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CN-121991350-A - Polyimide precursor and preparation method thereof, polyimide precursor glue solution and preparation method thereof, and polyimide film

CN121991350ACN 121991350 ACN121991350 ACN 121991350ACN-121991350-A

Abstract

The invention relates to the technical field of materials, in particular to a polyimide precursor and a preparation method thereof, a polyimide precursor glue solution and a preparation method thereof, and a polyimide film. The polyimide precursor has a structure shown in a formula (I), wherein m is n=x and y= (3:7) - (7:3), m is x=n and y= (1:9) - (3:2), ar 1 is an aliphatic group, ar 2 is an aromatic group containing nitrogen heterocycle, ar 3 is a first aromatic group, ar 4 is a second aromatic group, and R is a photosensitive group. The polyimide film prepared from the polyimide precursor can be compatible with low thermal expansion coefficient, high resolution and thermal stability.

Inventors

  • ZHANG JIANWEI
  • SHI LITAO
  • FAN WEIZHEN

Assignees

  • 广州天赐高新材料股份有限公司

Dates

Publication Date
20260508
Application Date
20241106

Claims (14)

  1. 1. A polyimide precursor, characterized in that the polyimide precursor has a structure represented by formula (I): Wherein m: n=x: y= (3:7) - (7:3), m: x=n: y= (1:9) - (3:2); Ar 1 is an aliphatic group; ar 2 is an aromatic group containing an nitrogen heterocycle; Ar 3 is a first aromatic group; ar 4 is a second aromatic group; r is a photosensitive group.
  2. 2. The polyimide precursor according to claim 1, wherein Ar 1 comprises At least one of them.
  3. 3. The polyimide precursor according to claim 1, wherein Ar 2 comprises At least one of them.
  4. 4. The polyimide precursor according to claim 1, wherein Ar 3 comprises At least one of them.
  5. 5. The polyimide precursor according to claim 1, wherein Ar 4 comprises At least one of them.
  6. 6. The polyimide precursor according to claim 1, wherein R is Wherein R 1 is any one of H, C 1 -C 3 alkyl; R 2 is C 1 -C 3 divalent alkyl; Optionally, R 1 is any one of H and methyl; R 2 is a C 1 -C 3 divalent alkyl group.
  7. 7. A method of preparing the polyimide precursor of any one of claims 1 to 6, comprising: Carrying out first mixing treatment on the dianhydride monomer a, the dianhydride monomer b and an alcohol compound with a photosensitive group to obtain an esterification product; Performing second mixing treatment on the esterification product, diamine monomer a and diamine monomer b to obtain polyamic acid; carrying out isomerization reaction on the polyamic acid to obtain an intermediate; Carrying out third mixing treatment on the intermediate and the alcohol compound with the photosensitive group to obtain the polyimide precursor; wherein the dianhydride monomer a has a structure shown in a formula (II); the dianhydride monomer b has a structure shown in a formula (III); The diamine monomer a has a structure shown in a formula (IV); the diamine monomer b has a structure shown in a formula (V); H 2 N-Ar 2 -NH 2 formula (IV) and H 2 N-Ar 4 -NH 2 formula (V).
  8. 8. The method according to claim 7, wherein the molar ratio of dianhydride monomer a to dianhydride monomer b is (1:9) - (3:2); Optionally, the ratio of the molar total of the dianhydride monomer a and the dianhydride monomer b to the molar amount of the alcohol compound having a photosensitive group in the first mixing treatment is 100 (5-50); Optionally, the alcohol compound having a photosensitive group has a structure represented by formula (VI): Optionally, the temperature of the first mixing treatment is 25-45 ℃; optionally, the time of the first mixing treatment is 1-4 hours.
  9. 9. The method according to claim 7, wherein the molar ratio of diamine monomer a, diamine monomer b is (3:7) - (7:3); optionally, the ratio of the molar total of the dianhydride monomer a and the dianhydride monomer b to the molar total of the diamine monomer a and the diamine monomer b is (1-1.05): 1; Optionally, the temperature of the second mixing treatment is from 0 ℃ to 45 ℃; Optionally, the second mixing treatment is for a time period of 10-20 hours.
  10. 10. The process of claim 7, wherein the isomerization reaction comprises reacting the polyamic acid with a basic catalyst, an isomerization reagent; Optionally, the mass ratio of the basic catalyst to the polyamic acid is (1-5): 100; optionally, the mass ratio of the isomerization reagent to the polyamic acid is (1-3): 1; optionally, the basic catalyst comprises at least one of triethylamine, pyridine, tetramethylaminopyridine; Optionally, the isomerising agent comprises dicyclohexylcarbodiimide and/or trifluoroacetic anhydride; Optionally, the isomerization reaction is at a temperature of 25-45 ℃; optionally, the isomerization reaction is for a period of time ranging from 1 to 6 hours.
  11. 11. The method according to claim 7, wherein the mass ratio of the alcohol compound having a photosensitive group to the intermediate in the third mixing treatment is (5-8): 1; Optionally, the temperature of the third mixing treatment is 35-55 ℃; Optionally, the time of the third mixing treatment is 10-24 hours.
  12. 12. Polyimide precursor dope, characterized in that it is prepared from the polyimide precursor according to any one of claims 1 to 6 or the polyimide precursor obtained by the method according to any one of claims 7 to 11.
  13. 13. A method for preparing a polyimide precursor gum solution, comprising: Mixing polyimide precursor with a photoinitiator to obtain polyimide precursor glue solution; Wherein the polyimide precursor is a polyimide precursor according to any one of claims 1 to 6 or a polyimide precursor obtained according to the method of any one of claims 7 to 11.
  14. 14. A polyimide film, characterized in that the polyimide film is produced from the polyimide precursor dope according to claim 12 or the polyimide precursor dope obtained by the production method according to claim 13; wherein the polyimide film has a structure represented by formula (VII):

Description

Polyimide precursor and preparation method thereof, polyimide precursor glue solution and preparation method thereof, and polyimide film Technical Field The invention relates to the technical field of materials, in particular to a polyimide precursor and a preparation method thereof, a polyimide precursor glue solution and a preparation method thereof, and a polyimide film. Background Polyimide (PI) is widely used in chip manufacturing and device packaging due to its low dielectric constant, high thermal stability and chemical resistance. The non-photosensitive polyimide needs to be matched with the traditional photoresist to realize the patterning on PI, however, the introduction of the photoresist makes the patterning process complex, the process difficulty is increased, and the stripping and subsequent etching processes of the photoresist also easily cause irreversible damage to the chip substrate. In this context, since the photosensitive polyimide (PSPI) material itself has photosensitivity, it can directly perform pattern transfer, greatly simplifying the chip process, and thus is receiving attention in chip manufacturing and packaging. Photosensitive polyimide is classified into positive photosensitive polyimide and negative photosensitive polyimide. The negative photosensitive polyimide is further divided into three types of ester type photosensitive polyimide, salt type photosensitive polyimide and self-sensitized type photosensitive polyimide. Among them, ester type photosensitive polyimide is the main stream of negative photoresist because of its higher glass transition temperature and better photolithographic resolution. However, most of the resin of ester type photosensitive polyimide contains aromatic benzene ring structure, so that the Coefficient of Thermal Expansion (CTE) is generally higher, and the metal substrate generally has lower CTE, so that the PSPI film is easy to warp or even fall off in the subsequent process due to the difference of the CTE and the CTE, and the application of the resin is greatly restricted. In the prior art, carboxyl and trifluoromethyl are simultaneously introduced into a resin molecular structure, so that the resin can be developed in an alkaline developer while the low thermal expansion coefficient is realized. However, the introduction of fluorine groups also causes the reduction of the mechanical properties of PI films, which cannot be applied to chip packaging scenes with high strength requirements, and in addition, the high-purity fluorine group monomers are generally high in price and high in cost, which also restricts the industrial large-scale application of the fluorine group monomers. In addition, the method of protecting by introducing hydroxyl and using tert-butoxycarbonyl can be used for preparing the positive PSPI resin with low thermal expansion coefficient, and the positive PSPI resin can be developed by an aqueous developer, however, the resin obtained in the high-temperature chemical imidization process has lower molecular weight, and the reaction control difficulty is higher, so that the mass production is difficult to realize industrially. Also, a blocked polyimide salt was prepared and compounded with a photoinitiator to synthesize a low coefficient of thermal expansion PSPI, which can be as low as 11ppm in CTE, but which has a sensitivity and resolution less than that of the ester PSPI, leaving only 20 μm at 700mJ/cm 2. The PI material has lower dielectric constant and thermal expansion coefficient by introducing the oligomeric silsesquioxane functional group into the end group of the polyimide polymer chain and the side chain of the diamine unit, however, the introduction of the oligomeric silsesquioxane functional group increases the difficulty of PI polymerization reaction and the storage stability is also influenced, so that the method is not suitable for large-scale preparation. Accordingly, it is desirable to provide a photosensitive polyimide that combines low thermal expansion coefficient, high resolution and thermal stability. Disclosure of Invention The present invention aims to solve one of the technical problems in the related art at least to some extent. Therefore, the invention provides a polyimide precursor and a preparation method thereof, polyimide precursor glue solution and a preparation method thereof, and a polyimide film, wherein the polyimide film prepared from the polyimide precursor has low thermal expansion coefficient, high resolution and thermal stability. To this end, a first aspect of the present invention provides a polyimide precursor having a structure represented by formula (I): Wherein m: n=x: y= (3:7) - (7:3), m: x=n: y= (1:9) - (3:2); Ar 1 is an aliphatic group; ar 2 is an aromatic group containing an nitrogen heterocycle; Ar 3 is a first aromatic group; ar 4 is a second aromatic group; r is a photosensitive group. The polyimide precursor has diamine with nitrogen heterocycle in the main chain and ali