A positive photoresist composition, its preparation method and use

Abstract

The application provides a positive photoresist composition, a preparation method and application thereof. The positive photoresist composition comprises an acrylic copolymer resin and a photosensitive agent. The acrylic copolymer resin comprises 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 transmittance, high adhesion and high hardness.

Description

Technical Field

[0001] The present 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 materials technology, microlenses are important optical components widely used in display devices and image sensors. The primary function of a microlens is to converge or diverge light, enabling precise control of light while also improving light transmittance. Microlens properties, such as refractive index, transmittance, and aging resistance, directly impact the performance of displays and image sensors. Therefore, developing microlens materials with high refractive index, high transmittance, and excellent aging resistance is crucial for improving the performance of displays and image sensors.

[0003] Positive photoresist compositions have higher resolution than negative photoresist compositions and are therefore often used as high-resolution microlens materials. The acrylic resin in the positive photoresist composition has good transparency, weather resistance, and ease of processing, but has a relatively low refractive index. Existing technologies primarily increase the refractive index of the acrylic resin by introducing heteroatoms such as sulfur and halogens, thereby enhancing the refractive index of the positive photoresist composition. However, these methods can cause the aging resistance of the acrylic resin and the positive photoresist composition thereof to decrease, particularly after high-temperature thermal aging, where its transmittance and anti-yellowing properties can significantly decrease. In addition, the adhesion and hardness of the positive photoresist composition also need to be further enhanced.

[0004] Therefore, how to make the positive photoresist composition have high refractive index, high transmittance, high adhesion and high hardness without sacrificing the 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 represented by Formula 1:

[0007] Formula 1,

[0008] 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 represented by Formula 1-1 and Formula 1-2, and n1 is any integer from 0 to 10.

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

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

[0011] Formula 2,

[0012] wherein R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups represented by 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.

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

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

[0015] Formula 3,

[0016] wherein R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups represented by formula 1-1 and formula 1-2, R5 is selected from any one of the groups represented by formula 3-1, formula 3-2, and formula 3-3, and n3 is any integer from 0 to 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 represented by Formula 4-1, Formula 4-2, and Formula 4-3; and / or, the second structural unit includes one or more of the structural units represented by Formula 5-1, Formula 5-2, and Formula 5-3; and / or, the third structural unit includes one or more of the structural units represented by 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 100,000 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 formed by copolymerizing 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 represented by Formula 10-1, Formula 10-2, and Formula 10-3; and / or the second acrylate monomer includes one or more of the compounds represented by Formula 11-1, Formula 11-2, and Formula 11-3; and / or the third acrylate monomer includes one or more of the compounds represented by 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, sensitizer, additives 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; exposing and developing the molding product in sequence to obtain the structural part; wherein the developer comprises an alkaline solution.

[0028] The implementation of the present invention has at least the following beneficial effects: the positive photoresist composition of the present invention includes an acrylic copolymer resin and a photosensitizer; the acrylic copolymer resin includes 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 extending the service life of display devices and image sensors, and is suitable for fields such as optical device manufacturing, display device manufacturing, image sensor manufacturing, and polymer material science research. DETAILED DESCRIPTION

[0029] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction 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 making creative efforts shall fall within the scope of protection of the present invention.

[0030] An embodiment of 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 shown in Formula 1:

[0031] Formula 1,

[0032] 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 represented by Formula 1-1 and Formula 1-2, and n1 is any integer from 0 to 10, for example, 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] wherein R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups represented by 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, for example, 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] Wherein, R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups represented by Formula 1-1 and Formula 1-2, R5 is selected from any one of the groups represented by Formula 3-1, Formula 3-2, and Formula 3-3, and n3 is any integer from 0 to 10, for example, 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] For example, the acrylic copolymer resin may include a compound represented by Formula 13:

[0044] Formula 13,

[0045] 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 represented by Formula 1-1 and Formula 1-2, R4 is selected from any one of a carboxyl group and a hydroxyl group, R5 is selected from any one of the groups represented by Formula 3-1, Formula 3-2, and Formula 3-3, n1 is any integer from 0 to 10, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, n2 is any integer from 0 to 10, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and n3 is any integer from 0 to 10, for example, 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 inventors' research, an acrylic copolymer resin containing the first, second, and third structural units can increase the refractive index of a positive photoresist composition, thereby improving the performance of display devices and image sensors, enabling more precise control of light convergence and divergence, and thus enhancing image quality and display effects. Furthermore, the acrylic copolymer resin containing the first, second, and third structural units can enhance the aging resistance of the positive photoresist composition, maintaining a high transmittance even after high-temperature thermal aging, thereby extending the service life of display devices and image sensors.

[0049] The first, second, and third structural units are repeating units of an acrylic copolymer resin, all containing aromatic groups such as benzene rings. The first structural unit primarily regulates the refractive index, improving the refractive index of the positive photoresist composition. The second structural unit primarily regulates development, enhancing the performance of display devices and image sensors. The third structural unit primarily crosslinks and cures, increasing the hardness and chemical solvent resistance of the acrylic copolymer resin, thereby improving the aging resistance 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, a high refractive index, high adhesion, and high hardness. Specifically, the cured product of the positive photoresist composition has good anti-aging performance, a high refractive index, high adhesion, and high hardness.

[0051] In some embodiments, the first structural unit includes one or more structural units represented by 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 structural units represented by 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 structural units represented by 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 the 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 consisting of any two of them, 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 formed by copolymerizing monomer raw materials including a first acrylate monomer, a second acrylate monomer, and a third acrylate 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] 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 represented by Formula 1-1 and Formula 1-2, and n1 is any integer from 0 to 10, for example, 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] wherein R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups represented by 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, for example, 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] Wherein, R1 is selected from any one of a hydrogen atom and a methyl group, R2 is selected from any one of the groups represented by Formula 1-1 and Formula 1-2, R5 is selected from any one of the groups represented by Formula 3-1, Formula 3-2, and Formula 3-3, and n3 is any integer from 0 to 10, for example, 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 first acrylate monomer accounts for 5% to 95% by weight of the monomer raw material, 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 compounds represented by Formula 10-1, Formula 10-2, or 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 thereof, 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 naphthoquinone diazide 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 one or more of hydrogen atoms, 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, diazonaphthoquinone compounds are obtained by esterification of diazonaphthoquinone sulfonic acid halides with phenolic compounds in a weak 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', 3,4,6,7'-tetrahydroxybenzophenone. One or more of 5,4' or 3,4,5,5'-hexahydroxybenzophenone, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol, and bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane.

[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, the 1,2-diazonaphthoquinone-5-sulfonic acid ester includes one or more of 2,3,4'-trihydroxybenzophenone-1,2-diazonaphthoquinone-5-sulfonic acid ester prepared by esterification reaction of trihydroxybenzophenone and 2-diazo-1-naphthol-5-sulfonic acid, 2,3,4,4'tetrahydroxybenzophenone-1,2-diazonaphthoquinone-5-sulfonic acid ester 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 and 2-diazo-1-naphthol-5-sulfonic acid.

[0105] Generally, naphthoquinone diazide compounds are obtained by the esterification reaction of naphthoquinone diazide sulfonic acid halide and phenolic compound 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 compound used to prepare the naphthoquinone diazide compound 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 in 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 methylpropyl 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 composed of any two thereof, 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 thereof, 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] An embodiment of the present invention further provides a method for preparing the positive photoresist composition, comprising 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, a first acrylate monomer, a second acrylate monomer, and a third acrylate monomer are first synthesized; then, the monomer raw materials including the first acrylate monomer, the second acrylate monomer, and the third acrylate monomer are copolymerized under the action of an initiator to obtain an acrylic copolymer resin; a photosensitizer, a sensitizer, an additive, and the acrylic copolymer resin are mixed, and 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] 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 component, comprising the following steps: subjecting a positive photoresist composition to a molding process to obtain a molding product; exposing and developing the molding product in sequence to obtain a structural component; wherein the developer comprises an alkaline solution.

[0126] In specific implementation, the positive photoresist composition is subjected to a molding process and exposure, and then developed with an alkaline developer. The exposed portion 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 portion.

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

[0128] Example 1

[0129] 1. Synthesis of the first acrylate monomer

[0130] Prepare a flask equipped with a mechanical stirrer, thermometer, and 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. After passing 5°C cooling water through the flask jacket, gradually add 13.0 g of hydroxyethyl methacrylate dropwise to the flask. Maintain the mixture at room temperature for 2 hours. Then, add 34.0 g of p-hydroxybiphenyl to the flask. Continue the reaction for 12 hours, then filter to obtain a clear solution. This clear solution is then poured into water, precipitated with water, and dried in a vacuum oven to yield the compound represented by Formula 10-1.

[0131] 2. Synthesis of the second acrylate monomer

[0132] Prepare a flask equipped with a mechanical stirrer, thermometer, and 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. After passing 5°C cooling water through the flask jacket, gradually add 13.0 g of hydroxyethyl methacrylate dropwise to the flask. Maintain the carbon black at room temperature for 2 hours and filter to obtain a clear solution. This clear solution is then added to water, precipitated with water, and dried in a vacuum oven to yield the compound represented by Formula 11-1.

[0133] 3. Synthesis of the third acrylate monomer

[0134] Prepare a flask equipped with a mechanical stirrer, thermometer, and cooling jacket. Under a nitrogen stream, add 240 g of tetrahydrofuran, 12.6 g of phloroglucinol, and 30.0 g of triethylamine. After passing 5°C cooling water through the flask jacket, gradually add 10.4 g of methacryloyl chloride dropwise to the flask. After maintaining the flask at room temperature for 2 hours, add 18.4 g of epichlorohydrin, heat to 100°C, stir for 1 hour, and filter to obtain a clear solution. This clear solution is then added to water, precipitated with water, and dried in a vacuum oven to yield the compound represented by 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 azobisisobutylcyanide, and 80.0 g of propylene glycol monomethyl ether acetate (PGMEA) as solvent 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.

[0137] 5. Preparation of positive photoresist composition

[0138] To a mixing tank equipped with a UV-blocking film and a stirrer, 100 parts by mass of the acrylic copolymer resin obtained in step 4 (calculated based on the mass of the acrylic copolymer resin in the acrylic copolymer resin solution), 25 parts by mass of a photosensitizer (TPA520, Miwon), 10 parts by mass of a sensitizer represented by Formula 15-1, 1 part by mass of γ-glycidoxypropyltrimethoxysilane (XIAMETER™ OFS-6040 Silane, DOW), and 0.5 parts by mass of BYK-333 were added. Propylene glycol monomethyl ether acetate was added as a solvent while stirring to obtain a mixture. The amount of solvent was adjusted to achieve a viscosity of 20 cPs. After uniform mixing, the mixture was filtered through a microporous filter with a pore size of 0.45 μm to prepare a positive photoresist composition in which the acrylic copolymer resin accounted for 20% by mass of the positive photoresist composition.

[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; other conditions remain the same, and 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 equipped with a mechanical stirrer, thermometer, and cooling jacket, 240 g of tetrahydrofuran, 26.1 g of 1,3,5-triphenyl isocyanate, and 0.1 g of dibutyltin dilaurate were added under a nitrogen stream. The flask temperature was raised to 65°C, and 13.0 g of hydroxyethyl methacrylate was gradually added dropwise. The reaction was then maintained at 65°C for 2 hours. 34.0 g of p-hydroxybiphenyl was then added to the flask, and the reaction continued at 65°C for 12 hours to obtain a reaction solution. The reaction solution was then poured into water, precipitated with water, and dried in a vacuum oven to obtain the compound represented by Formula 10-2.

[0144] 2. Synthesis of the second acrylate monomer

[0145] Prepare a flask equipped with a mechanical stirrer, thermometer, and cooling jacket. Add 240 g of tetrahydrofuran, 12.6 g of phloroglucinol, and 10.0 g of triethylamine under a nitrogen stream. Pour 5°C cooling water into the flask jacket. Then, gradually add 10.4 g of methacryloyl chloride dropwise to the reactor. Maintain the mixture at room temperature for 2 hours and filter to obtain a clear solution. This clear solution is then added to water, precipitated with water, and dried in a vacuum oven to yield the compound represented by Formula 11-2.

[0146] 3. Synthesis of the third acrylate monomer

[0147] After preparing a flask equipped with a mechanical stirrer, thermometer, and 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 reactor temperature was raised to 65°C, and 15.5 g of isocyanoethyl methacrylate was gradually added dropwise to the reactor. The reaction was then maintained at 65°C for 2 hours. 18.4 g of epichlorohydrin was then added to the flask, heated to 100°C, and stirred for 1 hour to obtain a reaction solution. The reaction solution was then poured into water, precipitated with water, and dried in a vacuum oven to obtain the compound represented by 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 with stirring for 24 hours to obtain an acrylic copolymer resin solution.

[0150] 5. Preparation of positive photoresist composition

[0151] To a mixing tank equipped with a UV-blocking film and a stirrer, 100 parts by mass of the acrylic copolymer resin obtained in step 4 (calculated based on the mass of the acrylic copolymer resin in the acrylic copolymer resin solution), 25 parts by mass of a photosensitizer (TPA520, Miwon), 10 parts by mass of a sensitizer represented by Formula 15-1, 1 part by mass of γ-glycidoxypropyltrimethoxysilane (XIAMETER™ OFS-6040 Silane, DOW), and 0.5 parts by mass of BYK-333 were added. Propylene glycol monomethyl ether acetate was added as a solvent while stirring to obtain a mixture. The amount of solvent was adjusted to achieve a viscosity of 20 cPs. After uniform mixing, the mixture was filtered through a microporous filter with a pore size of 0.45 μm to prepare a positive photoresist composition in which the acrylic copolymer resin accounted for 20% by mass of the positive photoresist composition.

[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; other conditions remain the same, and 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 equipped with a mechanical stirrer, thermometer, and 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 flask temperature was raised to 65°C, and 15.5 g of isocyanoethyl methacrylate was gradually added dropwise to the flask. The reaction temperature was then maintained at 65°C for 2 hours. 39.0 g of 4-biphenyl isocyanate was then added to the flask, and the reaction continued at 65°C for 12 hours to obtain a reaction solution. The reaction solution was then poured into water, precipitated with water, and dried in a vacuum oven to obtain the compound represented by Formula 10-3.

[0157] 2. Synthesis of the second acrylate monomer

[0158] Prepare a flask equipped with a mechanical stirrer, thermometer, and cooling jacket. Under a nitrogen stream, add 240 g of tetrahydrofuran, 12.6 g of phloroglucinol, and 0.1 g of dibutyltin dilaurate. Raise the flask temperature to 65°C, then gradually add 15.5 g of isocyanoethyl methacrylate dropwise. Maintain the temperature at 65°C for 2 hours to obtain a reaction solution. Add the reaction solution to water, obtain a precipitate with water, and dry it in a vacuum oven to obtain the compound represented by Formula 11-3.

[0159] 3. Synthesis of the third acrylate monomer

[0160] Prepare a flask equipped with a mechanical stirrer, thermometer, and 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. After passing 5°C cooling water through the flask jacket, gradually add 13.0 g of hydroxyethyl methacrylate dropwise to the flask. Maintain the mixture at room temperature for 2 hours. Then, add 14.8 g of glycidol and stir at room temperature for 12 hours. Filter to obtain a clear solution. Add the clear solution to water, obtain a precipitate with water, and dry it in a vacuum oven to obtain the compound represented by 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] To a mixing tank equipped with a UV-blocking film and a stirrer, 100 parts by mass of the acrylic copolymer resin obtained in step 4 (calculated based on the mass of the acrylic copolymer resin in the acrylic copolymer resin solution), 25 parts by mass of a photosensitizer (TPA520, Miwon), 10 parts by mass of a sensitizer represented by Formula 15-1, 1 part by mass of γ-glycidoxypropyltrimethoxysilane (XIAMETER™ OFS-6040 Silane, DOW), and 0.5 parts by mass of BYK-333 were added. Propylene glycol monomethyl ether acetate was added as a solvent while stirring to form a mixture. The amount of solvent was adjusted to achieve a viscosity of 20 cPs. After uniform mixing, the mixture was filtered through a Millipore filter with a pore size of 0.45 μm to prepare a positive photoresist composition in which the acrylic copolymer resin accounted for 20% by mass of the positive photoresist composition.

[0165] Example 6

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

[0175] Example 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; other conditions remain the same, and 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; other conditions remain the same, and the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0179] Example 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; other conditions remain the same, and the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0181] Example 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; other conditions remain the same, and the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0183] Example 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; other conditions remain the same, and 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; other conditions remain the same, and the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0187] Example 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; other conditions remain the same, and the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0189] Example 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; other conditions remain the same, and the mass percentage of the acrylic copolymer resin in the positive photoresist composition is 20%.

[0191] Example 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] Example 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] Example 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 propylene glycol monomethyl ether acetate (PGMEA) solvent 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 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] Example 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 propylene glycol monomethyl ether acetate (PGMEA) solvent 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 48 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%.

[0201] Comparative Example 1

[0202] The difference from Example 1 is that the first acrylate monomer is not added, and 10.0 g of methyl methacrylate (MMA) is added. Other conditions remain the same, and 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, and 5.0 g of methyl methacrylate (MMA) is added, while 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, and 10.0 g of methyl methacrylate (MMA) is added, while 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, and 5.0 g of methyl methacrylate (MMA) is added, while 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, and 10.0 g of methyl methacrylate (MMA) is added, while 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, and 5.0 g of methyl methacrylate (MMA) is added, while 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 performance of the prepared positive photoresist composition was tested by the following processes, and the results are shown in Table 2:

[0223] (1) Refractive index evaluation

[0224] After spin-coating a positive photoresist composition onto a silicon wafer substrate, the coated surface was pre-baked by heating (at 100°C for 90 seconds). After exposure without a photomask, the surface was developed with a 2.38% mass fraction aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C for 60 seconds, rinsed 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 measured using an ellipsometer at a wavelength of 550nm.

[0225] Evaluation criteria: ◎: Excellent, ●: Good, ▲: Fair, X: Poor. Based on 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 spin-coating a positive photoresist composition onto a glass substrate, the coated surface was pre-baked by heating (at 100°C for 90 seconds). After exposure without a photomask, the surface was developed with a 2.38% mass fraction aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C for 60 seconds, rinsed with pure water for 1 minute, and heated in a 230°C oven for 30 minutes to form a cured product. The cured product was then placed in a 150°C oven for heat aging for 240 hours. The transmittance of the cured product was measured using a UV-visible spectrophotometer at a wavelength of 400 nm.

[0228] Evaluation criteria: ◎: Excellent, ●: Good, ▲: Fair, X: Poor. Based on 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 for the cured product is the same as the transmittance test. The cured product was tested for hardness using a pencil hardness tester. A standard pencil (Mitsubishi pencils: 1-6H, HB, 1-6B) was used to scratch the product with a 750g load. The hardness was expressed based on the pencil's scratch marks. The hardness evaluation scale increases in order from 6B, 5B, 4B, 3B, 2B, B, HB, H, 2H, 3H, 4H, 5H, and 6H.

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

[0232] (4) Evaluation of substrate adhesion

[0233] The curing process for the cured product is the same as the transmittance test. Adhesion between the cured product and the substrate is tested using a cross-hatch test. Using the ATSM-D3359 method, 100 checkerboard scales are formed on the cured product using a corner knife using the checkerboard scale tape method. The product is then peeled off using 3M Scotch 600 tape. The number of peeled checkerboard scales that have fallen off is measured. The percentage of peeled checkerboard scales out of the total 100 peeled checkerboard scales is evaluated as follows: 5B: No peeling (0%), 4B: Less than 5% peeling, 3B: 5%-15% peeling (excluding 15%), 2B: 15%-35% peeling (excluding 35%), 1B: 35%-65% peeling, and 0B: >65% peeling.

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

[0235] (5) Development evaluation

[0236] After spin coating or slit coating a positive photoresist composition on a transparent substrate, the coated surface is heated and pre-baked (pre-baked 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. Evaluation based on pattern size is as follows: ◎: 1-5μm, ●: 6-15μm, ▲: 16-50μm, X: >50μm 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, 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 and dissolved for 1 min to obtain a sample, which was tested at a flow rate of 1 mL / min.

[0239] Table 1

[0240]

[0241] Table 2

[0242]

[0243] As can be seen from Table 2, compared with Comparative Examples 1 to 10, the positive photoresist compositions in Examples 1 to 22 include an acrylic copolymer resin 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, and a photosensitizer. The positive photoresist compositions have good aging resistance (i.e., their cured products still maintain a high transmittance after thermal aging at 150° C. for 240 hours), and have 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 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, and a photosensitizer. The positive photoresist composition has good anti-aging properties (i.e., its cured product still maintains a high transmittance after 240 hours of thermal aging at 150°C), and has high refractive index, high transmittance, high adhesion and high hardness.

[0245] Compared to Comparative Examples 1-6, the acrylic copolymer resin in the positive photoresist compositions of Examples 1-6 contains a first structural unit, which improves the aging resistance, refractive index, hardness, and adhesion of the positive photoresist compositions. For example, compared to Comparative Example 1, Example 1 uses a first acrylate monomer represented by Formula 10-1 to form the first structural unit, which improves the aging resistance, 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 as to further improve the anti-aging performance of the positive photoresist composition and further improve its refractive index and transmittance.

[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 above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above 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 represented by Formula 1-1 and Formula 1-2, and n1 is any integer from 1 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 represented by 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 1 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 represented by formula 1-1 and formula 1-2, R5 is selected from any one of the groups represented by formula 3-1, formula 3-2, and formula 3-3, and n3 is any integer from 1 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 structural units represented by 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 structural units represented by Formula 5-1 and Formula 5-2: Formula 5-1, Formula 5-2; And / or, the third structural unit includes one or more structural units represented by Formula 6-1 and Formula 6-2: Formula 6-1, Formula 6-2; and / or, the weight average molecular weight of the acrylic copolymer resin is 500 g / mol to 100,000 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; The structure of the first acrylate monomer is 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 represented by Formula 1-1 and Formula 1-2, and n1 is any integer from 0 to 10. Formula 1-1, Formula 1-2; The structure of the second acrylate monomer is 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 represented by 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 acrylate monomer is 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 represented by formula 1-1 and formula 1-2, R5 is selected from any one of the groups represented by 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; The mass percentage of the first acrylate monomer in the monomer raw material is 5% to 95%; The mass percentage of the second acrylate monomer in the monomer raw material is 5% to 95%; 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 and Formula 11-2: Formula 11-1, Formula 11-2; And / or, the third acrylate monomer includes one or more compounds represented by Formula 12-1 and Formula 12-2: Formula 12-1, Formula 12-2.

5. The positive photoresist composition according to claim 1, characterized in that The positive photoresist composition satisfies: 0<a≤0.3, wherein a is the mass ratio of the photosensitizer to the acrylic copolymer resin; and / or, the photosensitizer comprises 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 positive photoresist composition satisfies: 0.1≤a≤0.

2.

7. 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 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.

8. A method for preparing the positive photoresist composition according to any one of claims 1 to 7, characterized in that: The following steps are involved: The photosensitizer and the acrylic copolymer resin are mixed to obtain the positive photoresist composition.

9. The method for preparing the positive photoresist composition according to claim 8, wherein: 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.

10. A structural member, characterized in that: A cured product formed by curing the positive photoresist composition according to any one of claims 1 to 7 or the positive photoresist composition prepared according to the preparation method of the positive photoresist composition according to claim 8 or 9.

11. The structural member according to claim 10, 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%.

12. A method for preparing a structural member according to any one of claims 10 to 11, 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 exposed to light and then developed with a developer to obtain the structural component; wherein the developer includes an alkaline solution.

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