compound represented by Formula 10-1, 5.0 g of the compound represented by Formula 11-1, and 5.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0169] Example 8

[0170] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 40.0 g of the compound represented by Formula 10-1, 5.0 g of the compound represented by Formula 11-1, and 5.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0171] Example 9

[0172] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 2.0 g of the compound represented by Formula 10-1, 5.0 g of the compound represented by Formula 11-1, and 5.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0173] Example 10

[0174] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 1.0 g of the compound represented by Formula 10-1, 5.0 g of the compound represented by Formula 11-1, and 5.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0175] Embodiment 11

[0176] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 10.0 g of the compound represented by Formula 10-1, 45.0 g of the compound represented by Formula 11-1, and 5.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0177] Example 12

[0178] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 10.0 g of the compound represented by Formula 10-1, 60.0 g of the compound represented by Formula 11-1, and 5.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0179] Embodiment 13

[0180] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 10.0 g of the compound represented by Formula 10-1, 2.0 g of the compound represented by Formula 11-1, and 5.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0181] Embodiment 14

[0182] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 10.0 g of the compound represented by Formula 10-1, 1.0 g of the compound represented by Formula 11-1, and 5.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0183] Embodiment 15

[0184] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 10.0 g of the compound represented by Formula 10-1, 5.0 g of the compound represented by Formula 11-1, and 45.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0185] Example 16

[0186] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 10.0 g of the compound represented by Formula 10-1, 5.0 g of the compound represented by Formula 11-1, and 60.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0187] Embodiment 17

[0188] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 10.0 g of the compound represented by Formula 10-1, 5.0 g of the compound represented by Formula 11-1, and 2.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0189] Embodiment 18

[0190] The difference from Example 1 is that the added amounts of the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are changed to: 10.0 g of the compound represented by Formula 10-1, 5.0 g of the compound represented by Formula 11-1, and 1.0 g of the compound represented by Formula 12-1, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0191] Embodiment 19

[0192] The difference from Example 1 is that the mass percentage of the photosensitive agent is changed to 30, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0193] Embodiment 20

[0194] The difference from Example 1 is that the mass percentage of the photosensitive agent is changed to 40, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 19%.

[0195] Embodiment 21

[0196] The difference from Example 1 is that the synthesis process of the acrylic copolymer resin in step 4 is as follows:

[0197] 10.0 g of the compound represented by formula 10-1, 5.0 g of the compound represented by formula 11-1, 5.0 g of the compound represented by formula 12-1, 0.2 g of azobisisobutyl cyanide, and 80.0 g of solvent propylene glycol monomethyl ether acetate (PGMEA) were placed in a sandwich reactor, nitrogen was introduced to exclude oxygen, the temperature was raised to 65°C, and the reaction was stirred for 5 h to obtain an acrylic copolymer resin solution. Other conditions remained the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition was 20%.

[0198] Embodiment 22

[0199] The difference from Example 1 is that the synthesis process of the acrylic copolymer resin in step 4 is as follows:

[0200] 10.0 g of the compound represented by formula 10-1, 5.0 g of the compound represented by formula 11-1, 5.0 g of the compound represented by formula 12-1, 0.2 g of azobisisobutyl cyanide, and 80.0 g of solvent propylene glycol monomethyl ether acetate (PGMEA) were placed in a sandwich reactor, nitrogen was introduced to exclude oxygen, the temperature was raised to 65°C, and the reaction was stirred for 48 hours to obtain an acrylic copolymer resin solution. Other conditions remained the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition was 20%.

[0201] Comparative Example 1

[0202] The difference from Example 1 is that the first acrylate monomer is not added, 10.0 g of methyl methacrylate (MMA) is added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0203] Comparative Example 2

[0204] The difference from Example 2 is that the first acrylate monomer is not added, 5.0 g of methyl methacrylate (MMA) is added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0205] Comparative Example 3

[0206] The difference from Example 3 is that the first acrylate monomer is not added, 10.0 g of methyl methacrylate (MMA) is added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0207] Comparative Example 4

[0208] The difference from Example 4 is that the first acrylate monomer is not added, 5.0 g of methyl methacrylate (MMA) is added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0209] Comparative Example 5

[0210] The difference from Example 5 is that the first acrylate monomer is not added, 10.0 g of methyl methacrylate (MMA) is added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0211] Comparative Example 6

[0212] The difference from Example 6 is that the first acrylate monomer is not added, 5.0 g of methyl methacrylate (MMA) is added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0213] Comparative Example 7

[0214] The difference from Example 1 is that the first acrylate monomer is not added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0215] Comparative Example 8

[0216] The difference from Example 1 is that the second acrylate monomer is not added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0217] Comparative Example 9

[0218] The difference from Example 1 is that the third acrylate monomer is not added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0219] Comparative Example 10

[0220] The difference from Example 1 is that no photosensitizer is added, and other conditions remain the same, wherein the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 21%.

[0221] The type and amount of the first acrylate monomer, the type and amount of the second acrylate monomer, the type and amount of the third acrylate monomer, the weight average molecular weight of the acrylic copolymer resin, and the mass fraction of the photosensitive agent in each embodiment and comparative example are summarized in Table 1.

[0222] The prepared positive photoresist compositions were tested for performance through the following processes, and the results are shown in Table 2:

[0223] (1) Refractive index evaluation

[0224] After the positive photoresist composition was spin-coated on the silicon wafer substrate, the coated surface was heated and pre-dried (pre-dried at 100°C for 90 seconds), and after exposure without a photomask, it was developed at 25°C for 60 seconds with a tetramethylammonium hydroxide TMAH (2.38% mass fraction) aqueous solution, washed with pure water for 1 minute, and heated in an oven at 230°C for 30 minutes to form a cured product. The refractive index of the cured product was tested using an ellipsometer at a wavelength of 550nm.

[0225] Evaluation criteria: ◎: excellent, ●: good, ▲: fair, X: poor. According to the refractive index data, the evaluation is as follows: ◎: refractive index ≥ 1.60, ●: 1.55 ≤ refractive index < 1.60, ▲: 1.50 ≤ refractive index < 1.55, X: < 1.50.

[0226] (2) Transmittance evaluation

[0227] After the positive photoresist composition is spin-coated on the glass substrate, the coated surface is heated and pre-dried (pre-dried at 100°C for 90 seconds), and after exposure without a photomask, it is developed at 25°C for 60 seconds with a tetramethylammonium hydroxide TMAH (2.38% mass fraction) aqueous solution, washed with pure water for 1 minute, and heated in an oven at 230°C for 30 minutes to form a cured product. The cured product is placed in a 150°C oven for heat aging for 240 hours, and the transmittance of the cured product is tested at a wavelength of 400 nm using a UV-visible spectrophotometer.

[0228] Evaluation criteria: ◎: Excellent, ●: Good, ▲: Fair, X: Poor. According to the transmittance data, the evaluation is as follows: ◎: Transmittance > 95%, ●: 90% < Transmittance ≤ 95%, ▲: 85% ≤ Transmittance ≤ 90%, X: < 85%.

[0229] (3) Hardness evaluation

[0230] The curing process of the cured product is the same as the transmittance test. The hardness of the cured product is tested using a pencil hardness tester. The hardness test is performed by scratching with a standard pencil (Mitsubishi pencil: 1~6H, HB, 1~6B) at a load of 750g. The hardness is expressed based on the pencil without scratch marks. Hardness evaluation standard: The hardness increases in the order of 6B, 5B, 4B, 3B, 2B, B, HB, H, 2H, 3H, 4H, 5H, and 6H.

[0231] Evaluation criteria: ◎: Excellent, ●: Good, ▲: Fair, X: Poor. According to the hardness data, the evaluation is as follows: ◎: ≥3H, ●: 2H, ▲: H, X: ≤HB.

[0232] (4) Evaluation of substrate adhesion

[0233] The curing process of the cured product is the same as the transmittance test. The adhesion of the cured product to the substrate is tested by a cross-cut test. According to the ATSM-D3359 method, 100 checkerboard scales are formed on the cured product with a corner knife according to the checkerboard scale tape method, and then peeled with 3M's Scotch 600 tape, and the number of peeled checkerboard scales that have fallen off among the 100 peeled checkerboard scales is measured. According to the percentage of the number of peeled checkerboard scales that have fallen off in the 100 peeled checkerboard scales, the evaluation is as follows: 5B: no peeling (0%), 4B: peeling less than 5%, 3B: peeling 5%-15% (excluding 15%), 2B: peeling 15%-35% (excluding 35%), 1B: peeling 35%-65%, 0B: peeling>65%.

[0234] Evaluation criteria: ◎: Excellent (5B), ●: Good (4B), ▲: Fair (3B), X: Poor (<3B).

[0235] (5) Evaluation of development properties

[0236] After spin coating or slit coating the positive photoresist composition on the transparent substrate, the coated surface is heated and pre-dried (pre-dried at 100°C for 90 seconds), and then exposed through a photomask with a 1-50 μm pattern. After exposure, it is developed with a tetramethylammonium hydroxide TMAH (2.38% mass fraction) aqueous solution at 25°C for 60 seconds, washed with pure water for 1 minute, and heated in an oven at 230°C for 30 minutes to form a pattern.

[0237] Evaluation criteria: ◎: Excellent, ●: Good, ▲: Fair, X: Poor. According to the pattern formation size, the evaluation is as follows: ◎: 1-5um, ●: 6-15um, ▲: 16-50um, X: > 50um cannot be developed.

[0238] (6) Weight average molecular weight test: The weight average molecular weight of the acrylic copolymer resin in the examples and comparative examples was tested using an Agilent liquid chromatography system (1260 infinityII, Agilent Technologies, Inc., USA). 0.1 g of the acrylic copolymer resin was placed in a 40 mL sample bottle, 4 g of tetrahydrofuran (THF) was added, and the mixture was shaken for 1 min to dissolve. The sample was then tested at a flow rate of 1 mL / min.

[0239] Table 1

[0240]

[0241] Table 2

[0242]

[0243] It can be seen from Table 2 that, compared with Comparative Examples 1 to 10, the positive photoresist compositions in Examples 1 to 22 include an acrylic copolymer resin and a photosensitizer containing a first structural unit represented by Formula 1, a second structural unit represented by Formula 2, and a third structural unit represented by Formula 3. The positive photoresist composition has good anti-aging properties (i.e., its cured product still maintains a high transmittance after thermal aging at 150° C. for 240 hours), and has high refractive index, high transmittance, high adhesion and high hardness.

[0244] Specifically, compared with Comparative Examples 7 to 9, the positive photoresist composition in Example 1 includes an acrylic copolymer resin and a photosensitizer containing a first structural unit represented by Formula 1, a second structural unit represented by Formula 2, and a third structural unit represented by Formula 3. The positive photoresist composition has good anti-aging properties (i.e., its cured product still maintains a high transmittance after thermal aging at 150° C. for 240 hours), and has high refractive index, high transmittance, high adhesion and high hardness.

[0245] Compared with Comparative Examples 1 to 6, the acrylic copolymer resin in the positive photoresist composition in Examples 1 to 6 contains the first structural unit, which improves the anti-aging performance, refractive index, hardness, and adhesion of the positive photoresist composition. For example, compared with Comparative Example 1, the first acrylic ester monomer shown in Formula 10-1 is used in Example 1 to form the first structural unit, which improves the anti-aging performance, refractive index, hardness, and adhesion of the positive photoresist composition.

[0246] Compared with Example 20, Example 1 and Example 19 further control 0<a≤0.3, wherein a is the mass ratio of the photosensitive agent to the acrylic copolymer resin, so that the anti-aging performance of the positive photoresist composition is further improved, and its refractive index and transmittance are further improved.

[0247] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A positive photoresist composition, characterized in that: It includes an acrylic copolymer resin and a photosensitizer. The acrylic copolymer resin includes a first structural unit, a second structural unit, and a third structural unit. The first structural unit is shown in Formula 1: Formula 1, Wherein, R1 is selected from any one of a hydrogen atom and a methyl group, R2 and R3 are each independently selected from any one of the groups shown in Formula 1-1 and Formula 1-2, and n1 is any integer from 0 to 10. Formula 1-1, Formula 1-2; The second structural unit is shown in Formula 2: Formula 2, Wherein, R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups shown in Formula 1-1 and Formula 1-2, R4 is selected from any one of a carboxyl group and a hydroxyl group, and n2 is any integer from 0 to 10. Formula 1-1, Formula 1-2; The structure of the third structural unit is shown in Formula 3: Formula 3, Wherein, R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups shown in Formula 1-1 and Formula 1-2, R5 is selected from any one of the groups shown in Formula 3-1, Formula 3-2 and Formula 3-3, and n3 is any integer from 0 to 10. Formula 1-1, Formula 1-2, Formula 3-1, Formula 3-2, Formula 3-3.

2. The positive photoresist composition according to claim 1, characterized in that The first structural unit includes one or more of the structural units shown in Formula 4-1, Formula 4-2, and Formula 4-3: Formula 4-1, Formula 4-2, Formula 4-3; And / or, the second structural unit includes one or more of the structural units shown in Formula 5-1, Formula 5-2, and Formula 5-3: Formula 5-1, Formula 5-2 Formula 5-3; And / or, the third structural unit includes one or more of the structural units shown in Formula 6-1, Formula 6-2, and Formula 6-3: Formula 6-1, Formula 6-2 Formula 6-3; and / or, the weight average molecular weight of the acrylic copolymer resin is 500 g / mol to 100000 g / mol; And / or, the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 5%-95%.

3. The positive photoresist composition according to claim 1, characterized in that The acrylic copolymer resin is formed by copolymerizing monomer raw materials including a first acrylic ester monomer, a second acrylic ester monomer, and a third acrylic ester monomer; Preferably, the structure of the first acrylate monomer is as shown in Formula 7: Formula 7, Wherein, R1 is selected from any one of a hydrogen atom and a methyl group, R2 and R3 are each independently selected from any one of the groups shown in Formula 1-1 and Formula 1-2, and n1 is any integer from 0 to 10. Formula 1-1, Formula 1-2; Preferably, the structure of the second acrylate monomer is as shown in Formula 8: Formula 8, Wherein, R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups shown in Formula 1-1 and Formula 1-2, R4 is selected from any one of a carboxyl group and a hydroxyl group, and n2 is any integer from 0 to 10. Formula 1-1, Formula 1-2; Preferably, the structure of the third acrylate monomer is as shown in Formula 9: Formula 9, Wherein, R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups shown in Formula 1-1 and Formula 1-2, R5 is selected from any one of the groups shown in Formula 3-1, Formula 3-2 and Formula 3-3, and n3 is any integer from 0 to 10. Formula 1-1, Formula 1-2, Formula 3-1, Formula 3-2, Formula 3-3; Preferably, the mass percentage of the first acrylate monomer in the monomer raw material is 5% to 95%; Preferably, the mass percentage of the second acrylate monomer in the monomer raw material is 5% to 95%; Preferably, the mass percentage of the third acrylate monomer in the monomer raw material is 5% to 95%.

4. The positive photoresist composition according to claim 3, characterized in that: The first acrylate monomer includes one or more compounds represented by Formula 10-1, Formula 10-2, and Formula 10-3: Formula 10-1, Formula 10-2, Formula 10-3; And / or, the second acrylate monomer includes one or more compounds represented by Formula 11-1, Formula 11-2, and Formula 11-3: Formula 11-1, Formula 11-2, Formula 11-3; And / or, the third acrylate monomer includes one or more compounds represented by Formula 12-1, Formula 12-2, and Formula 12-3: Formula 12-1, Formula 12-2, Formula 12-3.

5. The positive photoresist composition according to claim 1, characterized in that: The positive photoresist composition satisfies: 0<a≤0.3, preferably 0.1≤a≤0.2, wherein a is the mass ratio of the photosensitizer to the acrylic copolymer resin; And / or, the photosensitizer includes a diazonaphthoquinone compound; And / or, the positive photoresist composition further comprises one or more of a sensitizer, an additive and a solvent, and the additive comprises one or more of a silane coupling agent and a leveling agent.

6. The positive photoresist composition according to claim 5, characterized in that: The degree of esterification of the naphthoquinone diazide compound is 50% to 85%; and / or, the sensitizer contains a hydroxyphenyl group; And / or, the mass ratio of the sensitizer to the acrylic copolymer resin is 0-0.3; and / or, the mass ratio of the additive to the acrylic copolymer resin is 0 to 0.1; And / or, the solvent includes propylene glycol monomethyl ether acetate and / or diethylene glycol methyl ethyl ether.

7. A method for preparing a positive photoresist composition according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: mixing a photosensitizer and an acrylic copolymer resin to obtain the positive photoresist composition; Preferably, the process of mixing the photosensitive agent and the acrylic copolymer resin comprises: mixing the photosensitive agent, the sensitizer, the additive and the acrylic copolymer resin, and then adding a solvent thereto to obtain the positive photoresist composition.

8. A structural member, characterized in that: A cured product comprising the positive photoresist composition according to any one of claims 1 to 6 or the positive photoresist composition prepared by the preparation method of the positive photoresist composition according to claim 7.

9. The structural member according to claim 8, characterized in that: The refractive index of the cured product is 1.55 to 1.65; And / or, the transmittance of the cured product after heat aging at 150±5° C. for 240±2 hours is greater than or equal to 90%.

10. A method for preparing a structural member according to any one of claims 8 to 9, characterized in that: The method comprises the following steps: subjecting a positive photoresist composition to a molding process to obtain a molding product; The molded product is sequentially exposed and developed to obtain the structural component; wherein the developer includes alkaline solution.

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