Photosensitive resin composition, method for manufacturing photosensitive resin composition and method for manufacturing hardened embossed pattern

Abstract

This invention relates to a negative photosensitive resin composition, which exhibits good amide formation even under low-temperature curing conditions below 200°C and yields a resin layer with high chemical resistance. The composition contains (B) a photopolymerization initiator in a ratio of 0.1 to 20 parts by weight relative to 100 parts by weight of (A) a polyamide precursor. (A) The polyamide precursor is a polyamide ester or polyamide salt with a specific structure. The weight-average molecular weight (Mw) of (A) the polyamide precursor, calculated using polystyrene equivalents measured by gel permeation chromatography (GPC), is 3,000 or more but less than 16,000.

Claims

1. A photosensitive resin composition, characterized in that: it contains a photosensitive polyimide precursor and a photopolymerization initiator, wherein the backbone of the repeating unit of the main chain of the photosensitive polyimide precursor is derived from the backbone of an acid dianhydride monomer or from the backbone of a diamine monomer; the photosensitive polyimide precursor has a main chain terminal substituent and a side chain substituent; the main chain terminal substituent is a reactive substituent that reacts with heat or light; the side chain substituent is a -CO- substituent at the carboxyl group terminal of the side chain of the main chain; when the main chain terminal originates from the backbone of the acid dianhydride monomer, the main chain terminal substituent is a -CO- substituent at the carboxyl group terminal of the backbone of the acid dianhydride monomer; when the main chain terminal originates from the backbone of the diamine monomer, the main chain terminal substituent is a -NH- substituent at the amino group terminal of the backbone of the diamine monomer. The above-mentioned photosensitive polyimide precursor contains the structure represented by the following general formula (A1) [Chem. 15] {In general formula (A1), X is a tetravalent organogroup, Y is a divalent organogroup, R5 and R6 are independently hydrogen atoms, a monovalent organogroup represented by the following general formula (R1): [Chem. 55] (In general formula (R1), R7, R8 and R9 are independently hydrogen atoms or C1 to C3 organogroups, and p is an integer selected from 1 to 10), or a saturated aliphatic group of C1 to C4; wherein, R5 and R6 are not both hydrogen atoms. In the above general formula (A1), X contains at least one organic group selected from (B1) to (B3): [Chemical 19] [Chemical 20] [Chemical 21], and / or Y contains at least one organic group selected from (C1) to (C3): [Chemical 22] (in general formula (C1), R10 to R13 are hydrogen atoms or monovalent aliphatic groups of C1 to C4, which may be different or the same) [Chemical 23] [Chemical 24] (in general formula (C3), R14 to R21 are hydrogen atoms, halogen atoms or monovalent organic groups of C1 to C4, which may be different or the same) The viscosity of the above photosensitive resin composition is 80 poise or less. The viscosity is measured at 25°C using an E-type viscometer (manufactured by Toki Sangyo, RE80 type).

2. The photosensitive resin composition of claim 1, wherein in the above general formula (A1), X contains at least one organic group selected from (B1) to (B3) above, and Y contains at least one organic group selected from (C1) to (C3) above.

3. The photosensitive resin composition of claim 1, wherein the reactive substituent comprises at least one selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkendienyl, styryl, ethynyl, imino, isocyanate, cyanate, cycloalkyl, epoxy, oxetyl, carbonate, hydroxyl, mercapto, hydroxymethyl, and alkoxyalkyl.

4. The photosensitive resin composition of claim 3, wherein the reactive substituent comprises at least one selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkendienyl, styryl, and ethynyl.

5. The photosensitive resin composition of claim 4, wherein the reactive substituent contains a methacrylic group.

6. The photosensitive resin composition of any one of claims 1 to 5, wherein the backbone at the end of the repeating unit of the main chain of the photosensitive polyimide precursor is derived from the backbone of the diamine monomer, and the substituent at the end of the main chain is derived from the -NH- substituent at the amino end of the backbone of the diamine monomer.

7. A photosensitive resin composition according to any one of claims 1 to 5, wherein at least one end of the main chain of the aforementioned photosensitive polyimide precursor has a structure of the following general formula (E1) or (F1); [Chemical 17] (wherein, a1 contains at least one group of amide bond, amide bond, urea bond, or carbamate bond, b1 is a reactive substituent that is crosslinked by heat or light, e1 is a monovalent organic group having 1 to 30 carbon atoms, R11 and R14 are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and R12 and R13 are each independently a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, an aromatic ring, or a portion of an aliphatic ring (wherein, R12 and R13 are not simultaneously hydrogen atoms)) [Chemical 18] (wherein, f1 contains at least one of amide bond, amide bond, urea bond, carbamate bond, and ester bond, g1 is a reactive substituent that is cross-linked by heat or light, and R15 to R19 are each independently a hydrogen atom, a monovalent organic group with 1 to 30 carbon atoms, or a part of an aromatic ring or an aliphatic ring (wherein, R16, R17, and R18 are not simultaneously hydrogen atoms)).

8. The photosensitive resin composition of claim 7, wherein b1 and g1 are reactive substituents with terminal double bonds.

9. The photosensitive resin composition of claim 8, wherein at least one end of the main chain of the photosensitive polyimide precursor contains the structure of the above general formula (F1).

10. The photosensitive resin composition of claim 9, wherein the above f1 contains at least one of amide, amide, urea, or carbamate groups.

11. The photosensitive resin composition of claim 7, wherein b1 contains at least one selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkyldienyl, styryl, ethynyl, imino, isocyanate, cyanate, cycloalkyl, epoxy, oxetyl, carbonate, hydroxyl, mercapto, hydroxymethyl, and alkoxyalkyl.

12. The photosensitive resin composition of claim 11, wherein b1 contains at least one selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkenyl, styryl, and ethynyl.

13. The photosensitive resin composition of claim 12, wherein the reactive substituent of b1 that is crosslinked by heat or light contains a methacrylic group.

14. The photosensitive resin composition of claim 7, wherein the reactive substituent of g1 that is crosslinked by heat or light contains at least one selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkendienyl, styryl, ethynyl, imino, isocyanate, cyanate, cycloalkyl, epoxy, oxetyl, carbonate, hydroxy, mercapto, hydroxymethyl, and alkoxyalkyl.

15. The photosensitive resin composition of claim 14, wherein the reactive substituent of g1 that is crosslinked by heat or light contains at least one selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkendienyl, styryl, and ethynyl.

16. The photosensitive resin composition of claim 15, wherein the reactive substituent of g1 that is crosslinked by heat or light contains a methacrylyl group.

17. The photosensitive resin composition of claim 1, wherein in the above general formula (A1), X contains the above general formula (B3) and Y contains the above general formula (C2).

18. The photosensitive resin composition of claim 1, wherein in the above general formula (A1), X contains the above general formula (B3) and Y contains the above general formula (C1).

19. The photosensitive resin composition of claim 1, wherein in the above general formula (A1), X contains the above general formula (B2) and Y contains the above general formula (C2).

20. The photosensitive resin composition of claim 1, wherein in the above general formula (A1), X contains the above general formula (B2), and Y contains at least one selected from the group consisting of the above general formulas (C1) and (C3).

21. The photosensitive resin composition of claim 1, wherein in the above general formula (A1), X contains the above general formula (B1) and Y contains the above general formula (C1).

22. The photosensitive resin composition of any one of claims 1 to 5 has a viscosity of 40 poise or less.

23. The photosensitive resin composition of claim 22 has a viscosity of 20 poise or less.

24. The photosensitive resin composition of any one of claims 1 to 5 has a viscosity of 1 poise or more.

25. A photosensitive resin composition comprising a photosensitive polyimide precursor having reactive substituents at the ends of the main chain that react with heat or light, wherein the photosensitive polyimide precursor contains a structure represented by the following general formula (A1): [Chemical 25] {In general formula (A1), X is a tetravalent organic group, Y is a divalent organic group, R5 and R6 are each independently hydrogen atoms, a monovalent organic group represented by the following general formula (R1) [Chemical 26] (in general formula (R1), R7, R8 and R9 are each independently hydrogen atoms or C1 to C3 organic groups, and p is an integer selected from 1 to 10), or a saturated aliphatic group of C1 to C4; wherein, R5 and R6 are not both hydrogen atoms. At least one end of the main chain of the above-mentioned photosensitive polyimide precursor has a structure represented by the following general formula (E1) or (F1); [Chem. 27] (wherein, a1 contains at least one of amide bond, amide bond, urea bond, and carbamate bond; b1 is a reactive substituent that is crosslinked by heat or light; e1 is a monovalent organic group with 1 to 30 carbon atoms; R11 and R14 are each independently hydrogen atoms or monovalent organic groups with 1 to 30 carbon atoms; and R12 and R13 are each independently hydrogen atoms, monovalent organic groups with 1 to 30 carbon atoms, or a portion of an aromatic ring or an aliphatic ring (wherein, R12 and R13 are not both hydrogen atoms)). [Chem. 28] (In the formula, f1 contains at least one of amide bond, amide bond, urea bond, carbamate bond, and ester bond, g1 is a reactive substituent that is cross-linked by heat or light, and R15 to R19 are each independently a hydrogen atom, a monovalent organic group with 1 to 30 carbon atoms, or a part of an aromatic ring or an aliphatic ring (wherein, R16, R17, and R18 are not hydrogen atoms at the same time)).

26. The photosensitive resin composition of claim 25, wherein b1 and g1 are reactive substituents with terminal double bonds.

27. The photosensitive resin composition of claim 25 or 26, wherein at least one end of the main chain of the photosensitive polyimide precursor contains the structure of the above general formula (F1).

28. The photosensitive resin composition of claim 27, wherein the above f1 contains at least one of amide, amide, urea, or carbamate groups.

29. A method for manufacturing a hardened embossed pattern, characterized by comprising the following steps: (1) a coating step of forming a photosensitive resin layer on a substrate by coating a photosensitive resin composition of any one of claims 1 to 28 onto the substrate; (2) an exposure step of exposing the photosensitive resin layer; (3) a development step of developing the exposed photosensitive resin layer to form an embossed pattern; and (4) a heating step of forming a hardened embossed pattern by heat treatment of the embossed pattern.

30. A method for manufacturing a photosensitive resin composition, characterized in that: it is a method for manufacturing a photosensitive resin composition as claimed in any one of claims 1 to 28, and the photosensitive polyimide precursor is synthesized by comprising the following steps: obtaining polyimide by performing a condensation polymerization reaction of a diamine monomer and an acid dianhydride monomer in an excess of one, and introducing the reactive substituent at the end of the main chain of the polyimide by reacting the amine or acid anhydride remaining at the end of the polyimide with a compound having a reactive substituent that reacts with heat or light.