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CN-121991349-A - Polyimide precursor and preparation method thereof, polyimide precursor glue solution and preparation method thereof, and polyimide film

CN121991349ACN 121991349 ACN121991349 ACN 121991349ACN-121991349-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 main chain contains a ketone carbonyl self-sensitization group and an abstractable active hydrogen group, and the ketone carbonyl self-sensitization group and the abstractable active hydrogen group can realize photo-crosslinking. Meanwhile, the polyimide precursor also has ester type photosensitive branched chains, and a crosslinking structure is easy to form under the action of a photocrosslinker and the like, so that double photosensitivity is realized. The polyimide film prepared from the polyimide precursor not only maintains the high resolution of ester type photosensitive polyimide, but also reduces the proportion of photosensitive branched chains in the structure, thereby reducing the film shrinkage effect after curing, and ensuring that the prepared polyimide film has both high resolution and lower film thickness shrinkage.

Inventors

  • ZHANG JIANWEI
  • SHI LITAO
  • FAN WEIZHEN
  • XU CHANGMING

Assignees

  • 广州天赐高新材料股份有限公司

Dates

Publication Date
20260508
Application Date
20241106

Claims (13)

  1. 1. A polyimide precursor, characterized in that the polyimide precursor has a structure represented by formula (I): Wherein, m: n= (3:7) - (7:3); Ar 1 is an aromatic group containing a ketocarbonyl group; Ar 2 is an aromatic group containing active hydrogen; Ar 3 is an 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 R is Wherein R 1 is any one of H, C 1 -C 3 alkyl; r 2 is C 1 -C 3 divalent alkyl; R 3 is C 1 -C 3 divalent alkyl; Optionally, R 1 is any one of H and methyl; r 2 is C 1 -C 3 divalent alkyl; r 3 is methylene.
  6. 6. A method of preparing the polyimide precursor according to any one of claims 1 to 5, comprising: (1) 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; (2) Performing second mixing treatment on the esterification product and diamine monomer to obtain polyamic acid; (3) Carrying out isomerization reaction on the polyamic acid to obtain an intermediate; (4) 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 has a structure shown in a formula (IV); h 2 N-Ar 2 —NH 2 formula (IV).
  7. 7. The method according to claim 6, wherein the molar ratio of dianhydride monomer a to dianhydride monomer b is (3:7) - (7:3); Optionally, in step (1), the ratio of the molar total of dianhydride monomer a and dianhydride monomer b to the molar amount of the alcohol compound having a photosensitive group is 100 (5-50); Optionally, the alcohol compound with a photosensitive group has a structure shown in a formula (V) or a 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.
  8. 8. The method according to claim 6, wherein the ratio of the molar total of the dianhydride monomer a and the dianhydride monomer b to the molar amount of the diamine monomer 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.
  9. 9. The process of claim 6, 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.
  10. 10. The method according to claim 6, wherein in the step (4), the mass ratio of the alcohol compound having a photosensitive group to the intermediate 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.
  11. 11. Polyimide precursor dope, characterized in that it is prepared from a polyimide precursor according to any one of claims 1 to 5 or a polyimide precursor obtained according to the method of any one of claims 6 to 10.
  12. 12. 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 5 or a polyimide precursor obtained according to the method of any one of claims 6 to 10.
  13. 13. A polyimide film, characterized in that the polyimide film is produced from the polyimide precursor dope according to claim 11 or the polyimide precursor dope obtained by the production method according to claim 12; 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. Wherein the self-sensitization photosensitive polyimide can realize the photosensitive effect without adding a photosensitive agent or a photoinitiator. However, most of the photosensitive groups are not crosslinked due to steric hindrance because of the distribution of the photosensitive groups on the molecular main chain and the small volume, resulting in poor photosensitivity of the self-sensitized photosensitive polyimide. In contrast, the photosensitive groups of the ester type photosensitive polyimide are distributed on the side chains of the molecules, and a crosslinking structure is easier to form under the action of the photocrosslinking agent, so that the ester type photosensitive polyimide has higher photosensitivity. However, additives such as the photosensitive branched structure and the photocrosslinker are removed in the heating process in the film curing process after exposure and development, so that the film thickness after curing is shrunk to a large extent, and the defect also restricts the application of the ester type photosensitive polyimide. In the prior art, photosensitive groups are introduced into a molecular chain to enable the molecular chain to have photosensitivity, then 4-hydroxy phthalic anhydride is used as a blocking agent to enable the tail end of a main chain to contain phenolic hydroxyl groups, unsaturated anhydride is introduced after imidization and reacts with the phenolic hydroxyl groups at the tail end of the main chain to generate carboxyl groups, so that the alkali-soluble negative photosensitive polyimide is formed. In addition, triamine and ternary anhydride monomers are introduced, self-sensitization groups are designed at the peripheral tail end of a hyperbranched macromolecular chain with a three-dimensional spherical structure, so that the problem that the self-sensitization type photosensitive polyimide is poor in photosensitivity is solved, however, the hyperbranched polyimide is difficult to synthesize, the molecular weight is difficult to control stably, and therefore, the self-sensitization type photosensitive polyimide cannot be applied on a large scale. And diamine with ketone carbonyl and another diamine monomer containing abstractable active hydrogen are mixed and polymerized with dianhydride, so that self-sensitized groups are distributed on side chains, thereby enhancing the photosensitivity of the self-sensitized polyimide, but the resin molecules are relatively rigid due to the existence of an aromatic ring structure on the side chains, and the film-formed resin has brittle texture, so that the application of the self-sensitized polyimide in the fields of chip manufacturing, packaging and the like is limited. Accordingly, it is desirable to provide a photosensitive polyimide that combines both higher sensitivity and lower film shrinkage. 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, a polyimide precursor glue solution and a preparation method thereof, and a polyimide film, wherein the polyimide film prepared from the polyimide precursor can achieve both high resolution and lower film thickness shrinkage. To this end, a first aspect of the present invention provides a polyimide precursor having a structure represented by formula (I): Wherein, m: n= (3:7) - (7:3); Ar 1 is an aromatic group containing a ketocarbonyl group;