Photosensitive resin composition, method for producing a polyimide cured film using the same, and polyimide cured film

Abstract

According to the present disclosure, there are provided: a photosensitive resin composition which has low dielectric properties, low cure shrinkage, good storage stability, and reduced phase separation during coating, and with which a cured relief pattern having high resolution and high copper adhesion can be formed; a method for producing a polyimide cured film using said composition; and a polyimide cured film. The photosensitive resin composition of the present disclosure includes 100 parts by mass of a copolymer resin containing polyimide and a polyimide precursor, 0.5–30 parts by mass of a photopolymerization initiator, and 100–1000 parts by mass of a solvent. The copolymer resin has a polyimide block portion and a polyimide precursor block portion with a specific structure, and the copolymer resin composed of the polyimide and the polyimide precursor satisfies the formula 0.10<n2 / (n2+n3)<0.90.

Claims

1. (A) 100 parts by mass of a copolymer resin containing polyimide and a polyimide precursor; (B) 0.5 to 30 parts by mass of a photopolymerization initiator; (C) 100 to 1000 parts by mass of solvent; A photosensitive resin composition comprising, The copolymer resin comprising the polyimide and the polyimide precursor has a structure represented by the following general formula (1): 【Chemistry 1】 In the formula (1), X １ , X ２ and X ３ are each independently a tetravalent organic group having 6 to 40 carbon atoms, Y １ and Y ２ are each independently a divalent organic group having 6 to 40 carbon atoms, n １ is an integer from 2 to 30, n ２ and n ３ are each independently an integer from 2 to 150, Z ３ , Z ４ , Z ５ , and Z ６ are each independently a monovalent organic group, and among Z ３ , Z ４ , Z ５ , and Z ６ , at least one is a photopolymerizable functional group. The copolymer resin containing the polyimide and the polyimide precursor has a coefficient of 0.10 < n ２ / (n ２ +n ３ A photosensitive resin composition satisfying < 0.

90.

2. The aforementioned photopolymerizable functional group The photosensitive resin composition according to claim 1, comprising a structure represented by the following general formula (2). 【Chemistry 2】 (In formula (2), R ５ , R ６ and R ７ Each is independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ (This is an integer between 2 and 10.)

3. The aforementioned n ２ / (n ２ +n ３ ) is 0.40 < n ２ / (n ２ +n ３ A photosensitive resin composition according to claim 1 or 2, satisfying < 0.

90.

4. The photosensitive resin composition according to claim 1 or 2, wherein the copolymer resin comprising (A) polyimide and polyimide precursor is free of halogen atoms.

5. The photosensitive resin composition according to claim 1 or 2, wherein in the polyimide of the polyimide-cured film obtained by heating and curing the photosensitive resin composition at 350°C, the imide group concentration U, which is the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing a structure derived from tetracarboxylic dianhydride and diamine, is 12 wt% to 26 wt%.

6. (A) The copolymer resin X containing polyimide and polyimide precursor １ , X ２ and X ３ However, it includes the structure shown in the following general formula (4), 【Transformation 3】 In formula (4), R ８ , R ９ These are each an organic group having 1 to 10 carbon atoms, and m ２ , m ３ m is an integer selected from 0 to 4. ２ +m ３ Satisfying ≥ 1, Z １ is selected from the group consisting of single bonds, organic groups having 1 to 30 carbon atoms, and organic groups containing heteroatoms, where two of the *s represent bonds to the main chain of the resin, and the other two represent bonds to the side chains in the general formula (1) above; and / or, Y １ and / or Y ２ However, it includes the structure shown in the following general formula (7), 【Chemistry 4】 In formula (7), R ８ , R ９ These are each an organic group having 1 to 10 carbon atoms, and m ２ , m ３ m is an integer selected from 0 to 4. ２ +m ３ Satisfying ≥ 1, Z １ The photosensitive resin composition according to claim 1 or 2, wherein is selected from the group consisting of single bonds, organic groups having 1 to 30 carbon atoms, and organic groups containing heteroatoms, and * means bonding to the main chain of the resin.

7. The photosensitive resin composition according to claim 1 or 2, wherein the copolymer resin comprising (A) polyimide and polyimide precursor has at its resin ends a reactive substituent that polymerizes with heat or light, which is different from the photopolymerizable functional group contained in its repeating unit.

8. (D) The photosensitive resin composition according to claim 1 or 2, further comprising a silane coupling agent.

9. (E) The photosensitive resin composition according to claim 1 or 2, further comprising a radical polymerizable compound.

10. (F) The photosensitive resin composition according to claim 1 or 2, further comprising a thermal crosslinking agent.

11. (G) The photosensitive resin composition according to claim 1 or 2, further comprising a filler.

12. The following steps (1) to (5): (1) A step of applying the photosensitive resin composition according to claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate; (2) A step of heating and drying the obtained photosensitive resin layer; (3) Exposing the photosensitive resin layer after heating and drying; (4) A step of developing the photosensitive resin layer after exposure; and (5) A step of heat-treating the photosensitive resin layer after development to form a polyimide cured film; A method for producing a polyimide cured film, including the following:

13. A method for producing a cured film, comprising applying the resin composition described in claim 1 or 2 onto a substrate, performing an exposure treatment, a developing treatment, and then a heat treatment, wherein the cured film has a dielectric loss tangent of 0.003 to 0.011 as measured by a perturbation-type split-cylinder resonator at 40 GHz.

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