Polyimide resin precursor, alkali-soluble resin and positive photosensitive composition

Abstract

The invention belongs to the technical field of photoetching, particularly relates to a polyimide resin precursor, alkali-soluble resin and application thereof, and also relates to a positive photosensitive composition. The polyimide resin precursor is formed by copolymerization of a diamine monomer, a dianhydride monomer and an end-capping reagent, the end-capping reagent comprises a formula A, a formula B and a formula Z, the formula A represents a reaction group between the end-capping reagent and the tail end of polyimide resin, the formula B represents a phenolic hydroxyl structure with an electron withdrawing group, and the formula Z represents a structure for connecting the formula A and the formula B; the structure of the end-capping reagent is shown as a formula (I). The polyimide precursor resin provided by the invention has higher alkali dissolution speed, and the efficiency of action with photosensitive substances is enhanced, so that the positive photosensitive resin composition containing the polyimide precursor resin ensures high film retention rate, and has higher sensitivity and resolution. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of photolithography, and in particular relates to a polyimide resin precursor, an alkali-soluble resin using the same and applications thereof, and also relates to a positive photosensitive composition. Background Art

[0002] Because polyimide resins not only possess excellent heat resistance and insulation properties, but also exhibit low stress and high elongation after film formation, they are widely used in surface protective films, interlayer insulating films, and insulating layers of semiconductor components, as well as in organic electroluminescent devices. In recent years, with the development of various industries, protective layers and insulating layers in components have also required higher exposure and development sensitivity and patterning resolution, thus placing higher demands on the sensitivity and resolution of photosensitive polyimide (PSPI). Generally speaking, resins such as polyimide and polybenzoxazole are widely used in semiconductor and other electronic devices due to their good alkali solubility, heat resistance, and high strength. Specifically, such as the redistribution layer (RDL) and bump layer in IC devices, the device's radiation protection layer and insulating layer, and the pixel definition layer (PDL) and planarization layer (PLN) in OLED devices. Although existing compositions can produce ideal patterns, it is difficult to meet the higher requirements for exposure sensitivity and development resolution.

[0003] Currently, known positive photosensitive resin compositions include: compositions comprising soluble polyimide precursor resins such as polyamic acid, polyamic acid / polyimide, and polyamic acid ester / polyamic acid, plus a photoacid generator (such as diazonaphthoquinone), a thermal crosslinker, and a solvent. Polyamic acid is highly soluble in alkaline solutions. While the addition of diazonaphthoquinone as a photoacid generator can somewhat improve alkali resistance in photosensitive resin compositions, ideal patterns are rarely achieved after exposure. While the addition of polyamide ester and polyimide to adjust alkali solubility is effective, achieving higher exposure sensitivity and development resolution is difficult.

[0004] During resin synthesis, existing solutions generally incorporate end-capping agents to adjust the resin's dissolution rate in aqueous alkaline solutions. (CN 107079560B, CN 107431020 B) These resins are end-capped with monoamines, anhydrides, monocarboxylic acids, monoacyl chlorides, or monoactive esters containing acidic groups, resulting in resins with acidic groups at the ends of their backbones. (CN 111812943 A, CN 112180684 A) Alkali-soluble resins also contain end-capping groups. By adjusting the type and amount of end-capping agent, the resin's dissolution rate in aqueous alkaline solutions can be easily adjusted. However, these end-capping agents are common and can only adjust the resin's dissolution rate in alkaline solutions, but cannot improve the resin's photolithographic performance or resolution.

[0005] Therefore, there is an urgent need in this field to develop a photosensitive resin material that has excellent heat resistance, chemical resistance, pattern stability, high sensitivity, and high resolution. Summary of the Invention

[0006] In order to solve the problems in the above-mentioned prior art, the inventors have devoted themselves to research, with the aim of providing a polyimide precursor resin, a positive photosensitive resin composition and its application. Through the design of molecular structure and functional groups, it is necessary to use phenol containing electron-withdrawing groups as a capping agent for resin synthesis, so that the polyimide precursor resin has a higher alkali solubility rate and enhanced efficiency of interaction with photosensitive substances, so that the positive photosensitive resin composition containing the polyimide precursor resin can ensure a high film retention rate and have higher sensitivity and resolution.

[0007] The present invention adopts the following technical solutions:

[0008] One of the purposes of the present invention is to provide a polyimide resin (PI) precursor, which is copolymerized by a diamine monomer, a dianhydride monomer, and a capping agent with a specific structure. The capping agent structure includes three parts: formula A, formula B, and formula Z. Formula A represents a reactive group between the capping agent and the end of the polyimide resin, formula B represents a phenolic hydroxyl structure with an electron-withdrawing group or group, and formula Z represents a structure for connecting formulas A and B.

[0009] The structure of the end-capping agent is shown in the following formula (I):

[0010]

[0011] In formula (I), Ring A is a C6-C30 aryl group; R0 is selected from amino, anhydride, carboxyl or acyl chloride;

[0012] Ra represents one to the maximum permissible number of substituent groups, and Ra are each independently selected from any one of hydrogen, halogen, trihalomethyl, halogen-containing hydrocarbon group, sulfonyl, formyl, acyl, carboxyl, hydroxyl, unsubstituted or halogen-substituted C6-C30 aryl;

[0013] Ring B is a C6-C30 aryl group;

[0014] Rb represents one to the maximum permissible number of substituent groups, at least one Rb is an electron-withdrawing group or group, each Rb is independently selected from any one of hydrogen, halogen, tertiary amine cation, trihalomethyl, halogen-containing hydrocarbon group, unsubstituted or halogen-substituted C6-C30 aryl group, hydroxyl, nitro, cyano, sulfonyl, formyl, acyl, and carboxyl, and at least one Rb is one of halogen, tertiary amine cation, trihalomethyl, and halogen-containing hydrocarbon group;

[0015] In formula (I), Z is a divalent organic group having 1 to 40 atoms; preferably, Z is selected from one of -CO-, -CHR-, -C2H3R-, -O-, -C3H5R-, -SO2-, -S-, Si(CH3)2-, -COO-, -CONH-, and -C6H3R-.

[0016] Further preferably, the capping agent has a structure as shown in formula (I'):

[0017]

[0018] R0 is selected from amino, anhydride, carboxyl or acyl chloride;

[0019] R1-R4 are each independently selected from any one of hydrogen, halogen, trihalomethyl, halogen-containing hydrocarbon group, sulfonyl, formyl, acyl, carboxyl, hydroxyl, unsubstituted or halogen-substituted C6-C30 aryl; more preferably, R1-R4 are each independently selected from hydrogen, carboxyl or hydroxyl.

[0020] R5-R8 contain at least one electron-withdrawing group or radical, and R5-R8 are each independently selected from any one of hydrogen, halogen, tertiary amine cation, trihalomethyl, halogen-containing hydrocarbon group, unsubstituted or halogen-substituted C6-C30 aryl group, hydroxyl, nitro, cyano, sulfonyl, formyl, acyl, and carboxyl, and at least one of R5-R8 is selected from halogen, trihalomethyl, or halogen-containing hydrocarbon group; preferably, 1-3 of R5-R8 are selected from halogen, trihalomethyl, or halogen-containing hydrocarbon group; most preferably, 1-2 of R5-R8 are selected from halogen, trihalomethyl, or halogen-containing hydrocarbon group. That is, the number of electron-withdrawing groups or radicals in R5-R8 is preferably 1-3, and most preferably 1-2.

[0021] Z is selected from one of -CO-, -CHR-, -C2H3R-, -O-, -C3H5R-, -SO2-, -S-, Si(CH3)2-, -COO-, -CONH-, -C6H3R-, and R is selected from hydrogen, C1-C10 alkyl or C6-C30 aryl; preferably, Z is selected from -CHR-, -SO2- or -CONH-.

[0022] More preferably, in the photoresist composition, the polyimide precursor resin is at least one copolymer selected from polyamic acid, polyamic acid ester, polyimide, and polyisoimide.

[0023] Still more preferably, in the photoresist composition, the proportion of the monomer end-capping agent represented by the structure of formula (I') in the polyimide precursor resin is 10-70%, more preferably 20-50%, and the proportion is a molar ratio.

[0024] In the photoresist composition of the present invention, the photosensitive substance preferentially forms hydrogen bonds with the phenolic structure having the strongest H-donating ability, and the structure of the phenolic hydroxyl group determines its H-donating ability. In the present invention, in the end-capping agent preferably having a structure as shown in formula (I), an electron-withdrawing group or group is connected to the phenolic hydroxyl ring B. Due to the electron-withdrawing inductive effect and the conjugation effect, the electron cloud density of the oxygen atom in the benzene ring and the hydroxyl group is reduced, making it easier for the hydrogen electrons in the hydroxyl group to delocalize to the benzene ring, thereby enhancing the ability to provide H, that is, enhancing the ability of the photosensitive substance to form a hydrogen bond with the phenolic hydroxyl group. Therefore, the ability of the photosensitive substance to form a hydrogen bond with the phenolic hydroxyl group in the end-capping agent (I) structure is stronger and more efficient. Therefore, the dissolution in the non-exposed area is better suppressed, which is beneficial to improving the residual film rate. In the exposed area, since the photosensitive substance decomposes into carboxylic acid after exposure, the dissolution of the exposed area is increased, which is beneficial to improving the sensitivity. Moreover, after exposure, the phenolic hydroxyl group in the end-capping agent having a structure as shown in formula (I) in the present invention has a stronger ability and speed to react with the alkaline solution, which accelerates the alkali dissolution rate of the polyimide precursor resin, thereby increasing the contrast between the alkali dissolution rates of the exposed area and the non-exposed area, thereby improving the contrast and resolution. In summary, it is precisely because of the presence of the capping agent (I) having the structure shown in formula (I) that not only the dissolution inhibition of the non-exposed area is enhanced, but also the dissolution promotion of the exposed area is enhanced, so that the performance of the photoresist composition can be fully improved.

[0025] Among them, "sensitivity" is an indicator that measures the sensitivity of photoresist to light during exposure, which refers to the minimum exposure amount that can obtain a better pattern. The higher the sensitivity, the smaller the exposure amount. Therefore, photoresists with higher sensitivity are advantageous in terms of production efficiency; "alkali dissolution rate" refers to the dissolution rate of the photoresist composition in alkaline developer; "residual film rate" refers to the ratio of the film thickness after development of the non-exposed area to the film thickness before development. The higher the film retention rate, the more resistant the photoresist composition to washing; "contrast" refers to the difference in alkali dissolution rate between the exposed area and the unexposed area of the photoresist film. Photoresists with high contrast are advantageous for forming clear patterns; "image resolution" refers to the size of the minimum pattern that the photoresist can obtain.

[0026] In the present invention, the expression of chemical elements includes the concept of isotopes with the same chemical properties. For example, the expression "hydrogen" also includes the concepts of "deuterium" and "tritium" with the same chemical properties.

[0027] In the present specification, the hydrocarbon group includes an alkane group, an alkene group, an aromatic hydrocarbon group, an alkane group containing a substituent, an alkene group containing a substituent, an aromatic hydrocarbon group containing a substituent, and the like. Examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, vinyl, propenyl, butenyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, triphenylenyl, pyrenyl, peryl, fluoranthenyl, biphenyl, phenylene, terphenyl, triphenyl, fluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, 2-biphenyl, 3-biphenyl and 4-biphenyl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl; 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 9-fluorenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, etc.

[0028] In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or with multiple substituents. When there are multiple substituents (at least 2), they may be the same or different substituents. When the same expression is mentioned below, it has the same meaning, and the selection range of the substituents is as shown above and will not be repeated one by one.

[0029] In the present invention, the C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) tetravalent aromatic group includes a C6-C30 aryl group (e.g., phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, anthracenyl, phenanthrenyl, triphenylene, naphthacene, etc.) or an aryl group connected by a bridging bond (single bond, O, S, sulfoxide, sulfone, substituted or unsubstituted alkylene, etc.). Similar examples are provided below for the "C6-C30 divalent aromatic group."

[0030] The C4-C20 (e.g., C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc.) tetravalent alicyclic group, "alicyclic group" means a non-aromatic saturated or unsaturated cyclic structure, including a monocyclic, bridged, spirocyclic, or condensed ring, and exemplarily includes but is not limited to cyclobutane, cyclopentane, cyclohexane, bicyclooctane, etc. Similar examples are provided below for "C4-C20 divalent alicyclic group."

[0031] The C1-C20 straight chain or branched chain alkyl group can be a straight chain or branched chain alkyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc., illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl or n-decyl, etc.

[0032] Specific examples of the C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy group include monovalent groups obtained by connecting the above-mentioned straight-chain or branched-chain alkyl groups to O.

[0033] More preferably, the capping agent having a structure such as formula (I) is selected from the following structures, but is not limited to the following structures:

[0034]

[0035]

[0036]

[0037] A second object of the present invention is to provide an alkali-soluble resin, which comprises a portion (a1), which is a polyimide resin precursor and may also include a copolymer selected from polyamic acid, polyamic acid ester, polyimide, polyisoimide, and a copolymer composed of polyamic acid, polyamic acid ester, polyimide, and polyisoimide.

[0038] The polyimide precursor resin is copolymerized by diamine monomer, dianhydride monomer and a capping agent having a structure as shown in formula (I), and the polyimide precursor resin is at least one selected from polyamic acid, polyamic acid ester, polyimide, polyisoimide and copolymers of the above resins.

[0039] Specifically, the preparation method of the polyimide precursor is to obtain a tetracarboxylic dianhydride residue or a diamine residue through the reaction of tetracarboxylic dianhydride or tetracarboxylic acid with a diamine, and then the tetracarboxylic dianhydride residue or diamine residue is reacted with a capping agent portion of the structure represented by formula (I), or is left untreated, or is esterified, or is chemically or thermally imidized to obtain a polyimide precursor.

[0040] Further preferably, the alkali-soluble resin also contains part (a2), which includes one or more of ordinary end-capped or unend-capped polyimide precursor resins, phenolic, acrylic, epoxy, polyurethane and other resins, and the polyimide precursor resin is at least one selected from polyamic acid, polyamic acid ester, polyimide, polyisoimide and copolymers between the resins.

[0041] Still further preferably, in the main structure of the alkali-soluble resin (a1), the polyimide precursor resin includes polyamic acid and polyamide ester having a structure as shown in Formula II, the polyamic acid and polyamide ester-polyimide copolymer has a structure as shown in Formula III, and the polyimide has a structure as shown in Formula IV:

[0042]

[0043] In Formula II, Formula III, and Formula IV, R 10 、R 12 、R 14 、R 16 Each independently represents a C4-C60 (e.g., C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C35, C36, C38, C40, C42, C45, C48, C50, C52, C55 or C58, etc.) tetravalent organic group;

[0044] R 11 、R 13 、R 15 、R 17 Each independently represents a group represented by formula V, or R 11 、R 13 、R 15 、R 17 Each is independently selected from any one of a C3-C60 (e.g., C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C35, C36, C38, C40, C42, C45, C48, C50, C52, C55 or C58, etc.) divalent organic group, or a substituted or unsubstituted C4-C20 (e.g., C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc.) divalent alicyclic group;

[0045] R 11 、R 13 、R 15 、R 17The substituted substituents are each independently selected from at least one of halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) straight or branched alkyl, and unsubstituted or halogen-substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy;

[0046]

[0047] * represents the attachment site of the group;

[0048] In Formula V, A is selected from any one of a single bond, -O-, -S-, a sulfone group, a substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9) divalent aliphatic hydrocarbon group, a substituted or unsubstituted C3-C20 (e.g., C4, C5, C6, C7, C8, C9, C10, C12, C14, C15, C17, or C18) divalent alicyclic group, or a substituted or unsubstituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28) divalent aromatic group;

[0049] The substituents substituted in A are each independently selected from at least one of halogen, unsubstituted or halogen-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) linear or branched alkyl, unsubstituted or halogen-substituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) aryl, and unsubstituted or halogen-substituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) phenolic group;

[0050] In formula V, R 31 、R 32Each is independently selected from any one of halogen, nitro, cyano, carboxyl, unsubstituted or halogen-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9, etc.) straight or branched alkyl, unsubstituted or halogen-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9, etc.) alkoxy, unsubstituted or halogen-substituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) aryl, amide, benzyl ether or benzyl alcohol;

[0051] In formula V, R 33 、R 34 Each independently selected from any one of a C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) linear or branched alkylene group, a C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkyleneoxy group, and a C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) Si-containing divalent group;

[0052] In formula V, R 35 、R 36 Each independently selected from *-CH2-OC m H 2m+1 , m is an integer from 0 to 8, for example, 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0053] In formula V, R 37 、R 38 Each is independently selected from any one of halogen, hydroxyl, nitro, cyano, carboxyl, unsubstituted or halogen-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9, etc.) straight or branched alkyl, unsubstituted or halogen-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9, etc.) alkoxy, unsubstituted or halogen-substituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) aryl, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9, etc.) ester or amide;

[0054] In formula V, k1, k2, s1, s2, p1, p2, q1, and q2 are each independently selected from an integer of 0 to 4, for example, 0, 1, 2, 3, or 4;

[0055] In formula V, n1 and n2 are each independently 0 or 1; when n1 and n2 are 0, it means that the benzene ring is directly connected to -CO- through a single bond.

[0056] Still more preferably, in Formula II, Formula III, and Formula IV, the R 10 、R 12 、R 14 、R 16 Each is independently selected from any one of a substituted or unsubstituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28) tetravalent aromatic group, and a substituted or unsubstituted C4-C20 (e.g., C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc.) tetravalent alicyclic group;

[0057] More preferably, the R 10 、R 12 、R 14 、R 16 The substituted substituents are each independently selected from at least one of halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) straight or branched alkyl, and unsubstituted or halogen-substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy.

[0058] Most preferably, the R 10 、R 12 、R 14 、R 16 Each is independently selected from any one of the following groups:

[0059] * represents the attachment site of the group;

[0060] Among them, R 21 、R 22 、R 23 、R 24 、R 25 、R 26Each is independently selected from any one of hydrogen, halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) straight or branched alkyl, and unsubstituted or halogen-substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy;

[0061] More preferably, R 21 、R 22 、R 23 、R 24 、R 25 、R 26 Each is independently selected from hydrogen, fluorine, methyl, methoxy, perfluoromethyl or perfluoromethoxy.

[0062] L 21 Selected from single bond, -O-, -S-, sulfone sulfoxide unsubstituted or R'-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) linear or branched alkylene, unsubstituted or R'-substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) arylene, *-L 22 -Ar 21 -L 23 Any of -*.

[0063] L 22 , L 23 Each is independently selected from any one of -O-, -S-, sulfone, sulfoxide, unsubstituted or R'-substituted C1-C10 (eg, C2, C3, C4, C5, C6, C7, C8 or C9, etc.) linear or branched alkylene.

[0064] Ar 21 Any one selected from unsubstituted or R'-substituted C6-C20 (eg, C6, C9, C10, C12, C14, C16, or C18, etc.) arylene groups.

[0065] R' is selected from at least one of halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) straight or branched alkyl, and unsubstituted or halogen-substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy.

[0066] Preferably, the L 21 Selected from single bond, -O-, -CH2-, Any one of .

[0067] Preferably, the R 10 、R 12 、R 14 、R 16 Each is independently selected from any one of the following groups:

[0068]

[0069] Wherein, * represents the attachment site of the group.

[0070] More preferably, the group represented by formula V has any one of the following structures:

[0071]

[0072]

[0073]

[0074] Wherein, * represents the attachment site of the group.

[0075] More preferably, in Formula II, Formula III, and Formula IV, the R 11 、R 13 、R 15 、R 17 Each is independently selected from the group shown in formula V, or each is independently selected from any one of the groups shown below:

[0076]

[0077] Where * represents the attachment site of the group;

[0078] Among them, R 41 、R 42Each is independently selected from any one of halogen, hydroxyl, unsubstituted or halogen-substituted C1-C20 (for example, C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C17 or C19, etc.) straight or branched alkyl, unsubstituted or halogen-substituted C1-C20 (for example, C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C17 or C19, etc.) alkoxy, and is further preferably hydroxyl, fluorine, methyl, methoxy, perfluoromethyl or perfluoromethoxy.

[0079] Among them, L 41 is selected from a single bond, -O-, -S-, a sulfone group, a sulfoxide group, an unsubstituted or halogen-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight or branched alkylene group, an unsubstituted or halogen-substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) arylene group, *-L 42 -Ar 41 -L 43 -Any of *;

[0080] The L 42 , L 43 Each is independently selected from any one of -O-, -S-, a sulfone group, a sulfoxide group, an unsubstituted or halogen-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9, etc.) linear or branched alkylene group;

[0081] The Ar 41 Any one selected from unsubstituted or R″-substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C16 or C18, etc.) arylene groups;

[0082] The R″ is selected from any one of halogen, hydroxy, unsubstituted or halogen-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9, etc.) straight or branched alkyl, and unsubstituted or halogen-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9, etc.) alkoxy.

[0083] u1 and u2 are each independently selected from integers of 0-4, for example, 0, 1, 2, 3 or 4.

[0084] More preferably, the L 41 Selected from single bond, -O-, -CH2-,

[0085] Any one of .

[0086] Continuing to preferably, in Formula II, Formula III, and Formula IV, the R 11 、R 13 、R 15 、R 17 Each is independently selected from the group shown in formula V, or each is independently selected from any one of the groups shown below:

[0087]

[0088]

[0089] * represents the attachment site of the group.

[0090] Continuing to preferably, in the main structure of the alkali-soluble resin (a1), the number of structural units represented by formula II is f, and the number of structural units represented by formula IV is g, and f and g are each independently an integer of 2-200, for example, 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, 130, 150, 170 or 190, etc.

[0091] Continuing to preferably, in the main structure of the alkali-soluble resin (a1), the structural unit represented by formula III includes a polyimide segment:

[0092]

[0093] Also includes polyamide polyester segments When R 19 When it is hydrogen, it is a polyamic acid ester segment.

[0094] The two fragments are connected by chemical bonds, and the number of chemical bonds is independently an integer from 2 to 200, such as 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, 130, 150, 170 or 190.

[0095] Preferably, the weight average molecular weight of the alkali-soluble resin (a1) is 2000-100000, for example, 3000, 5000, 8000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 70000, 80000 or 90000, more preferably 5000-50000.

[0096] Preferably, the alkali-soluble resin (a1) includes a polyimide precursor resin (polyamic acid and / or polyamic acid ester, preferably comprising a structural unit represented by formula II), which can be prepared by methods well known in the art, exemplarily including the following routes: (1) directly polymerizing a diamine with a dianhydride to obtain a polyamic acid, which is then subjected to an esterification reaction to obtain a polyamic acid ester; (2) reacting a dianhydride with an alcohol to obtain a dicarboxylic acid diester, which is then reacted with thionyl chloride to obtain a diacyl chloride diester, which is then polymerized with a diamine compound to obtain a polyamic acid ester; (3) reacting a dianhydride with an alcohol to obtain a dicarboxylic acid diester, which is then reacted with a diamine compound in the presence of a dehydrating agent such as cyclohexylcarbodiimide to obtain a polyamic acid ester.

[0097] Preferably, the preparation method of the polyimide precursor resin comprises: firstly, diamine monomer (NH2-R 11 -NH2) and dianhydride monomers The polyamide acid is polymerized to obtain polyamic acid; and the polyamic acid is subjected to esterification reaction to obtain the polyimide precursor resin.

[0098] Preferably, the reagent for the esterification reaction includes N,N-dimethylformamide dimethyl acetal.

[0099] Preferably, the polyimide precursor resin introduces (I') a capping agent at the end group.

[0100] Contains or does not contain (a2) partially blocked or unblocked polyimide precursor resin (polyamic acid, polyamic acid ester, polyimide, polyisoimide, and copolymers thereof), one or more resins such as phenolic, acrylic, epoxy, and polyurethane. The main structure of the alkali-soluble resin (a2) polyimide precursor resin is consistent with the main structure of the alkali-soluble resin (a1), as described above;

[0101] Preferably, the alkali-soluble resin (a2) polyimide precursor resin can introduce a capping agent at the end group. As the primary monoamine of the capping group, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-amino-4,6-dihydroxypyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, etc. can be listed; as the dianhydride of the capping group, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, etc. can be listed. They can be used alone or in combination of two or more.

[0102] A third object of the present invention is to provide a positive photosensitive resin composition, comprising an alkali-soluble resin, a photosensitizer, a crosslinking agent, an auxiliary agent and a solvent, wherein the alkali-soluble resin is the alkali-soluble resin comprising a polyimide resin precursor as described above.

[0103] Furthermore, the positive photosensitive resin composition of the present invention further includes a sensitivity regulator.

[0104] Furthermore, in the positive photosensitive resin composition of the present invention, the weight average molecular weight of the alkali-soluble resin is 2,000-100,000.

[0105] A fourth object of the present invention is to provide a positive photosensitive composition comprising the following components: (a) an alkali-soluble resin, (b) a photoacid generator, (c) a crosslinking agent, and (d) an organic solvent.

[0106] Those skilled in the art can adjust the proportions of the components in the photosensitive composition as needed. Taking the total weight of the photoresist composition as 100%, the weight content of the components in the photoresist composition is: photoacid generator 1-8%; sensitivity regulator 0.1-2%; alkali-soluble resin 4-30%; cross-linking agent 0.4-10%; solvent 55-95%; and auxiliary agent 0.01-0.5%.

[0107] In the positive photosensitive composition of the present invention, the photoacid generator is a diazonaphthoquinone sensitizer well known to those skilled in the art, for example, it can be an ester of diazonaphthoquinone sulfonyl chloride and trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, 1,1,1-tris(4-hydroxyphenyl)ethane, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene), etc.

[0108] In the above-mentioned photoresist composition of the present invention, the sensitivity regulator is a small molecule compound that can improve the sensitivity and is well known to those skilled in the art. Specifically, it can be a small molecule phenolic resin, phenol, naphthol, methylphenol, dimethylphenol, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,1,1-tris(4-hydroxyphenyl)ethane, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene), etc.

[0109] In the above-mentioned photoresist composition of the present invention, the crosslinking agent is well known to those skilled in the art, and includes amino crosslinking agents, epoxy crosslinking agents, ether crosslinking agents, urea crosslinking agents, etc. Specifically, it can include hexamethylenetetramine, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 1,4-butanediol diglycidyl ether, hexamethoxymethylmelamine, trialkoxycarbonylaminotriazine 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0110] In the above-mentioned photoresist composition of the present invention, the solvent is well known to those skilled in the art, and can be, for example, selected from one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol diethyl ether ethyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol tert-butyl ether, chloroform, toluene, xylene, methyl lactate, ethyl lactate, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, 2-heptanone, N-dimethylacetamide, N-methylpyrrolidone, benzyl alcohol, and dimethyl sulfoxide.

[0111] In the above-mentioned photoresist composition of the present invention, in order to improve the performance of the photoresist composition, some auxiliary agents can be selected, for example, one or more selected from leveling agents, defoaming agents, coupling agents, and ultraviolet absorbers. The specific types and amounts of auxiliary agents that can be selected are those familiar to those skilled in the art. For example, the leveling agent can be selected from acrylic leveling agents, silane leveling agents, and fluorine-containing leveling agents. The defoaming agent can be selected from silicone defoamers, polyether defoamers, and polyether-modified polysiloxane defoamers. The coupling agent can be selected from trimethoxysilylbenzoic acid, vinyltrimethoxysilane, vinyltriacetoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidylpropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. The UV absorber may be selected from 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, phenyl o-hydroxybenzoate, 2,4-dihydroxybenzophenone, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, etc. Auxiliary agents such as photoacid generators, thermal acid generators, photobase generators, and thermal base generators may be included to promote the crosslinking reaction between the resin and the crosslinking agent and / or the ring closure reaction of the resin during the curing process.

[0112] A fifth object of the present invention is to provide an application of the above-mentioned positive photosensitive composition in a flat panel display device or a semiconductor device.

[0113] Preferably, the positive photosensitive composition is used for stress buffer materials, passivation layers, pixel defining layers, and planarization layers in semiconductor devices.

[0114] Preferably, the positive photosensitive composition can form a cured film after coating, pre-baking, photolithography, development, and curing, and can be permanently retained in the semiconductor device or flat panel display device (display panel). The cured film has high sensitivity, high contrast, and excellent substrate adhesion, and can be used in the packaging process of flexible semiconductors, flat panel displays and other devices. DETAILED DESCRIPTION

[0115] The technical solutions of the present invention are further illustrated below by specific embodiments. Those skilled in the art will appreciate that the embodiments are intended only to aid understanding of the present invention and should not be construed as limiting the present invention. Unless otherwise specified, in the following examples and comparative examples, temperatures are in degrees Celsius and parts and percentages are by weight. Mass spectral data (m / z) of the target product were obtained using an Agilent Qtof G6530 mass spectrometer.

[0116] Synthesis example 1

[0117] Capping agent 1 was synthesized by the following method. 12.1 g of 3-aminobenzaldehyde and 15.6 g of 2,6-difluorobenzene were dissolved in 100 ml of 1,2-dichloroethane, 0.5 g of iodine was added, 8.2 g of phosphorous acid was added dropwise, the temperature was raised to 60 ° C and the reaction was continued for 5 h, the temperature was lowered to room temperature, the reaction mixture was washed with purified water 3 times, and the crude product was obtained by rotary evaporation. The crude product was dissolved in a mixed solvent of 100 mL of methanol and 50 mL of tetrahydrofuran, 7.56 g of sodium borohydride was added, the reaction mixture was heated at 0-10 ° C for 10 h, the reaction mixture was quenched with water, the reaction mixture was washed with water 3 times, and the capping agent 1 was obtained by column chromatography. The mass spectrometry test results were: m / z value (M+H): 236.09. The reaction formula is as follows:

[0118]

[0119] Synthesis example 2

[0120] Capping agent 2 was synthesized by the following method. 12.1 g of 3-aminobenzaldehyde and 27.6 g of 2,4-ditrifluoromethylphenol were dissolved in 150 ml of 1,2-dichloroethane, 0.5 g of iodine was added, 8.2 g of phosphorous acid was added dropwise, the temperature was raised to 60 ° C and the reaction was carried out for 5 hours, the temperature was lowered to room temperature, the mixture was washed with purified water 3 times, and the crude product was obtained by rotary evaporation. The crude product was dissolved in a mixed solvent of 100 mL of methanol and 50 mL of tetrahydrofuran, 7.56 g of sodium borohydride was added, the mixture was reacted at 0-10 ° C for 10 hours, water was added to quench the mixture, the mixture was washed with water 3 times, and the capping agent 2 was obtained by column chromatography. The mass spectrometry test results were: m / z value (M+H): 336.08. The reaction formula is as follows:

[0121]

[0122] Synthesis example 3

[0123] Capping agent 3 was synthesized by the following method. 19.4 g of 4-formylphthalic acid and 15.6 g of 2,6-difluorophenol were dissolved in 150 ml of 1,2-dichloroethane, 0.5 g of iodine was added, 8.2 g of phosphorous acid was added dropwise, the temperature was raised to 60 ° C and the reaction was carried out for 5 hours, the temperature was lowered to room temperature, the reaction was washed with purified water 3 times, and the crude product was obtained by rotary evaporation. The crude product was dissolved in 150 ml of tetrahydrofuran, 10% palladium carbon was added, hydrogen was introduced to maintain the pressure at 1-2 MPa, the reaction was carried out at 50-60 ° C for 24 hours, filtered and concentrated, 100 ml of dimethyl sulfoxide and 25.5 g of acetic anhydride were added, the reaction was carried out at 120-130 ° C for 10 hours, and the capping agent 3 was obtained by column chromatography. The mass spectrometry test results were: m / z value (M+Na): 313.03. The reaction formula is as follows:

[0124]

[0125] Preparation Example 1

[0126] An alkali-soluble resin A1, specifically a polyimide precursor resin, is prepared as follows:

[0127] Under nitrogen protection, 6.04 g of diamine compound 1 was dissolved in 20 mL of N-methylpyrrolidone (NMP), cooled to 0°C, and a mixture of 3.87 g of 3,3,4,4-diphenyl ether tetraanhydride and 12 g of anhydrous NMP was quickly added to the reaction system. The reaction was maintained at 0°C for 4 hours. The temperature was raised to 20°C, and a mixture of 0.15 g of end-capping agent 1 and 0.4 g of NMP was added to the reaction solution and reacted for 2 hours. The temperature was raised to 60°C, and 2.68 g of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. The reaction was maintained at 60°C for 2 hours. The temperature was lowered to room temperature, and the reaction solution was poured into 300 mL of deionized water. The precipitate was collected by filtration and dried in vacuo at 50°C for 24 hours to obtain the alkali-soluble resin A1 with a weight-average molecular weight of 9200.

[0128] Diamine compound 1: Capping agent 1:

[0129] Preparation Example 2

[0130] An alkali-soluble resin A2, specifically a polyimide precursor resin, is prepared as follows:

[0131] Under nitrogen protection, 6.04 g of diamine compound 1 was dissolved in 20 mL of N-methylpyrrolidone (NMP), cooled to 0°C, and a mixture of 3.87 g of 3,3,4,4-diphenyl ether tetraanhydride and 12 g of anhydrous NMP was quickly added to the reaction system. The reaction was maintained at 0°C for 4 hours. The temperature was raised to 20°C, and a mixture of 0.235 g of end-capping agent 1 and 0.4 g of NMP was added to the reaction solution and reacted for 2 hours. The temperature was raised to 60°C, and 2.68 g of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. The reaction was maintained at 60°C for 2 hours. The temperature was lowered to room temperature, and the reaction solution was poured into 300 mL of deionized water. The precipitate was collected by filtration and dried in vacuo at 50°C for 24 hours to obtain the alkali-soluble resin A2 with a weight-average molecular weight of 9400.

[0132] Diamine compound 1: Capping agent 1:

[0133] Preparation Example 3

[0134] An alkali-soluble resin A3, specifically a polyimide precursor resin, whose preparation method differs from that of Preparation Example 1 only in that diamine compound 1 is replaced by an equimolar amount of diamine compound 2. Other raw materials and process parameters are the same as those of Preparation Example 1, and the alkali-soluble resin A3 is obtained, with a weight-average molecular weight of 9000.

[0135] Diamine compound 2: Capping agent 1:

[0136]

[0137] Preparation Example 4

[0138] An alkali-soluble resin A4, specifically a polyimide precursor resin, is prepared by a method different from that of Preparation Example 1, wherein the end-capping agent 1 is replaced with an equimolar amount of the end-capping agent 2. The other raw materials and process parameters are the same as those of Preparation Example 1, and the alkali-soluble resin A4 is obtained, having a weight-average molecular weight of 9600.

[0139] Diamine compound 1: Capping agent 2:

[0140] Preparation Example 5

[0141] An alkali-soluble resin A5, specifically a polyimide precursor resin, is prepared as follows:

[0142] Under nitrogen protection, 6.04 g of diamine compound 1 was dissolved in 20 mL of N-methylpyrrolidone (NMP), cooled to 0°C, and a mixture of 3.87 g of 3,3,4,4-diphenyl ether tetraanhydride and 12 g of anhydrous NMP was quickly added to the reaction system. The reaction was maintained at 0°C for 4 hours. The temperature was raised to 20°C, and a mixture of 0.78 g of end-capping agent 1, 1.13 g of end-capping agent 2, and 0.4 g of NMP was added to the reaction solution and reacted for 2 hours. The temperature was raised to 60°C, and 2.68 g of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. The reaction was maintained at 60°C for 2 hours. The temperature was then lowered to room temperature, and the reaction solution was poured into 300 mL of deionized water. The precipitate was collected by filtration and dried in vacuo at 50°C for 24 hours to obtain the alkali-soluble resin A5 with a weight-average molecular weight of 9500.

[0143] Preparation Example 6

[0144] An alkali-soluble resin B1, specifically a polyimide precursor resin, is prepared as follows:

[0145] Under nitrogen protection, 7.25 g of diamine compound 1 was dissolved in 20 mL of N-methylpyrrolidone (NMP), cooled to 0°C, and a mixture of 3.1 g of 3,3,4,4-diphenyl ether tetraanhydride and 12 g of anhydrous NMP was quickly added to the reaction system. The reaction was maintained at 0°C for 4 hours. The temperature was raised to 20°C, and a mixture of 0.21 g of end-capping agent 3 and 0.4 g of NMP was added to the reaction solution and reacted for 2 hours. The temperature was raised to 60°C, and 2.68 g of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. The reaction was maintained at 60°C for 2 hours. The temperature was lowered to room temperature, and the reaction solution was poured into 300 mL of deionized water. The precipitate was collected by filtration and dried in vacuo at 50°C for 24 hours to obtain the alkali-soluble resin B1 with a weight-average molecular weight of 9300.

[0146] Diamine compound 1: Capping agent 3:

[0147] Preparation Example 7

[0148] An alkali-soluble resin C1, specifically a polyimide precursor resin, is prepared as follows:

[0149] Under nitrogen protection, 6.04 g of diamine compound 1 was dissolved in 20 mL of N-methylpyrrolidone (NMP), the temperature was lowered to 0°C, and a mixture of 3.87 g of 3,3,4,4-diphenyl ether tetraanhydride and 12 g of anhydrous NMP was quickly added to the reaction system, and the reaction was maintained at 0°C for 6 hours. The temperature was raised to 60°C, and 2.68 g of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system, and the reaction was maintained at 60°C for 2 hours. The temperature was lowered to room temperature, and the reaction solution was poured into 300 mL of deionized water. The precipitate was collected by filtration and dried in vacuo at 50°C for 24 hours to obtain the alkali-soluble resin C1 with a weight-average molecular weight of 9000.

[0150] Diamine compound 1:

[0151] Preparation Example 8

[0152] An alkali-soluble resin C2, specifically a polyimide precursor resin, is prepared as follows:

[0153] Under nitrogen protection, 6.04 g of diamine compound 1 was dissolved in 20 mL of N-methylpyrrolidone (NMP), cooled to 0°C, and a mixture of 3.87 g of 3,3,4,4-diphenyl ether tetraanhydride and 12 g of anhydrous NMP was quickly added to the reaction system. The reaction was maintained at 0°C for 4 hours. The temperature was raised to 20°C, and a mixture of 0.073 g of end-capping agent 4 and 0.4 g of NMP was added to the reaction solution and reacted for 2 hours. The temperature was raised to 60°C, and 2.68 g of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. The reaction was maintained at 60°C for 2 hours. The temperature was lowered to room temperature, and the reaction solution was poured into 300 mL of deionized water. The precipitate was collected by filtration and dried in vacuo at 50°C for 24 hours to obtain the alkali-soluble resin C2 with a weight-average molecular weight of 9200.

[0154] Diamine compound 1: Capping agent 4: 4-aminophenol

[0155] Example 1

[0156] A positive photosensitive composition comprising the following components: 10 g of the alkali-soluble resin A1 provided in Preparation Example 1, 2 g of a photosensitive compound, 1.5 g of a crosslinking agent, 85 g of γ-butyrolactone, 0.2 g of a silane coupling agent (γ-glycidyl ether propyl trimethoxysilane) and a leveling agent (Dow Corning DC-7); wherein the photosensitive compound is Q is * represents the attachment site of the group; the cross-linking agent is

[0157] The preparation method of the positive photosensitive resin composition is as follows: all components are mixed according to the formula amount and fully dissolved to obtain the positive photosensitive composition.

[0158] Examples 2-9, Comparative Examples 1-3:

[0159] A positive photosensitive composition is provided, which differs from Example 1 only in the type of alkali-soluble resin and / or ; the types and amounts of other components are the same as those in Example 1, and the specific components are shown in Table 1.

[0160] The photolithography experiments were carried out under the same conditions, including the following steps:

[0161] First, a glass substrate was prepared. After irradiation with a UV cleaner for 1 minute and cleaning with deionized water, the surface was dried at 150°C for 10 minutes. A photoresist composition was then evenly applied to the glass substrate surface by spin coating. Pre-baking was performed at 120°C for 200 seconds to obtain a 1.5μm thick film. Exposure was performed using 365nm UV light with a mask at a distance of 0μm from the coating. A 2.38% TMAH (tetramethylammonium hydroxide) developer was used. Development was performed at 23°C for 40 seconds, followed by rinsing with water and drying. The film was then tested for optimal exposure and film retention.

[0162] Among them, the optimal exposure is an indicator for evaluating the sensitivity of the photoresist, which refers to the exposure amount that resolves a 1:1 pattern under a photomask with L / S = 1:1; the film retention rate is an indicator for evaluating the wash resistance of the photoresist. The film thickness before and after development can be tested using an ellipsometer, and the ratio of the film thickness after development to the film thickness before development can be calculated, which is the film retention rate.

[0163] The properties of the positive photosensitive compositions prepared in Examples 1-9 and Comparative Examples 1-3 are shown in Table 1 below.

[0164] Table 1:

[0165]

[0166] Combined with the above performance data, it can be seen that compared with the resin formula synthesized by the existing technical scheme (Comparative Examples 1-3, resins C1 and C2), the sensitivity, film retention rate and resolution of the polyimide precursor resin and composition provided by the present invention have obvious technical advantages. For Examples 1-7, the resins are all polyimide precursor resins with electron-withdrawing end-capping agents in the present invention, and the performance is the best; for Examples 8-9, the resins are all polyimide precursor resins with electron-withdrawing end-capping agents in the present invention mixed with resins of the prior art, and the performance is second only to that of Comparative Examples 1-3, the resins are all resins of the prior art, and the performance is the worst.

[0167] The reason for this is that the alkali-soluble resin (a1) in the present invention is partially capped with a phenolic hydroxyl end-capping agent connected to an electron-withdrawing group or group. Since the electron-withdrawing group or group makes it easier for the hydrogen electrons in the hydroxyl group to delocalize to the benzene ring, the ability to provide H is enhanced, that is, the ability of the photosensitive material to form hydrogen bonds with the phenolic hydroxyl group is enhanced. Therefore, dissolution in the non-exposed area is better suppressed, which is conducive to improving the film retention rate. In the exposed area, the photosensitive material decomposes into carboxylic acid, which increases the dissolution of the exposed area. In addition, the phenolic hydroxyl group in the polyimide precursor containing the electron-withdrawing end-capping agent in the present invention has a stronger ability and speed to react with the alkaline solution, which accelerates the alkali dissolution rate of the phenolic resin, thereby improving not only the sensitivity but also the contrast of the alkali dissolution rate between the exposed and non-exposed areas, thereby improving the contrast and resolution. It is precisely because of the presence of this end-capping agent that not only the dissolution inhibition of the non-exposed area is strengthened, but also the dissolution promotion of the exposed area is strengthened, so that the above-mentioned properties can be simultaneously and fully improved.

[0168] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the polyimide precursor resin with an electron-withdrawing group end-capping agent, the positive photosensitive composition, and its applications. However, the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for various raw materials in the products of the present invention, addition of auxiliary components, and selection of specific methods, etc., are all within the scope of protection and disclosure of the present invention.

Claims

1. A polyimide resin precursor, the polyimide resin precursor being copolymerized by a diamine monomer, a dianhydride monomer, and a capping agent, the capping agent comprising three parts: Formula A, Formula B, and Formula Z, wherein Formula A represents a reactive group between the capping agent and the end of the polyimide resin, Formula B represents a phenolic hydroxyl structure with an electron-withdrawing group, and Formula Z represents a structure for connecting Formulas A and B; The structure of the end-capping agent is shown in the following formula (I): In formula (I), ring A is a C6-C30 aryl group; R0 is selected from amino, anhydride, carboxyl or acyl chloride; Ra represents one to the maximum permissible number of substituent groups, and Ra are each independently selected from any one of hydrogen, halogen, trihalomethyl, halogen-containing hydrocarbon group, sulfonyl, formyl, acyl, carboxyl, hydroxyl, unsubstituted or halogen-substituted C6-C30 aryl; Ring B is a C6-C30 aryl group; Rb represents one to the maximum permissible number of substituent groups, each Rb is independently selected from any one of hydrogen, halogen, tertiary amine cation, trihalomethyl, halogen-containing hydrocarbon group, unsubstituted or halogen-substituted C6-C30 aryl group, hydroxyl, nitro, cyano, sulfonyl, formyl, acyl, and carboxyl, and at least one Rb is one of halogen, tertiary amine cation, trihalomethyl, and halogen-containing hydrocarbon group; In formula (I), Z is a divalent organic group having 1 to 40 atoms.

2. The polyimide resin precursor according to claim 1, characterized in that The capping agent has a structure as shown in formula (I'): R0 is selected from amino, anhydride, carboxyl or acyl chloride; R1-R4 are each independently selected from any one of hydrogen, halogen, trihalomethyl, halogen-containing hydrocarbon group, sulfonyl, formyl, acyl, carboxyl, hydroxyl, unsubstituted or halogen-substituted C6-C30 aryl; More preferably, R1-R4 are each independently selected from hydrogen, carboxyl or hydroxyl; R5-R8 contain at least one electron-withdrawing group or group, and R5-R8 are independently selected from any one of hydrogen, halogen, tertiary amine cation, trihalomethyl, halogen-containing hydrocarbon group, unsubstituted or halogen-substituted C6-C30 aromatic group, hydroxyl, nitro, cyano, sulfonyl, formyl, acyl, and carboxyl group, and at least one of R5-R8 is selected from halogen, trihalomethyl or halogen-containing hydrocarbon group; preferably, 1-3 of R5-R8 are selected from halogen, trihalomethyl or halogen-containing hydrocarbon group; most preferably, 1-2 of R5-R8 are selected from halogen, trihalomethyl or halogen-containing hydrocarbon group. Z is selected from one of -CO-, -CHR-, -C2H3R-, -O-, -C3H5R-, -SO2-, -S-, Si(CH3)2-, -COO-, -CONH-, and -C6H3R-; R is selected from hydrogen, C1-C10 alkyl, or C6-C30 aryl; Preferably, Z is selected from -CHR-, -SO2- or -CONH-.

3. The polyimide resin precursor according to any one of claims 1 to 4, characterized in that The capping agent is selected from the following structures:

4. An alkali-soluble resin comprising the polyimide resin precursor according to claim 1, further comprising a member selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyisoimide, and a copolymer consisting of polyamic acid, polyamic acid ester, polyimide, and polyisoimide.

5. The polyimide precursor resin according to claim 1, characterized in that The end-capping agent in the polyimide precursor resin is used in a capping ratio of 10-70% as shown in the structure of formula (I); Preferably, the end-capping ratio of the end-capping agent represented by the structure of formula (I) in the polyimide precursor resin is 20-50%.

6. A positive photosensitive resin composition comprising an alkali-soluble resin, a photosensitizer, a crosslinking agent, an auxiliary agent and a solvent, characterized in that: The alkali-soluble resin is the alkali-soluble resin comprising a polyimide resin precursor as claimed in claim 1.

7. A positive photosensitive resin composition according to claim 6, characterized in that: The weight average molecular weight of the alkali-soluble resin is 2,000-100,000.

8. The method for preparing the polyimide resin precursor according to claim 1, comprising: First, diamine monomers and dianhydride monomers are polymerized to obtain polyamic acid; Then, an end-capping agent having a structure as shown in formula (I) is introduced into the end group of the polyamic acid; Finally, the polyamic acid is subjected to an esterification reaction to obtain the polyimide precursor resin; Preferably, the reagent for the esterification reaction includes N,N-dimethylformamide dimethyl acetal; Preferably, the diamine monomer is NH2-R 11 -NH2; the dianhydride monomer is 9. A positive photosensitive resin composition, characterized in that The positive photosensitive resin composition comprises an alkali-soluble resin, a photoacid generator, a cross-linking agent, an organic solvent, a sensitivity regulator and an auxiliary agent; The alkali-soluble resin is the alkali-soluble resin according to claim 4; Preferably, the positive photosensitive resin composition comprises the following components by weight percentage:

10. Use of the positive photosensitive composition according to claim 9 in a flat panel display device or a semiconductor device.

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