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CN-122011388-A - Polyimide precursor, preparation method thereof and polyimide precursor composition

CN122011388ACN 122011388 ACN122011388 ACN 122011388ACN-122011388-A

Abstract

The embodiment of the application discloses a polyimide precursor, a preparation method thereof and a polyimide precursor composition, belonging to the technical field of polyimide, wherein the structural formula of the polyimide precursor is shown as formula I. The polyimide precursor provided by the embodiment of the application can realize low shrinkage, low dielectric loss and low dielectric constant under low-temperature curing, and meets the performance requirements.

Inventors

  • Diao Yingxue
  • HE CHUAN
  • LI JIE
  • LI KE
  • XIAO RUIZHU
  • WEI CHUNLAN
  • SHAN LIANG
  • SUN RONG

Assignees

  • 深圳先进电子材料国际创新研究院

Dates

Publication Date
20260512
Application Date
20260413

Claims (10)

  1. 1. The polyimide precursor is characterized in that the structural formula of the polyimide precursor is shown as formula I: A formula I; Wherein, the Derived from dianhydride monomers; R 1 and R 2 are independently derived from an alcohol compound comprising a styryl-containing alcohol; the weight average molecular weight of the polyimide precursor is 10000-50000.
  2. 2. The polyimide precursor according to claim 1, wherein the dianhydride monomer contains a cyclic aliphatic group and/or an aromatic group, and the number of carbon atoms of the dianhydride monomer is 6 to 30; And/or the dianhydride monomer comprises 3,3', 4' -benzophenone tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, m-terphenyl 3,3', 4' -tetracarboxylic dianhydride, p-terphenyl 3,3',4, the step of setting the position of the base plate, 4' -tetracarboxylic dianhydride, 1, 3-hexafluoro 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1, 3-hexafluoro 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, at least one of 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride and 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride; And/or the diamine monomer contains a cyclic aliphatic group and/or an aromatic group, and the dianhydride monomer has 6-30 carbon atoms; And/or the number of the groups of groups, the diamine monomer comprises 4,4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 2,4 '-diaminodiphenyl ether, 2' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfone, and at least one of 3,4' -diaminodiphenyl sulfone, 3 '-diaminodiphenyl sulfone, 2,4' -diaminodiphenyl sulfone, 2 '-diaminodiphenyl sulfone and 4,4' -diaminodiphenyl sulfide; And/or the alcohol compound further comprises at least one of alcohol containing methacrylate groups and alcohol without free radical polymerization capability, wherein the mass percent of the alcohol containing methacrylate groups is less than or equal to 50%, the mass percent of the alcohol containing styrene groups is 50% -100%, and the mass percent of the alcohol without free radical polymerization capability is less than or equal to 20%.
  3. 3. The polyimide precursor according to claim 2, wherein the styryl group-containing alcohol, the methacrylate group-containing alcohol and the alcohol having no radical polymerization ability have a functionality of 1; And/or, the methacrylate group-containing alcohol comprises hydroxyethyl methacrylate; And/or the styryl-containing alcohol comprises at least one of 4-vinylphenyl methanol, 4-vinylphenyl ethanol, and 4-vinylphenyl propanol; and/or the free radical polymerization-capable alcohol comprises at least one of ethanol, propanol, n-butanol, and triglyme.
  4. 4. A polyimide precursor according to any one of claims 1 to 3, which has a structural formula represented by formula II: A formula II; wherein R 3 and R 4 are each independently selected from alkyl groups having 1 to 3 carbon atoms, and R 5 is selected from substituted or unsubstituted And One of them.
  5. 5. The polyimide precursor according to claim 4, wherein the polyimide precursor has a structural formula shown in any one of formulas III to IV: Formula III; Formula IV.
  6. 6. A method for producing the polyimide precursor according to any one of claims 1 to 5, comprising: Adding dianhydride monomer into a first solvent, and then adding an alcohol compound and an organic base, and reacting to obtain a first mixed solution, wherein the alcohol compound comprises alcohol containing styryl; Adding a condensing agent into the first mixed solution, and obtaining a second mixed solution through reaction; Adding diamine monomer into a second solvent to obtain diamine monomer solution, adding the diamine monomer solution into the second mixed solution, and reacting to obtain a third mixed solution; and filtering and drying the third mixed solution to obtain the polyimide precursor.
  7. 7. The method for producing a polyimide precursor according to claim 6, wherein the molar ratio of the dianhydride monomer, the alcohol compound and the diamine monomer is 1 (0.9 to 1.5): 0.8 to 1.
  8. 8. A polyimide precursor composition comprising the polyimide precursor according to any one of claims 1 to 5, and/or comprising the polyimide precursor produced by the process for producing a polyimide precursor according to any one of claims 6 to 7.
  9. 9. The polyimide precursor composition of claim 8, further comprising a crosslinking agent, a photoinitiator, a thermal alkaline generator, and a third solvent.
  10. 10. The polyimide precursor composition according to claim 9, wherein the mass ratio of the polyimide precursor, the crosslinking agent, the photoinitiator, the thermal alkaline generator, and the third solvent is 100 (5-20): 1-5): 0.2-4: (100-300); And/or the crosslinking agent includes at least one of diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4 butanediol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and tricyclo [5.2.1.02,6] decane dimethanol diacrylate; and/or, the photoinitiator comprises at least one of oxime ester photoinitiators, phosphine oxide photoinitiators and alkylaryl ketone photoinitiators; And/or the thermal alkaline generator comprises at least one of DBU-phthalate, DBU-phenolate, DBU-p-toluenesulfonate, bis (2-morpholinoethyl) ether and 1-N-BOC-morpholine; And/or the third solvent comprises at least one of N-methyl pyrrolidone, gamma-butyrolactone, dimethyl sulfoxide and ethyl lactate.

Description

Polyimide precursor, preparation method thereof and polyimide precursor composition Technical Field The application relates to the technical field of polyimide, in particular to a polyimide precursor, a preparation method thereof and a polyimide precursor composition. Background Negative photosensitive polyimide has become one of the important raw materials in the chip manufacturing and packaging fields due to its excellent mechanical and thermal properties. With the development of microelectronic technology to higher integration level and the development of fanout wafer level packaging, 2.5D packaging and other technologies, negative photosensitive polyimide materials are required to meet the requirements of low dielectric constant, low expansion coefficient, high flatness, low curing temperature and the like. Disclosure of Invention The application provides a polyimide precursor, a preparation method thereof and a polyimide precursor composition, and aims to solve the problems of higher polyimide shrinkage, higher dielectric loss and higher dielectric constant in the low-temperature curing process. According to a first aspect of the present application, there is provided a polyimide precursor having a structural formula as shown in formula I: A formula I; Wherein, the Derived from dianhydride monomers; r 1 and R 2 are independently derived from alcohol compounds including styryl-containing alcohols; The polyimide precursor has a weight average molecular weight of 10000-50000. Optionally, the dianhydride monomer contains a cyclic aliphatic group and/or an aromatic group, and the number of carbon atoms of the dianhydride monomer is 6-30; And/or dianhydride monomers including 3,3', 4' -benzophenone tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, m-terphenyl 3,3', 4' -tetracarboxylic dianhydride, p-terphenyl 3,3',4,4' -tetracarboxylic dianhydride, 1, 3-hexafluoro 2,2 bis (2, 3 dicarboxyphenyl) propane dianhydride 1, 3-hexafluoro 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride at least one of 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride and 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride; And/or the diamine monomer contains a cyclic aliphatic group and/or an aromatic group, and the carbon number of the dianhydride monomer is 6-30; and/or the number of the groups of groups, diamine monomers include 4,4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 2,4 '-diaminodiphenyl ether, 2' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfone at least one of 3,4' -diaminodiphenyl sulfone, 3 '-diaminodiphenyl sulfone, 2,4' -diaminodiphenyl sulfone, 2 '-diaminodiphenyl sulfone and 4,4' -diaminodiphenyl sulfide; And/or the alcohol compound further comprises at least one of alcohol containing methacrylate groups and alcohol without free radical polymerization capability, wherein the mass percent of the alcohol containing methacrylate groups is less than or equal to 50%, the mass percent of the alcohol containing styryl groups is 50% -100%, and the mass percent of the alcohol without free radical polymerization capability is less than or equal to 20%. Alternatively, the functionality of the styryl-containing alcohol, the methacrylate-group-containing alcohol, and the alcohol without free radical polymerization capability are all 1; and/or, the methacrylate group-containing alcohol includes hydroxyethyl methacrylate; and/or the styryl-containing alcohol comprises at least one of 4-vinylbenzyl alcohol, and 4-vinylphenyl propanol; and/or the alcohol without free radical polymerization capability comprises at least one of ethanol, propanol, n-butanol, and triglyme. Optionally, the polyimide precursor has a structural formula shown in formula II: A formula II; wherein R 3 and R 4 are each independently selected from alkyl groups having 1 to 3 carbon atoms, and R 5 is selected from substituted or unsubstituted AndOne of them. Optionally, the polyimide precursor has a structural formula shown in any one of formulas III to IV: Formula III; Formula IV. According to a second aspect of the present application, there is provided a method for producing a polyimide precursor as described above, comprising: the dianhydride monomer is added into a first solvent, then an alcohol compound and an organic base are added, and a first mixed solution is obtained through reaction, wherein the alcohol compound comprises alcohol containing styryl. Adding a condensing agent into the first mixed solution, and obtaining a second mixed solution through reaction; Adding diamine monomer into a third solvent to obtain diamine monomer solution, adding the diamine monomer solution into a second mixed solution, and reacting to obtain a third mixed solution; And filtering and drying the third mixed solution to obtain the polyimide precursor. Alternatively, the molar rati