CN-122029234-A - Resin composition

CN122029234ACN 122029234 ACN122029234 ACN 122029234ACN-122029234-A

Abstract

A resin composition comprising a soluble polyimide and a solvent, wherein the soluble polyimide has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and wherein when the structural unit represented by the following formula (1) is a structural unit represented by the following formula (1B), the soluble polyimide further has at least one of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4), the structural unit represented by the formula (3) does not include the structural unit represented by the formula (1), and the structural unit represented by the formula (4) does not include the structural unit represented by the formula (2). (In formula (1), m represents 0 or 1, in formula (2), R 1 and R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, in formula (3), a 1 represents a 4-valent organic group, and in formula (4), a 2 represents a 2-valent organic group).

Inventors

ISHII HIDEHIRO
Atsuta Kenta
Hashigo Makoto
OGINO HIROSHI
Sen kanro

Assignees

日产化学株式会社

Dates

Publication Date: 20260512
Application Date: 20240829
Priority Date: 20231011

Claims (13)

1. A resin composition comprising a soluble polyimide and a solvent, wherein the soluble polyimide has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and wherein when the structural unit represented by the following formula (1) is a structural unit represented by the following formula (1B), the soluble polyimide further has at least one of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4), the structural unit represented by the formula (3) does not include the structural unit represented by the formula (1), and the structural unit represented by the formula (4) does not include the structural unit represented by the formula (2), In the formula (1), m represents 0 or 1, In the formula (2), R 1 and R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, In the formula (3), A 1 represents a 4-valent organic group, In the formula (4), A 2 represents a 2-valent organic group, In the case where m represents 0, a 1 and a 2 have at least 2 benzene rings and at least 1 ether bond or ester bond, and 1 such ether bond or ester bond is present between any 2 benzene rings of the at least 2 benzene rings.
2. The resin composition according to claim 1, wherein the soluble polyimide is a reaction product of a monomer comprising a tetracarboxylic dianhydride represented by the following formula (1-a) and a diamine represented by the following formula (2-a), and, in the case where the tetracarboxylic dianhydride represented by the following formula (1-a) is a tetracarboxylic dianhydride represented by the following formula (M-3), the monomer further comprises at least any one of a tetracarboxylic dianhydride represented by the following formula (3-a) and a diamine represented by the following formula (4-a), the tetracarboxylic dianhydride represented by the following formula (3-a) does not include the tetracarboxylic dianhydride represented by the following formula (1-a), the diamine represented by the following formula (4-a) does not include the diamine represented by the following formula (2-a), In the formula (1-a), m has the same meaning as m in the formula (1), In the formula (2-a), R 1 and R 2 have the same meanings as R 1 and R 2 in the formula (2), respectively, In the formula (3-a), A 1 has the same meaning as A 1 in the formula (3), In the formula (4-a), A 2 has the same meaning as A 2 in the formula (4).
3. The resin composition according to claim 1 or 2, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (1A), The soluble polyimide further has at least any one of the structural unit represented by the formula (3) and the structural unit represented by the formula (4), The structural unit shown in the formula (3) is at least one structural unit selected from the following formulas (3A) to (3E), The structural unit represented by the formula (4) is at least one structural unit selected from the following formulas (4A) to (4J), In the formula (3C), X represents a 2-valent organic group having at least 2 benzene rings, 。
4. The resin composition according to claim 1 or 2, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (1A), The soluble polyimide does not have the structural unit represented by the formula (3) and the structural unit represented by the formula (4), 。
5. The resin composition according to claim 1 or 2, wherein the structural unit represented by the formula (1) is a structural unit represented by the formula (1B), The structural unit shown in the formula (3) is at least one structural unit selected from the following formulas (3A) to (3C), The structural unit represented by the formula (4) is at least one structural unit selected from the following formulas (4A) to (4H), In the formula (3C), X represents a 2-valent organic group having at least 2 benzene rings, 。
6. The resin composition according to claim 1 or 2, wherein the resin composition further comprises a silane coupling agent.
7. The resin composition according to claim 1 or 2, wherein the resin composition is used for sealing of a semiconductor chip.
8. A resin film obtained from the resin composition according to claim 1 or 2.
9. The resin film according to claim 8, wherein a linear thermal expansion coefficient measured by a thermo-mechanical analysis is 40ppm/K or less at 50 ℃ to 100 ℃, and a glass transition temperature measured by a thermo-mechanical analysis is 350 ℃ or more, and a weight reduction rate after heating at 400 ℃ for 3 hours is 5% or less.
10. The resin film according to claim 8, wherein a linear thermal expansion coefficient measured by a thermo-mechanical analysis is 40ppm/K or less at 50 ℃ to 100 ℃, and a glass transition temperature measured by a thermo-mechanical analysis is 350 ℃ or more, and a weight reduction rate after heating at 400 ℃ for 3 hours is 2% or less.
11. The resin film according to claim 8, wherein the indentation elastic modulus at 400 ℃ measured by nanoindentation is 1GPa or more.
12. A semiconductor device comprising a semiconductor chip provided on a substrate, and the resin film according to claim 8 covering the semiconductor chip.
13. The semiconductor device according to claim 12, wherein a silicon nitride film or a silicon oxynitride film is further provided over the resin film.

Description

Resin composition Technical Field The invention relates to a resin composition, a resin film and a semiconductor device. Background For the purpose of imparting reliability such as water resistance and ion resistance, a protective film may be formed on a semiconductor chip. For example, in a semiconductor device having a semiconductor element formed on a semiconductor substrate and a protective film formed on the semiconductor element, a semiconductor device has been proposed in which the protective film includes a polyimide resin film and a silicon nitride film (see patent document 1). Patent document 1 describes that a polyimide resin as a protective film is applied to the surface of a semiconductor substrate (see right column of page 1). However, in general, polyimide resins are insoluble or poorly soluble in solvents, and polyimide resins are contained in a coating liquid in a state of polyamic acid soluble or easily soluble in solvents. On the other hand, in a CMOS (complementary metal oxide semiconductor) sensor or the like as an example of a semiconductor chip, after forming a protective film, annealing is performed at about 400 ℃. As a polyimide resin having high heat resistance and solvent solubility, a polyimide resin obtained by imidizing a tetracarboxylic dianhydride of 3,3', 4' -diphenylsulfone tetracarboxylic dianhydride (A) and 3,3', 4' -biphenyl tetracarboxylic dianhydride (B) with a fluorene skeleton diamine (C) represented by a specific structural formula in the presence of a reaction solvent, wherein the molar ratio of (A) to (B) is in the range of (A): (B) =40:60 to 80:20, and the molar ratio of (C) to the total molar ratio of (A) to (B) is in the range of 90 to 110, has been proposed. Prior art literature Patent literature Patent document 1 Japanese patent laid-open No. 62-293726 Patent document 2 Japanese patent application laid-open No. 2009-10387 Patent document 3 Japanese patent application laid-open No. 2014-159519 Disclosure of Invention Technical problem to be solved by the invention In view of annealing the semiconductor chip after the formation of the protective film at about 400 ℃, a polyimide film as the protective film of the semiconductor chip is required to have high heat resistance and also high hardness at high temperature. In addition, when forming a protective film on a semiconductor chip, it is required that the formed protective film does not generate cracks. In addition, as a method for forming a protective film of polyimide, there is a method of imidizing after coating a coating liquid containing polyamic acid as a polyimide precursor, but imidization takes time and dimensional change (for example, shrinkage) occurs at the time of imidization, so in order to form a protective film of polyimide, a coating liquid containing polyimide is preferable. From the above-described points, a resin composition containing a solvent-soluble polyimide is required that is capable of forming a polyimide film that is less likely to crack, has high heat resistance, and is also high in hardness at high temperatures. The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition containing a soluble polyimide, which is capable of forming a resin film that is less likely to cause cracking, has high heat resistance and is also high in hardness at high temperatures, a resin film obtained from the resin composition, and a semiconductor device having the resin film. Technical scheme for solving technical problems The present inventors have conducted intensive studies to achieve the above technical problems, and as a result, have found that the above technical problems can be solved by using a resin composition containing a specific solvent-soluble polyimide and a solvent, and have completed the present invention. That is, the present invention includes the following. [1] A resin composition comprising a soluble polyimide and a solvent, wherein the soluble polyimide has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and when the structural unit represented by the following formula (1) is a structural unit represented by the following formula (1B), the soluble polyimide further has at least one of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4), the structural unit represented by the following formula (3) does not include the structural unit represented by the following formula (1), and the structural unit represented by the following formula (4) does not include a structural unit other than the structural unit represented by the following formula (2). [ Chemical 1] (In the formula (1), m represents 0 or 1, In the formula (2), R 1 and R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, In the formula (3), A 1 represents a 4-valent organic group, In