Polyimide precursor resin composition and method for producing the same

Abstract

The purpose of the present disclosure is to provide a method for manufacturing a polyimide (PI) precursor resin composition that has excellent resolution performance, a broad range of available exposure and good handling properties. Provided is a method for manufacturing a PI precursor resin composition that comprises a PI precursor resin, an exposure light absorber, a photopolymerization initiator and a solvent. The PI precursor resin is selected from among materials having an absorbance parameter Xp for a light species within a range of 0.001-0.20, the exposure light absorber is selected from among materials having an absorbance parameter Xt for the light species within a range of 0.01-0.05, and the photopolymerization initiator is selected from among materials having an absorbance parameter Xr for the light species within a range of 0-0.04. On the basis of an assumed thickness D of a film that is formed by applying the PI precursor resin composition and desolventing, the addition amount (parts by mass) α of the exposure light absorber and the addition amount (parts by mass) β of the photopolymerization initiator are determined so as to satisfy the formula: 0.7 ≤ (Xp + Xt × α + Xr × β) × D ≤ 2.2.

Description

[Technical Field]

[0001] The present disclosure relates to a polyimide precursor resin composition and a method for producing the same. [Background technology]

[0002] Polyimide (PI) resins have excellent heat resistance, electrical properties, and chemical resistance, and are therefore used as insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, interlayer insulating films, and other applications. Photosensitive polyimides, which are polyimide resins imparted with photosensitivity, are available in the form of polyimide precursor resin compositions (also called "varnishes") containing polyimide precursor resins and photosensitizers. Polyimide relief patterns can be formed by applying the varnish, exposing it to light, developing it, and subjecting it to thermal imidization treatment through curing. While relief pattern formation with non-photosensitive polyimides requires the application and removal of resist materials, photosensitive polyimide precursor resins have the advantage of significantly shortening the process.

[0003] On the other hand, in recent years, the mounting method (packaging structure) of semiconductor devices on printed wiring boards has also changed in view of improvements in integration density and computing functionality, as well as the miniaturization of chip sizes. Specifically, the conventional mounting method using metal pins and lead-tin eutectic solder has been replaced by structures in which a polyimide coating directly contacts solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher-density mounting. Furthermore, structures such as FO (fan-out) have been proposed, in which the surface of a semiconductor chip has multiple redistribution layers with an area larger than the area of ​​the semiconductor chip (see, for example, Patent Documents 1 and 2).

[0004] As packages become smaller and denser, high resolution performance is required for the resin film that forms the rewiring layer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-167191 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-129767 Summary of the Invention [Problem to be solved by the invention]

[0006] When a negative-tone photosensitive resin composition is used as the PI precursor resin composition, if the exposure light does not converge appropriately at the bottom of the film during exposure patterning, the exposure light reflected from the bottom of the film may leave residue at the development opening, resulting in poor development. Furthermore, if the exposure light does not reach the bottom of the film, photocrosslinking at the bottom of the film may be insufficient, resulting in a tapered shape defect known as undercutting. Therefore, one of the objectives of the present disclosure is to provide a PI precursor resin composition that has excellent resolution performance, a wide usable exposure dose range, and excellent handleability. These issues become more pronounced when the PI precursor resin composition is applied thinly or when a PI precursor resin composition with low exposure light absorbance is used. [Means for solving the problem]

[0007] The inventors have discovered that a PI precursor resin composition containing a PI precursor resin, an exposure ray absorber, a photopolymerization initiator, and a solvent can be provided with excellent resolution, a wide range of usable exposure doses, and easy handling by determining the composition using a specific method based on the light absorbance parameters of the PI precursor resin, the exposure ray absorber, and the photopolymerization initiator for the type of light used for exposure. Examples of embodiments of the present disclosure are listed below in items [1] to

[43] . [1] A method for producing a polyimide (PI) precursor resin composition containing a PI precursor resin, an exposure ray absorber, a photopolymerization initiator, and a solvent, the method comprising the steps of: identifying the type of light used for exposure; selecting the PI precursor resin from resins having an absorbance parameter Xp in the range of 0.001 to 0.20 for the specified light ray species, selecting the exposure ray absorber from materials having an absorbance parameter Xt in the range of 0.01 to 0.05 for the specified light ray species, and selecting the photopolymerization initiator from materials having an absorbance parameter Xr in the range of 0 to 0.04 for the specified light ray species; Based on the absorbance parameter Xp of the selected PI precursor resin, the absorbance parameter Xt of the selected exposure ray absorber, the absorbance parameter Xr of the selected photopolymerization initiator, and the assumed thickness D of a prebaked film obtained by coating the PI precursor resin composition and removing the solvent, the following formula: 0.7≦(Xp+Xt×α+Xr×β)×D≦2.2 determining the parts by mass α of the exposure ray absorber and the parts by mass β of the photopolymerization initiator to be added based on 100 parts by mass of the PI precursor resin so as to satisfy the following: preparing a PI precursor resin composition containing the determined PI precursor resin, the determined addition weight part α of the exposure radiation absorber, the determined addition weight part β of the photopolymerization initiator, and a solvent; A method for producing a PI precursor resin composition, comprising: [2] The PI precursor resin is a compound represented by the following formula (1): [ka] {In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom, a monovalent organic group represented by the following general formula (2), or a saturated aliphatic group having 1 to 4 carbon atoms.} [ka] {In the formula, R3, R4, and R5 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.} The method according to item 1, wherein the structural unit is represented by [3] 3. The manufacturing method according to item 1 or 2, wherein the light beam used for the exposure is i-line. [4] 4. The manufacturing method according to any one of items 1 to 3, wherein the assumed thickness D is set to 1 μm or more and less than 7 μm, and the added mass parts α of the exposure ray absorber and the added mass parts β of the photopolymerization initiator are determined. [5] The photopolymerization initiator is represented by the following general formula (5): [ka] {where, R 16 , R 17 , and R 18 are each a monovalent organic group, and R 16 , and R 17 may be linked to each other to form a ring structure. 5. The method according to any one of items 1 to 4, wherein the compound has an oxime ester structure represented by the formula: [6] 6. The method according to any one of items 1 to 5, wherein the PI precursor resin composition further contains a nitrogen-containing heterocyclic rust inhibitor. [7] 7. The method according to any one of items 1 to 6, wherein the exposure ray absorber is a compound having a 1,2-naphthoquinone diazide structure. [8] 8. The method according to any one of items 1 to 7, wherein the PI precursor resin composition further contains a photopolymerizable compound. [9] Y1 in the above formula (1) is represented by the following formula (3): [ka] {In the formula, R6~R 13 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R to R 13 At least one of is a methyl group, a trifluoromethyl group, or a methoxy group. 9. The method according to any one of items 1 to 8, wherein the divalent organic group is represented by the formula:

[10] Y1 in the above formula (1) is represented by the following formula (4): [ka] {where, R 14 , R 15 are each independently a methyl group, a trifluoromethyl group, or a methoxy group. 10. The method according to any one of items 1 to 9, wherein the divalent organic group is represented by the formula:

[11] The exposure ray absorber is represented by the following general formulas (6) to (10): [ka] {In formula (6), X1 and X2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, X3 and X4 each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, r1, r2, r3, and r4 each independently represent an integer of 0 to 5, at least one of r3 and r4 is an integer of 1 to 5, r1+r3=5, and r2+r4=5.} [ka] {In formula (7), Z represents a tetravalent organic group having 1 to 20 carbon atoms; X5, X6, X7, and X8 each independently represent a monovalent organic group having 1 to 30 carbon atoms; r6 is an integer of 0 or 1; r5, r7, r8, and r9 each independently represent an integer of 0 to 3; r10, r11, r12, and r13 each independently represent an integer of 0 to 2; and at least one of r10, r11, r12, and r13 is 1 or 2.} [ka] {In formula (8), r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, r14 × r15 Ls each independently represent a monovalent organic group having 1 to 20 carbon atoms, r15 Ts each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and r15 Ss each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.} [ka] {In formula (9), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group.} [ka] In formula (10), r17, r18, r19, and r20 each independently represent an integer of 0 to 2, and at least one of r17, r18, r19, and r20 is 1 or 2; X 10 ~X 19 each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y1 to Y3 each independently represents at least one divalent group selected from the group consisting of a single bond, -O-, -S-, -SO-, -SO2-, -CO-, -CO2-, cyclopentylidene, cyclohexylidene, phenylene, and a divalent organic group having 1 to 20 carbon atoms.} 11. The method according to any one of items 1 to 10, wherein the hydroxy compound is 1,2-naphthoquinone diazide-4-sulfonic acid ester and / or 1,2-naphthoquinone diazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of:

[12] 12. The method according to any one of items 1 to 11, wherein the exposure ray absorber is a 1,2-naphthoquinone diazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of the above formulas (6) to (10).

[13] 13. The method according to any one of items 1 to 12, wherein the esterification rate of the exposure ray absorber is 80% or more.

[14] The hydroxy compound represented by the general formula (6) is represented by the following general formula (11): [ka] {In formula (11), each r20 independently represents an integer of 0 to 2, and each X9 independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.} 14. The method according to any one of items 1 to 13, wherein the manufacturing method is represented by the following formula:

[15] A method for producing a relief pattern film, the method comprising: A step of producing a PI precursor resin composition containing a PI precursor resin, an exposure ray absorber, a photopolymerization initiator, and a solvent by the method according to any one of items 1 to 14; a coating step of obtaining a coating film of the PI precursor resin composition; a drying step of removing the solvent from the coating film to obtain a photosensitive resin layer having a thickness of D'; an exposure step of exposing the photosensitive resin layer to the specified light ray species; a development step of developing the photosensitive resin layer after the exposure to obtain a relief pattern film; A method for producing a relief pattern film, comprising:

[16] After removing the solvent, the coating film has a thickness of D'. 0.7≦(Xp+Xt×α+Xr×β)×D'≦2.2 Item 16. The method for producing a relief pattern film according to Item 15,

[17] A PI precursor resin composition containing a PI precursor resin, an exposure ray absorber in an amount of α parts by mass, a photopolymerization initiator in an amount of β parts by mass, and a solvent, based on 100 parts by mass of the PI precursor resin, the absorbance parameter Xp of the PI precursor resin for i-line; an absorbance parameter Xt of the exposure ray absorber for i-line; The absorbance parameter Xr of the photopolymerization initiator for i-line, parts by weight α of the exposure radiation absorber; The relationship with the mass parts β of the photopolymerization initiator is 0.7≦(Xp+Xt×α+Xr×β)×10≦2.2 0.001≦Xp≦0.20 0.01≦Xt≦0.05 0≦Xr≦0.04 The PI precursor resin composition.

[18] A polyimide (PI) precursor resin composition comprising: a polyimide precursor resin; an exposure ray absorber in an amount of α parts by mass, a photopolymerization initiator in an amount of β parts by mass, and a solvent, based on 100 parts by mass of the PI precursor resin; the absorbance parameter Xp of the PI precursor resin for i-line; an absorbance parameter Xt of the exposure ray absorber for i-line; The absorbance parameter Xr of the photopolymerization initiator for i-line, parts by weight α of the exposure radiation absorber; The relationship with the mass parts β of the photopolymerization initiator is 0.7≦(Xp+Xt×α+Xr×β)×5≦2.2 0.001≦Xp≦0.20 0.01≦Xt≦0.05 0≦Xr≦0.04 The PI precursor resin composition.

[19] The PI precursor resin is a compound represented by the following formula (1): [ka] {In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom, a monovalent organic group represented by the following general formula (2), or a saturated aliphatic group having 1 to 4 carbon atoms.} [ka] {In the formula, R3, R4, and R5 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.} Item 19. The PI precursor resin composition according to item 17 or 18, having a structural unit represented by the following formula:

[20] The photopolymerization initiator is represented by the following general formula (5): [ka] {where, R 16 , R 17 , and R 18 are each a monovalent organic group, and R16 , and R 17 may be linked to each other to form a ring structure. 20. The PI precursor resin composition according to any one of items 17 to 19, having an oxime ester structure represented by the following formula: [twenty one] 21. The PI precursor resin composition according to any one of items 17 to 20, further comprising a nitrogen-containing heterocyclic rust inhibitor. [twenty two] 22. The PI precursor resin composition according to any one of items 17 to 21, wherein the exposure ray absorber is a compound having a 1,2-naphthoquinone diazide structure. [twenty three] 23. The PI precursor resin composition according to any one of items 17 to 22, further comprising a photopolymerizable compound. [twenty four] Y1 in the above formula (1) is represented by the following formula (3): [ka] {In the formula, R6~R 13 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R to R 13 At least one of is a methyl group, a trifluoromethyl group, or a methoxy group. 24. The PI precursor resin composition according to any one of items 17 to 23, wherein the divalent organic group is represented by the following formula: [twenty five] Y1 in the above formula (1) is represented by the following formula (4): [ka] {where, R 14 , R 15 are each independently a methyl group, a trifluoromethyl group, or a methoxy group. 25. The PI precursor resin composition according to any one of items 17 to 24, wherein R is a divalent organic group represented by the following formula:

[26] The exposure ray absorber is represented by the following general formulas (6) to (10): [ka] {In formula (6), X1 and X2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, X3 and X4 each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, r1, r2, r3, and r4 each independently represent an integer of 0 to 5, at least one of r3 and r4 is an integer of 1 to 5, r1+r3=5, and r2+r4=5.} [ka] {In formula (7), Z represents a tetravalent organic group having 1 to 20 carbon atoms; X5, X6, X7, and X8 each independently represent a monovalent organic group having 1 to 30 carbon atoms; r6 is an integer of 0 or 1; r5, r7, r8, and r9 each independently represent an integer of 0 to 3; r10, r11, r12, and r13 each independently represent an integer of 0 to 2; and at least one of r10, r11, r12, and r13 is 1 or 2.} [ka] {In formula (8), r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, r14 × r15 Ls each independently represent a monovalent organic group having 1 to 20 carbon atoms, r15 Ts each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and r15 Ss each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.} [ka] {In formula (9), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group.} [ka] In formula (10), r17, r18, r19, and r20 each independently represent an integer of 0 to 2, and at least one of r17, r18, r19, and r20 is 1 or 2; X 10 ~X 19each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y1 to Y3 each independently represents at least one divalent group selected from the group consisting of a single bond, -O-, -S-, -SO-, -SO2-, -CO-, -CO2-, cyclopentylidene, cyclohexylidene, phenylene, and a divalent organic group having 1 to 20 carbon atoms.} 26. The PI precursor resin composition according to any one of items 17 to 25, wherein the hydroxyl group is 1,2-naphthoquinonediazide-4-sulfonic acid ester and / or 1,2-naphthoquinonediazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of:

[27] 27. The PI precursor resin composition according to any one of items 17 to 26, wherein the exposure ray absorber is a 1,2-naphthoquinonediazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of the above formulas (6) to (10).

[28] 28. The PI precursor resin composition according to any one of items 17 to 27, wherein the esterification rate of the exposure ray absorber is 80% or more.

[29] The hydroxy compound represented by the general formula (6) is represented by the following general formula (11): [ka] {In formula (11), each r16 independently represents an integer of 0 to 2, and each X9 independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.} 29. The PI precursor resin composition according to any one of items 17 to 28, represented by the formula:

[30] 29. A cured film of the PI precursor resin composition according to any one of items 17 to 29.

[31] A prebaked film containing a polyimide (PI) precursor resin composition having a thickness D' of 1 μm≦D'≦20 μm, The PI precursor resin composition contains a PI precursor resin, α parts by mass of an exposure ray absorber relative to 100 parts by mass of the PI precursor resin, and β parts by mass of a photopolymerization initiator relative to 100 parts by mass of the PI precursor resin, The PI precursor resin has an absorbance parameter Xp for i-line in the range of 0.001≦Xp≦0.20, the exposure ray absorber has an absorbance parameter Xt for i-line in the range of 0.01≦Xt≦0.05; The photopolymerization initiator has an absorbance parameter Xr for i-line in the range of 0≦Xr≦0.04, The following formula: 0.7≦(Xp+Xt×α+Xr×β)×D'≦2.2 Meet the pre-baked film.

[32] The PI precursor resin is a compound represented by the following formula (1): [ka] {In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom, a monovalent organic group represented by the following general formula (2), or a saturated aliphatic group having 1 to 4 carbon atoms.} [ka] {In the formula, R3, R4, and R5 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.} Item 32. The prebaked film according to item 31, having a structural unit represented by the formula:

[33] Item 33. The prebaked film according to item 31 or 32, wherein the thickness D' of the prebaked film is 1 μm≦D'<7 μm.

[34] The photopolymerization initiator is represented by the following general formula (5): [ka] {where, R 16 , R 17 , and R 18are each a monovalent organic group, and R 16 , and R 17 may be linked to each other to form a ring structure. 34. The prebaked film according to any one of items 31 to 33, having an oxime ester structure represented by the following formula:

[35] 35. The prebaked film according to any one of items 31 to 34, wherein the PI precursor resin composition further contains a nitrogen-containing heterocyclic rust inhibitor.

[36] 36. The prebaked film according to any one of items 31 to 35, wherein the exposure ray absorber is a compound having a 1,2-naphthoquinone diazide structure.

[37] 37. The prebaked film according to any one of items 31 to 36, wherein the PI precursor resin composition further contains a photopolymerizable compound.

[38] Y1 in the above formula (1) is represented by the following formula (3): [ka] {In the formula, R6~R 13 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R to R 13 At least one of is a methyl group, a trifluoromethyl group, or a methoxy group. 38. The prebaked film according to any one of items 31 to 37, wherein R is a divalent organic group represented by the following formula:

[39] Y1 in the above formula (1) is represented by the following formula (4): [ka] {where, R 14 , R 15 are each independently a methyl group, a trifluoromethyl group, or a methoxy group. 39. The prebaked film according to any one of items 31 to 38, wherein R is a divalent organic group represented by the formula:

[40] The exposure ray absorber is represented by the following general formulas (6) to (10): [ka] {In formula (6), X1 and X2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, X3 and X4 each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, r1, r2, r3, and r4 each independently represent an integer of 0 to 5, at least one of r3 and r4 is an integer of 1 to 5, r1+r3=5, and r2+r4=5.} [ka] {In formula (7), Z represents a tetravalent organic group having 1 to 20 carbon atoms; X5, X6, X7, and X8 each independently represent a monovalent organic group having 1 to 30 carbon atoms; r6 is an integer of 0 or 1; r5, r7, r8, and r9 each independently represent an integer of 0 to 3; r10, r11, r12, and r13 each independently represent an integer of 0 to 2; and at least one of r10, r11, r12, and r13 is 1 or 2.} [ka] {In formula (8), r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, r14 × r15 Ls each independently represent a monovalent organic group having 1 to 20 carbon atoms, r15 Ts each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and r15 Ss each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.} [ka] {In formula (9), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group.} [ka] In formula (10), r17, r18, r19, and r20 each independently represent an integer of 0 to 2, and at least one of r17, r18, r19, and r20 is 1 or 2; X 10 ~X 19each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y1 to Y3 each independently represents at least one divalent group selected from the group consisting of a single bond, -O-, -S-, -SO-, -SO2-, -CO-, -CO2-, cyclopentylidene, cyclohexylidene, phenylene, and a divalent organic group having 1 to 20 carbon atoms.} 39. The prebaked film according to any one of items 31 to 39, wherein the hydroxyl group is a 1,2-naphthoquinone diazide-4-sulfonic acid ester and / or a 1,2-naphthoquinone diazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of:

[41] 41. The prebaked film according to any one of items 31 to 40, wherein the exposure ray absorber is a 1,2-naphthoquinone diazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of the above formulas (6) to (10).

[42] 42. The prebaked film according to any one of items 31 to 41, wherein the esterification rate of the exposure ray absorber is 80% or more.

[43] The hydroxy compound represented by the general formula (6) is represented by the following general formula (11): [ka] {In formula (11), each r20 independently represents an integer of 0 to 2, and each X9 independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.} 43. The pre-baked film according to any one of items 31 to 42, which is represented by the following formula: [Effects of the Invention]

[0008] According to the present disclosure, it is possible to provide a method for producing a PI precursor resin composition that has excellent resolution performance, a wide range of usable exposure doses, and excellent handleability. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is an FIB photograph of the cross-sectional shape of the pattern obtained in Example 1. [Figure 2] FIG. 2 is a sensitivity curve plotting the relative film thickness at each exposure dose of the relief pattern obtained in Example 50. DETAILED DESCRIPTION OF THE INVENTION

[0010] <<Method for producing PI precursor resin composition>> The present disclosure provides a method for producing a PI precursor resin composition comprising (A) a polyimide (PI) precursor resin, (B) an exposure ray absorber, (C) a photopolymerization initiator, and (D) a solvent, and the method includes the following steps: a step of identifying the type of light used for exposure; a material selection step of selecting a polyimide precursor resin, an exposure ray absorber, and a photopolymerization initiator; a content determination step of determining the parts by mass α of the exposure ray absorber to be added and the parts by mass β of the photopolymerization initiator to be added; and a step of preparing the PI precursor resin composition.

[0011] <Light ray type identification process> In the light beam type identification step, the type of light beam to be used for exposing the PI precursor resin composition is identified. Any light beam type can be used as long as it can crosslink the polymerizable groups of the polyimide precursor resin by the action of a photopolymerization initiator when the PI precursor resin composition is exposed, thereby rendering the polyimide precursor resin insoluble in a developer. Examples of light beam types include g-line (436 nm), h-line (405 nm), i-line (wavelength 365 nm), and KrF excimer laser (wavelength 248 nm). From the viewpoints of insolubilization of the polyimide precursor resin and resolution performance, i-line is preferred.

[0012] <Material selection process> In the material selection process, (A) polyimide precursor resin, (B) exposure ray absorber, and (C) photopolymerization initiator are selected according to the absorbance parameters for the selected light ray species. (D) Solvent can be selected arbitrarily, regardless of the selected light ray species. In addition to these, other materials, such as (E) photopolymerizable compound, thermal base generator, (H) nitrogen-containing heterocyclic rust inhibitor, (F) hindered phenol compound, organotitanium compound, adhesion promoter, sensitizer, or (G) polymerization inhibitor, or combinations thereof, may also be selected regardless of the selected light ray species. Other materials, including (E), (F), and (G), can also be selected arbitrarily, regardless of the selected light ray species.

[0013] (A) Selection of polyimide precursor resin The polyimide precursor resin is a resin component contained in a negative-type photosensitive resin composition and is converted to polyimide by a thermal cyclization treatment. The polyimide precursor resin is selected from resins having an absorbance parameter Xp in the range of 0.001 to 0.20 for a specified light species. The absorbance of the polyimide precursor resin can be measured by adjusting the polyimide precursor resin to 1000 mg / L using N-methyl-2-pyrrolidone as a solvent and measuring it with a UV-visible spectrophotometer using a 1 cm cell. The absorbance parameter Xp of the polyimide precursor resin is defined as the value obtained by dividing the obtained absorbance value at 365 nm by 10. The polyimide precursor resin is selected from resins having an absorbance parameter Xp in the range of preferably 0.001 to 0.15, more preferably 0.005 to 0.10, and even more preferably 0.005 to 0.05. The structure of the polyimide precursor resin is not limited as long as it is a polyimide precursor resin that can be used in a negative-tone photosensitive resin composition, but it is preferable that it is not alkali-soluble. The non-alkali-soluble polyimide precursor resin can achieve high chemical resistance. When the negative-tone photosensitive resin composition contains two or more polyimide precursor resins, the mixture of the two or more polyimide precursor resins may have an absorbance parameter Xp of 0.001 to 0.20 for a specified light ray species. It is preferable that all of the two or more polyimide precursor resins be selected so that the absorbance parameter Xp for the specified light ray species is within the range of 0.001 to 0.20.

[0014] The polyimide precursor resin is preferably a polyamide having a structure represented by the following general formula (1). [ka] {In formula (1), X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group.}

[0015] In the general formula (1), at least one of R1 and R2 is represented by the following general formula (2): [ka] {In formula (2), R3, R4, and R5 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.} It is preferable that the compound has a structural unit represented by the following formula:

[0016] The proportion of hydrogen atoms in R1 and R2 in general formula (1) is preferably 20% or less, more preferably 15% or less, and even more preferably 5% or less, based on the total number of moles of R1 and R2. Furthermore, the proportion of monovalent organic groups represented by general formula (2) in R1 and R2 in general formula (1) is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, based on the total number of moles of R1 and R2. It is preferable that the proportion of hydrogen atoms and the proportion of organic groups of general formula (2) be within the above ranges from the viewpoints of photosensitive properties and storage stability.

[0017] In general formula (1), n1 is not limited as long as it is an integer of 2 to 150, but from the viewpoint of the photosensitivity and mechanical properties of the negative photosensitive resin composition, it is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

[0018] In general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the -COOR1 group, the -COOR2 group, and the -CONH- group are located at the ortho positions relative to each other, or an alicyclic aliphatic group. Specific examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, such as those represented by the following general formula (I): [ka] wherein R6 is a hydrogen atom, a fluorine atom, or a C1 to C 10 Monovalent hydrocarbon groups, and C1-C 10where l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.}, but is not limited thereto. The structure of X1 may be one type or a combination of two or more types. The X1 group having the structure represented by the above formula (I) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0019] As the X1 group, among the structures represented by the above formula (I), particularly, those represented by the following formula: [ka] In the formula, R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and m is an integer selected from 0 to 3. It is particularly preferred that the polyimide precursor resin contains a tetravalent organic group represented by the following formula:

[0020] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (II): [ka] wherein R6 is a hydrogen atom, a fluorine atom, or a C1 to C 10 Monovalent hydrocarbon groups, and C1-C 10 and n is an integer selected from 0 to 4.}, but is not limited to these. The structure of Y1 may be one type or a combination of two or more types. The Y1 group having the structure represented by the above formula (II) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0021] As the Y1 group, among the structures represented by the above formula (II), particularly, those represented by the following formula: [ka] A divalent group represented by the formula: {wherein R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4} is preferred from the viewpoints of heat resistance, chemical resistance, and resolution.

[0022] As the Y group, among the structures represented by the above formula (II), those represented by the following formula (3): [ka] {In the formula, R6~R 13 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R to R 13 At least one of the groups is a methyl group, a trifluoromethyl group, or a methoxy group. A divalent group represented by the following formula is more preferred. When the polyimide precursor resin has such a rigid structure, swelling of the film during development can be suppressed, and extremely high resolution can be achieved.

[0023] As the Y group, among the structures represented by the above formula (II), those represented by the following formula (4): [ka] {where, R 14 , R 15 are each independently a methyl group, a trifluoromethyl group, or a methoxy group. A divalent group represented by the following formula is more preferred. When the polyimide precursor resin has such a rigid structure, swelling of the film during development can be suppressed, and extremely high resolution can be achieved.

[0024] (A) Method for preparing polyimide precursor resin The polyimide precursor resin can be obtained by first reacting a tetracarboxylic acid dianhydride containing the aforementioned tetravalent organic group X1 with a photopolymerizable alcohol having an unsaturated double bond and, optionally, an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester).Then, the partially esterified tetracarboxylic acid and a diamine containing the aforementioned divalent organic group Y1 are subjected to amide polycondensation.

[0025] (Preparation of Acid / Ester Forms) The tetracarboxylic acid dianhydride containing a tetravalent organic group X1, which is suitably used for preparing the polyimide precursor resin, includes, for example, a tetracarboxylic acid dianhydride having the structure represented by the above general formula (I), as well as pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylsulfone ... Examples of suitable dianhydrides include phenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and preferably pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited to these. These may be used alone or in combination of two or more.

[0026] Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare a polyimide precursor resin include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclopropyl acrylate, 2-hydroxy-3-hydroxy ... Examples of the methacryloyloxypropyl acrylate include 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0027] The above-mentioned photopolymerizable alcohols having an unsaturated double bond can also be mixed with alcohols not having an unsaturated double bond, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

[0028] As the polyimide precursor resin, a non-photosensitive polyimide precursor resin prepared only from the above-mentioned alcohols having no unsaturated double bonds may be used by mixing with the photosensitive polyimide precursor resin. From the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor resin is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

[0029] The esterification reaction of the acid anhydride can be carried out by stirring, dissolving, and mixing a tetracarboxylic dianhydride and an alcohol in a solvent as described below in the presence of a basic catalyst such as pyridine, thereby obtaining the desired acid / ester. The stirring, dissolving, and mixing are preferably carried out at a temperature of 20 to 50°C for 4 to 24 hours, for example.

[0030] (Preparation of Polyimide Precursor Resin) The acid / ester compound (typically present as a solution in a solvent, as described below) can be converted into a polyanhydride by adding and mixing with an appropriate dehydration condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, under ice cooling. A polyimide precursor resin can be obtained by adding dropwise a diamine containing a divalent organic group Y1 dissolved or dispersed in a separate solvent to the polyanhydride of the acid / ester compound, followed by amide polycondensation. Alternatively, a polyimide precursor resin can be obtained by converting the acid moiety of the acid / ester compound into an acid chloride using thionyl chloride or the like, followed by reaction with a diamine compound in the presence of a base, such as pyridine.

[0031] As another synthesis method, a polyimide precursor resin can also be obtained by first reacting a tetracarboxylic dianhydride with a diamine compound to obtain a polyamic acid, and then using an appropriate dehydration condensation agent, for example, trifluoroacetic anhydride, to introduce the above-mentioned alcohol into the carboxylic acid moiety in the side chain of the obtained polyamic acid.

[0032] Diamines containing a divalent organic group Y1 include diamines having the structure shown in the above general formula (II), as well as, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, sulfon, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfon bis(4-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoro Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, and 9,9-bis(4-aminophenyl)fluorene, as well as compounds in which some of the hydrogen atoms on the benzene ring have been substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl and 2,2'-dimethyl-4,Examples of the diaminobiphenyl include, but are not limited to, 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

[0033] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off as needed. A poor solvent, such as water, aliphatic lower alcohol, or a mixture thereof, is then added to the resulting polymer component to precipitate the polymer component. The polymer is then purified by repeated redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor resin. To improve the degree of purification, the polymer solution may be passed through a column packed with anion and / or cation exchange resins swollen with an appropriate organic solvent to remove ionic impurities.

[0034] The molecular weight of the polyimide precursor resin, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. A weight average molecular weight of 8,000 or more provides good mechanical properties, while a weight average molecular weight of 150,000 or less provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are preferred as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. The standard monodisperse polystyrene is preferably selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0035] (B) Selection of exposure light absorber The exposure ray absorber is selected from materials whose absorbance parameter Xt for the specified light ray species is in the range of 0.01 to 0.05. By keeping the absorbance within this range, the film absorbance can be precisely adjusted within the appropriate addition amount. If the absorbance parameter Xt is less than 0.01, a large amount must be added to adjust the absorbance, resulting in side effects such as precipitation of the exposure ray absorber or inhibition of other performance characteristics. On the other hand, if the absorbance parameter Xt is greater than 0.05, the addition of a small amount dramatically changes the film absorbance, making precise adjustment difficult. The absorbance of the exposure ray absorber can be measured by adjusting the concentration of the exposure ray absorber to 10 mg / L in N-methyl-2-pyrrolidone as a solvent and using a 1 cm cell with a UV-visible spectrophotometer. The absorbance value at 365 nm obtained is divided by 10, and the resulting value is defined as the absorbance parameter Xt of the exposure ray absorber. The exposure ray absorber is selected from materials having an absorbance parameter Xt preferably in the range of 0.015 to 0.040, more preferably 0.015 to 0.03, and even more preferably 0.015 to 0.025. When the negative photosensitive resin composition contains two or more exposure ray absorbers, the mixture of the two or more exposure ray absorbers may have an absorbance parameter Xt in the range of 0.01 to 0.05 for the specified light ray species. It is preferable to select all of the two or more exposure ray absorbers so that their absorbance parameters Xt in the range of 0.01 to 0.05 for the specified light ray species.

[0036] The exposure light absorber is preferably at least one compound selected from the group consisting of 2-(2'-hydroxyphenyl)benzotriazole compounds, hydroxyphenyltriazine compounds, 2-hydroxybenzophenone compounds, cyanoacrylate compounds, azobenzene compounds, polyphenol compounds, and compounds having a quinone azide group. Specific examples of the exposure light absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol], 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 6-(2-benzotriazolyl)-4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'- 2-(2'-hydroxyphenyl)benzotriazole compounds such as methylene bisphenol, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, and 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole; hydroxyphenyltriazine compounds such as 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4,6-tris(4-butoxy-2-hydroxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, bemotrizinol, and 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine; 2-hydroxybenzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate; Examples include cyanoacrylate compounds, azobenzene compounds, polyphenol compounds such as catechin, rutin, cyanidin, and curcumin, and compounds having a quinone azide group (hereinafter also referred to as "quinone diazide compounds").

[0037] In particular, from the viewpoint of resolution performance, the exposure ray absorber is preferably a quinone diazide compound. Examples of quinone diazide compounds include compounds having a 1,2-benzoquinone diazide structure and compounds having a 1,2-naphthoquinone diazide structure, and these are known substances as disclosed in U.S. Pat. Nos. 2,772,972, 2,797,213, and 3,669,658. From the viewpoint of resolution performance and the cross-sectional shape of the formed pattern, the quinone diazide compound is more preferably at least one compound selected from the group consisting of 1,2-naphthoquinone diazide-4-sulfonic acid esters of polyhydroxy compounds having a specific structure described in detail below and 1,2-naphthoquinone diazide-5-sulfonic acid esters of the polyhydroxy compounds (hereinafter also referred to as "NQD compounds"). The reason for this is thought to be, without being limited by theory, that the NQD compound absorbs the exposure light, undergoes an intramolecular rearrangement reaction, and loses its light-absorbing ability, thereby allowing for the appropriate adjustment of the amount of light reaching the bottom of the film. Another advantage of the NQD compound is that it has better solubility in solvents than other exposure light absorbers. Therefore, even when using a polyimide precursor resin with low exposure light absorbance or when the film thickness is thin, it is possible to adjust the absorbance of the coating film by adding a large amount of the NQD compound.

[0038] The NQD compound can be obtained by converting a naphthoquinone diazide sulfonic acid compound into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride, and then condensing the resulting naphthoquinone diazide sulfonyl chloride with a polyhydroxy compound, as described above. For example, the polyhydroxy compound can be esterified by reacting a predetermined amount of 1,2-naphthoquinone diazide-5-sulfonyl chloride or 1,2-naphthoquinone diazide-4-sulfonyl chloride with a solvent such as dioxane, acetone, or tetrahydrofuran in the presence of a basic catalyst such as triethylamine, and then washing the resulting product with water and drying it.

[0039] The compound having a quinone diazide group is preferably a 1,2-naphthoquinone diazide-4-sulfonic acid ester and / or a 1,2-naphthoquinone diazide-5-sulfonic acid ester compound of at least one hydroxy compound selected from the group consisting of the following general formulas (6) to (10): [ka] In formula (6), X1 and X2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, preferably 1 to 30 carbon atoms; X3 and X4 each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, preferably 1 to 30 carbon atoms; r1, r2, r3, and r4 each independently represent an integer of 0 to 5; at least one of r3 and r4 is an integer of 1 to 5; r1+r3=5; and r2+r4=5.

[0040] [ka] {In formula (7), Z represents a tetravalent organic group having 1 to 20 carbon atoms; X5, X6, X7, and X8 each independently represent a monovalent organic group having 1 to 30 carbon atoms; r6 is an integer of 0 or 1; r5, r7, r8, and r9 each independently represent an integer of 0 to 3; r10, r11, r12, and r13 each independently represent an integer of 0 to 2; and at least one of r10, r11, r12, and r13 is 1 or 2.}

[0041] [ka] {In formula (8), r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, r14 × r15 Ls each independently represent a monovalent organic group having 1 to 20 carbon atoms, r15 Ts each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and r15 Ss each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.}

[0042] [ka] {In formula (9), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group.} In formula (9), A is preferably represented by the following chemical formula: [ka] represents at least one divalent group selected from the three groups represented by the following formula:

[0043] [ka] In formula (10), r17, r18, r19, and r20 each independently represent an integer of 0 to 2, and at least one of r17, r18, r19, and r20 is 1 or 2; X 10 ~X 19each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y1 to Y3 each independently represents at least one divalent group selected from the group consisting of a single bond, -O-, -S-, -SO-, -SO2-, -CO-, -CO2-, cyclopentylidene, cyclohexylidene, phenylene, and a divalent organic group having 1 to 20 carbon atoms.}

[0044] In the general formula (10), Y1 to Y3 each independently represent the following general formula: [ka] {where, X 20 and X 21 each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and a substituted aryl group; X 22 , X 23 , X 24 and X 25 each independently represents a hydrogen atom or an alkyl group, r21 is an integer of 1 to 5, and X 26 , X 27 , X 28 and X 29 each independently represents a hydrogen atom or an alkyl group. Preferably, the divalent organic group is at least one selected from the three divalent organic groups represented by the following formula:

[0045] As the compound represented by the above general formula (6), hydroxy compounds represented by the following formulae (11) and (17) to (20) are preferred, and the hydroxy compound represented by formula (11) is more preferred. [ka] In formula (11), each r20 independently represents an integer of 0 to 2, and each X9 independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. When a plurality of X9s are present, the plurality of X9s may be the same or different.

[0046] In formula (11), X9 is represented by the following chemical formula: [ka] wherein r18 is an integer of 0 to 2, and X 31 represents at least one monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group, and a cycloalkyl group, and when r18 is 2, two X 31 may be the same as or different from each other. It is preferable that the alkyl group is a monovalent organic group represented by the following formula:

[0047] [ka] {In formula (17), X 32 represents at least one monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.}

[0048] [ka] In formula (18), each r19 is independently an integer of 0 to 2, and X 33 are each independently a hydrogen atom or the following general formula: [ka] (wherein r20 is an integer of 0 to 2, and X 35 represents at least one selected from the group consisting of a hydrogen atom, an alkyl group, and a cycloalkyl group, and when r20 is 2, two X 35 may be the same or different from each other.) and X represents a monovalent organic group represented by 34 represents at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.}

[0049] [ka] The compound represented by the above formula (20) is p-cumylphenol.

[0050] As the compound represented by formula (11) above, hydroxy compounds represented by the following formulae (21) to (23) are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in PI precursor resin compositions (these are NQDs of polyhydroxy compounds described in JP 2004-109849 A). [ka] [ka] [ka]

[0051] As the compound represented by the above formula (17), a hydroxy compound represented by the following formula (24) is preferred because it has high sensitivity when converted into an NQD product and low precipitation tendency in a PI precursor resin composition (this is an NQD product of a polyhydroxy compound described in JP-A-2001-356475): [ka]

[0052] As the compound represented by (18) above, hydroxy compounds represented by the following formulae (25) to (27) are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in PI precursor resin compositions (these are NQDs of polyhydroxy compounds described in JP-A-2005-8626). [ka] [ka] [ka]

[0053] In the above general formula (7), Z is not particularly limited as long as it is a tetravalent organic group having 1 to 20 carbon atoms. From the viewpoint of sensitivity, however, it is preferable that Z is a tetravalent organic group having the following formula: [ka] It is preferable that the aryl group is a tetravalent group having a structure represented by the following formula:

[0054] Among the compounds represented by the general formula (7) above, the hydroxy compounds represented by the following formulae (28) to (31) are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in PI precursor resin compositions (these are NQDs of polyhydroxy compounds described in JP-A-2001-92138). [ka] [ka] [ka] [ka]

[0055] As the compound represented by the general formula (8) above, a hydroxy compound represented by the following formula (32) is preferred because it has high sensitivity when converted into an NQD product and low precipitation tendency in a PI precursor resin composition (this is an NQD product of a polyhydroxy compound described in JP 2004-347902 A). [ka] {In the formula, each r40 independently represents an integer of 0 to 9.}

[0056] As the compound represented by the general formula (9), the hydroxy compounds represented by the following formulas (33) and (34) are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in the PI precursor resin composition. [ka] [ka]

[0057] Specific examples of the compound represented by the general formula (10) include NQDs of polyhydroxy compounds described in JP 2001-109149 A. Among these compounds, NQDs of polyhydroxy compounds represented by the following formula (35) are preferred because of their high sensitivity and low precipitation tendency in PI precursor resin compositions: [ka]

[0058] In quinone diazide compounds, the 1,2-naphthoquinone diazide sulfonyl group is excellent in resolution whether it is a 1,2-naphthoquinone diazide-5-sulfonyl group or a 1,2-naphthoquinone diazide-4-sulfonyl group, but the 1,2-naphthoquinone diazide-5-sulfonyl group is even better in resolution.

[0059] In the quinone diazide compound, the average esterification rate of the naphthoquinone diazide sulfonyl ester of the hydroxy compound is preferably from 60% to 100%, more preferably from 80% to 100%, from the viewpoint of resolution. This is presumably because swelling during development is suppressed by esterification of the hydroxy groups in the quinone diazide compound (B').

[0060] In this embodiment, it is preferable to select one or both of a 1,2-naphthoquinone diazide-4-sulfonic acid ester compound and a 1,2-naphthoquinone diazide-5-sulfonic acid ester compound. Alternatively, a 1,2-naphthoquinone diazide sulfonic acid ester compound having both a 1,2-naphthoquinone diazide-4-sulfonyl group and a 1,2-naphthoquinone diazide-5-sulfonyl group in the same molecule may be used, or a mixture of a 1,2-naphthoquinone diazide-4-sulfonic acid ester compound and a 1,2-naphthoquinone diazide-5-sulfonic acid ester compound may be used.

[0061] (C) Photopolymerization initiator The photopolymerization initiator is selected from materials whose absorbance parameter Xr for the specified light species is in the range of 0 to 0.04. The absorbance of the photopolymerization initiator can be measured by adjusting the photopolymerization initiator to 10 mg / L using N-methyl-2-pyrrolidone as a solvent and using a 1 cm cell with a UV-visible spectrophotometer. The absorbance value at 365 nm obtained is divided by 10, and the resulting value is defined as the absorbance parameter Xr of the photopolymerization initiator. The photopolymerization initiator is selected from compounds whose absorbance parameter Xr is preferably in the range of 0 to 0.03, more preferably 0 to 0.02, and even more preferably 0 to 0.01. When the negative-type photosensitive resin composition contains two or more photopolymerization initiators, the mixture of the two or more photopolymerization initiators may have an absorbance parameter Xr for the specified light species in the range of 0 to 0.04. It is preferable to select the two or more photopolymerization initiators so that all of them have an absorbance parameter Xr within the range of 0 to 0.04 for the specified light ray species.

[0062] The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples thereof include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime; Preferred examples of the photoacid generator include, but are not limited to, oximes such as 1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide; and photobase generators such as 9-anthrylmethyl-N,N-diethylcarbamate. Among the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.

[0063] Among the oxime photopolymerization initiators, from the viewpoint of photosensitivity, those represented by the following general formula (5): [ka] {where, R 16 , R 17 , and R 18 are each a monovalent organic group, and R 16 , and R 17may be linked to each other to form a ring structure. It is preferable that the compound has an oxime ester structure represented by the following formula:

[0064] Among the compounds having the oxime ester structure of the above formula (5), from the viewpoint of photosensitivity, at least one compound selected from the group consisting of the following formulae (5A), (5B), and (5C) is more preferred. [ka] {In formula (5A), R1 is a methyl group or a phenyl group, R2 is a hydrogen atom or a monovalent organic group having 1 to 12 carbon atoms, and R3 is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group.} [ka] {In formula (5B), Z is a sulfur or oxygen atom, R4 represents a methyl group or a phenyl group, and R5 to R7 each independently represent a hydrogen atom or a monovalent organic group.} [ka] In formula (5C), R8 is an aromatic group having 6 to 20 carbon atoms or a monovalent organic group derived from a heterocyclic compound having 5 to 20 carbon atoms, R9 is an alkyl group having 1 to 5 carbon atoms, and R 10 is a monovalent organic group having an alkyl group having 1 to 10 carbon atoms or a saturated alicyclic structure having 3 to 10 carbon atoms, and R 11 represents a methyl group, an ethyl group, a propyl group, or a phenyl group.}

[0065] (D) Solvent Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, and propylene glycol. Examples of solvents that can be used include glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 3-methoxy-N,N-dimethylpropanamide, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, and mesitylene. Among these, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, 3-methoxy-N,N-dimethylpropanamide, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred from the viewpoints of resin solubility, resin composition stability, and substrate adhesion.

[0066] Among these solvents, those that completely dissolve the produced polymer are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, 3-methoxy-N,N-dimethylpropanamide, tetramethylurea, gamma-butyrolactone, etc. One type of solvent may be used, or two or more types of solvents may be mixed and used.

[0067] In the PI precursor resin composition, the amount of solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of the polyimide precursor resin.

[0068] The PI precursor resin composition may further contain components other than the above components (A) to (D) (hereinafter also referred to as "other components"). Examples of other components other than components (A) to (D) include, but are not limited to, (E) photopolymerizable compounds, thermal base generators, (H) nitrogen-containing heterocyclic rust inhibitors, (F) hindered phenol compounds, organotitanium compounds, adhesion promoters, sensitizers, and (G) polymerization inhibitors. Among the materials included in the "other components," materials with an absorbance parameter Xt of 0.01 to 0.05 are generally classified as "exposure ray absorbers." However, among the materials included in the "other components," even if the absorbance parameter Xt is 0.01 to 0.05, compounds that absorb light themselves and donate the obtained energy to other compounds to improve the sensitivity of the system are classified as "sensitizers." The use of a sensitizer increases the system's sensitivity, narrowing the usable exposure dose range and promoting residue formation at the bottom of unexposed areas, resulting in the opposite effect to that of an exposure light absorber. Furthermore, among the materials included in the "other components," even if the absorbance parameter Xt is 0.01 to 0.05, nitrogen-containing heterocyclic compounds having an interaction site with the copper interface, such as an imino group or amino group, are classified as (H) "nitrogen-containing heterocyclic rust inhibitors." Furthermore, among the materials included in the "other components," even if the absorbance parameter Xt is 0.01 to 0.05, compounds having an interaction site with the silicon wafer interface, such as an alkoxysilane structure, are classified as "adhesion additives." These "nitrogen-containing heterocyclic rust inhibitors" and "adhesion additives" are unevenly distributed near the wafer interface and therefore do not have the effect of adjusting the absorbance of the entire film. Therefore, substances classified as "sensitizers," "nitrogen-containing heterocyclic rust inhibitors," and "adhesion aids" are not considered to be "exposure ray absorbers" even if the absorbance parameter Xt value is 0.01 to 0.05.

[0069] (E) Photopolymerizable compound The PI precursor resin composition preferably further contains a photopolymerizable compound. The photopolymerizable compound is a monomer that has a photopolymerizable unsaturated bond and can assist in crosslinking of the polyimide precursor resin by exposure to light. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator. Examples of the photopolymerizable compound include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di-, or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, and diacrylate and dimethacrylate of 1,6-hexanediol. Examples of the acrylate or methacrylate include diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri-, or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0070] When the PI precursor resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond, the blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass per 100 parts by mass of the polyimide precursor resin. If the blending amount is 1 part by mass or more, good sensitivity can be obtained during exposure, and if it is 50 parts by mass or less, excellent in-plane uniformity of the coating film can be obtained.

[0071] Thermal base generator The PI precursor resin composition may contain a base generator. A base generator is a compound that generates a base upon heating. The inclusion of a thermal base generator can further promote imidization of the PI precursor resin composition.

[0072] The thermal base generator is not particularly limited in type, but examples thereof include an amine compound protected by a tert-butoxycarbonyl group, or the thermal base generators disclosed in WO 2017 / 038598. However, the thermal base generator is not limited to these, and other known thermal base generators can also be used.

[0073] Examples of amine compounds protected by a tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine Aminoamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ether Examples of the tert-butoxycarbonyl protecting agent include, but are not limited to, tert-butoxycarbonyl ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a tert-butoxycarbonyl group.

[0074] The amount of the thermal base generator is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the (A) polyimide precursor resin. The amount is preferably 0.1 part by mass or more from the viewpoint of the imidization-accelerating effect, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the PI precursor resin composition.

[0075] (H) Nitrogen-containing heterocyclic rust inhibitor When a cured film is formed on a copper or copper alloy substrate using a PI precursor resin composition, the PI precursor resin composition may optionally contain a nitrogen-containing heterocyclic rust inhibitor to suppress discoloration of the copper. Examples of nitrogen-containing heterocyclic rust inhibitors include azole compounds and purine derivatives. However, 2-(2'-hydroxyphenyl)benzotriazole compounds are not included in the nitrogen-containing heterocyclic rust inhibitors because they do not have a coordination site for copper. The nitrogen-containing heterocyclic rust inhibitor is preferably a compound having an imino group or an amino group.

[0076] Examples of the azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, ... ,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like.

[0077] Among these, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, and 5-amino-1H-tetrazole are preferred. These azole compounds may be used alone or in combination of two or more.

[0078] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, guanine oxime, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and derivatives thereof.

[0079] When the PI precursor resin composition contains the above-mentioned azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor resin, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity. When the blending amount of the azole compound relative to 100 parts by mass of the (A) polyimide precursor resin is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the PI precursor resin composition is formed on copper or a copper alloy. On the other hand, when the blending amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0080] (F) Hindered phenol compounds To inhibit discoloration on copper surfaces, the PI precursor resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and the like.

[0081] Examples of the hindered phenol compound include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxybenzyl) 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-di 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,Examples of suitable hydroxybenzoates include, but are not limited to, 6-(1H,3H,5H)-trione and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0082] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass per 100 parts by mass of the (A) polyimide precursor resin, and from the viewpoint of photosensitivity, more preferably 0.5 to 10 parts by mass. When the amount of the hindered phenol compound per 100 parts by mass of the (A) polyimide precursor resin is 0.1 part by mass or more, for example, when the PI precursor resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0083] Organotitanium Compounds The PI precursor resin composition may contain an organotitanium compound, which allows the formation of a photosensitive resin layer that has excellent chemical resistance even when cured at low temperatures.

[0084] Usable organotitanium compounds include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they improve the storage stability of the PI precursor resin composition and allow for good patterns to be obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate. Among these, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. Titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

[0085] When an organotitanium compound is added, the amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the (A) polyimide precursor resin. When the amount is 0.05 part by mass or more, good heat resistance and chemical resistance are exhibited, while when the amount is 10 parts by mass or less, excellent storage stability is achieved.

[0086] Adhesion aid To improve the adhesion between a film formed using the PI precursor resin composition and a substrate, the PI precursor resin composition may optionally contain an adhesion promoter. Examples of adhesion promoters include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, and benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl). ]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, and the like; and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate, and the like.

[0087] Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the PI precursor resin composition contains an adhesion aid, the amount of the adhesion aid blended is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of the (A) polyimide precursor resin.

[0088] Examples of silane coupling agents include, but are not limited to, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxy Examples thereof include 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, and 4-mercaptobutyltrippropoxysilane.

[0089] The silane coupling agent is not limited to, but examples thereof include N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, and N-(3-ethoxydimethoxysilylethyl) Examples thereof include urea, N-(3-trippropoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-trippropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2).

[0090] Examples of silane coupling agents include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methacryloylsilane), bis(triethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[ 3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenyl silanetriol, methyl phenyl silanediol, ethyl phenyl silanediol, n-propyl phenyl silanediol, isopropyl phenyl silanediol, n-butyldiphenyl silanediol, isobutylphenyl silanediol, tert-butylphenyl silanediol, diphenyl silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol, n-butylmethyl phenyl silanol, isobutylmethyl phenyl silanol, tert-butylmethyl phenyl silanol, ethyl n-propyl phenyl silanol, ethyl isopropyl phenyl silanol, n-butylethyl phenyl silanol, isobutylethyl phenyl silanol, tert-butylethyl phenyl silanol,Examples of the silanol include, but are not limited to, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

[0091] The silane coupling agents listed above may be used alone or in combination. Among the silane coupling agents listed above, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the silane coupling agents represented by the following formula: [ka] A silane coupling agent having a structure represented by the following formula is preferred.

[0092] When a silane coupling agent is used, the amount to be added is preferably 0.01 to 20 parts by mass per 100 parts by mass of the (A) polyimide precursor resin.

[0093] sensitizer The PI precursor resin composition may optionally contain a sensitizer to improve photosensitivity, such as Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene indole. Non, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of, for example, 2 to 5 types.

[0094] When the PI precursor resin composition contains a sensitizer for improving photosensitivity, the amount of the sensitizer added is preferably 0.1 to 25 parts by mass per 100 parts by mass of the (A) polyimide precursor resin.

[0095] (G) Polymerization inhibitor The PI precursor resin composition may optionally contain a polymerization inhibitor to improve the viscosity and photosensitivity stability of the PI precursor resin composition, especially during storage in a solvent-containing solution. Examples of polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0096] <Content determination process> In the content determination step, the following formula (1): 0.7≦(Xp+Xt×α+Xr×β)×D≦2.2 (1) According to the above formula, the mass parts α of the exposure ray absorber and β of the photopolymerization initiator are determined based on the absorbance parameter Xp of the polyimide precursor resin, the absorbance parameter Xt of the exposure ray absorber, the absorbance parameter Xr of the photopolymerization initiator, and the assumed thickness D of the prebaked film obtained by coating the PI precursor resin composition and removing the solvent. The mass parts α and β are expressed as parts by mass based on 100 parts by mass of the polyimide precursor resin. The inventors discovered that because the degree of absorption of light beams (e.g., i-line) varies depending on the skeleton of the PI precursor resin, it is necessary to adjust the light absorption characteristics of the entire resin composition to fall within the above-mentioned specific range using other components in accordance with the absorbance parameter of the PI precursor resin. This allows for the production of a PI precursor resin composition that is suitable for the intended film thickness, has excellent resolution performance, and can be used over a wide range of exposure doses. The reason for this is thought to be, without being limited by theory, that by setting the absorbance of the PI precursor resin composition coating film within the range of the above formula (1), the amount of light reaching the bottom of the film during exposure can be adjusted, thereby suppressing diffuse reflection from the substrate underlying the bottom of the film and preventing unintended crosslinking reactions in the unexposed areas.

[0097] The value of (Xp + Xt × α + Xr × β) × D is preferably in the range of 0.7 to 2.2, more preferably in the range of 0.7 to 1.4. If the value of formula (1) is less than 0.7, diffuse reflection from the underlying substrate at the bottom of the film during exposure causes a large amount of residue to form at the development opening, making it difficult to achieve good resolution. Furthermore, if a PI precursor resin composition is prepared to satisfy formula (1) using only a photopolymerization initiator without an exposure ray absorber, the sensitivity to exposure rays increases, narrowing the range of usable exposure dose and reducing handleability. On the other hand, if the value of formula (1) exceeds 2.2, photocuring at the bottom of the film becomes insufficient, resulting in a problem of tapered shape called undercut. If the value of formula (1) is within the range of 0.7 to 1.4, a pattern with an ideal tapered shape can be obtained, along with good resolution. In the present disclosure, an ideal tapered shape refers to a pattern with a wall angle of approximately 70° to 80°. If the wall angle is 70° or more, the wiring under the PI cured film is well covered, reducing the risk of exposing the lower wiring. If the wall angle is 80° or less, the sputtered seed layer of the RDL wiring formed on the upper layer of the PI cured film adheres well, reducing the risk of poor formation of the RDL wiring.

[0098] The assumed thickness D of the prebaked film is the assumed thickness of the prebaked film obtained by coating the PI precursor resin composition and removing the solvent. In this specification, the actual thickness of the prebaked film obtained by coating the PI precursor resin composition and removing the solvent is referred to as D'. The assumed thickness D of the prebaked film is preferably set to 1 μm to 20 μm, more preferably 1 μm to 10 μm, and even more preferably 1 μm to less than 7 μm.

[0099] The blending amount α of the exposure ray absorber determined by the above formula (1) may be, for example, 0.1 parts by mass or more and 20 parts by mass or less, 1 part by mass or more and 10 parts by mass or less, or 1 part by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polyimide precursor resin, when the exposure ray is set to i-ray and the assumed thickness D of the prebaked film is set to 10 μm.

[0100] The blending amount β of the photopolymerization initiator determined by the above formula (1) may be, for example, 0.1 parts by mass or more and 10 parts by mass or more, 1 part by mass or more and 8 parts by mass or less, or 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the polyimide precursor resin, when the exposure radiation is set to i-line and the assumed thickness D of the prebaked film is set to 10 μm.

[0101] <Step of preparing PI precursor resin composition> In the PI precursor resin composition preparation step, the PI precursor resin composition is prepared to contain a determined PI precursor resin, a determined addition weight part α of an exposure radiation absorber, a determined addition weight part β of a photopolymerization initiator, a solvent, and optionally other materials. More specifically, the PI precursor resin composition can be obtained by, for example, adding and mixing each material in a selected solvent. The viscosity of the PI precursor resin composition may be adjusted to, for example, 10 to 100 poise. If necessary, the PI precursor resin composition may be filtered.

[0102] <<Method for manufacturing a relief pattern film>> The method for producing a relief pattern film of the present disclosure includes: (1) a step of producing a PI precursor resin composition containing a PI precursor resin, an exposure ray absorber, a photopolymerization initiator, and a solvent by the above-mentioned method for producing a PI precursor resin composition; (2) a coating step of obtaining a coating film of the PI precursor resin composition; (3) a drying step of removing the solvent in the coating film to obtain a prebaked film having a thickness D'; (4) an exposure step of exposing the prebaked film to a specified light beam; and (5) a development step of developing the photosensitive resin layer after exposure to obtain a relief pattern film.

[0103] (1) A step of producing a PI precursor resin composition This step is a step of producing a PI precursor resin composition by the above-described step of producing a PI precursor resin composition according to the present disclosure.

[0104] (2)Coating process In this step, the PI precursor resin composition is applied to a substrate to form a coating film of the PI precursor resin composition. The application method can be a conventional method for applying PI precursor resin compositions, such as using a spin coater, bar coater, blade coater, curtain coater, or screen printer, or spray coating with a spray coater.

[0105] (3) Drying process In this step, the solvent in the coating film of the PI precursor resin composition is removed to obtain a prebaked film with an actual thickness D'. The actual thickness D' is the same as or close to the expected thickness D, and may be, for example, within a range of about ±5% of the expected thickness D. The thickness D' is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm, and even more preferably 1 μm to less than 7 μm. Examples of methods for removing the solvent include air drying, heat drying in an oven or on a hot plate, and reduced pressure or vacuum drying. Specifically, air drying or heat drying can be performed at 20°C to 150°C for 1 minute to 1 hour. The prebaked film with a thickness D' after solvent removal preferably satisfies 0.7≦(Xp+Xt×α+Xr×β)×D'≦2.2, and even more preferably 0.7≦(Xp+Xt×α+Xr×β)×D'≦1.4.

[0106] (4) Exposure process In this process, the photosensitive resin layer formed above is exposed to a specified type of light. The exposure is performed using an exposure device such as a contact aligner, mirror projection, or stepper, either through a patterned photomask or reticle, or directly using an ultraviolet light source. This exposure causes the polyimide precursor contained in the PI precursor resin composition in the exposed areas to crosslink due to the action of the photopolymerization initiator, making it insoluble in a developer.

[0107] (5)Developing process In this process, the photosensitive resin layer is developed after exposure to obtain a relief pattern film. The unexposed portions of the exposed photosensitive resin layer are developed and removed by contacting them with a developer. Any of the conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment, can be used as the development method. Furthermore, after development, post-development baking may be performed at any combination of temperature and time, as needed, for the purpose of adjusting the shape of the relief pattern, etc.

[0108] The developer used for development is preferably, for example, a good solvent for the PI precursor resin composition, or a combination of the good solvent and a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the PI precursor resin composition. Furthermore, two or more types of each solvent, for example, several types, can also be used in combination.

[0109] <<Method for producing cured film (cured relief pattern)>> The method for producing a cured film according to the present disclosure includes (5) a step of curing the relief pattern film produced in the above-described development step to form a cured film (cured relief pattern).

[0110] (6) Hardened relief pattern formation process In this step, the relief pattern obtained by the development is heat-treated to dissolve the photosensitive component and imidize the polyimide precursor resin, thereby converting it into a cured relief pattern made of polyimide. Heat treatment can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. The heat treatment temperature is preferably 250°C or lower, more preferably 200°C or lower. Air or an inert gas such as nitrogen or argon can be used as the atmospheric gas during heat curing.

[0111] <Polyimide> According to the present disclosure, the above-mentioned method for producing a cured film also provides a cured film of a PI precursor resin composition. The cured film is, in other words, a cured relief pattern of polyimide. The imidization rate of the polyimide is preferably 80 to 100%. The structure of the polyimide contained in the cured film (cured relief pattern) formed from the polyimide precursor resin composition is preferably represented by the following general formula: [ka] {In the above general formula, X1 and Y1 are the same as X1 and Y1 in general formula (1), and m is a positive integer.}

[0112] For the same reason, the preferred X1 and Y1 in general formula (1) are also preferred in polyimides having a structure represented by the above general formula. In the above general formula, the number m of repeating units is not particularly limited, but may be an integer of 2 to 150.

[0113] Semiconductor Device The present disclosure also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern. For example, a semiconductor device can be provided having a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described method for producing a cured relief pattern. It is also possible to provide a method for producing a semiconductor device using a semiconductor element as the substrate and including the above-described method for producing a cured relief pattern of the present disclosure as part of its process. A semiconductor device can be produced by forming the cured relief pattern formed by the method for producing a cured relief pattern of the present disclosure as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for producing a semiconductor device.

[0114] 《Display device》 The present disclosure provides a display device including a display element and a cured film disposed on the display element, the cured film having the above-described cured relief pattern. The cured relief pattern may be laminated directly on the display element or may be laminated via another layer. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA-type liquid crystal display devices, and partition walls for cathodes of organic EL elements.

[0115] The PI precursor resin composition of the present disclosure is preferably a PI precursor resin composition for forming an insulating member or an interlayer insulating film. In addition to being applied to the semiconductor device described above, the PI precursor resin composition is also useful for applications such as an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper-clad board, a solder resist film, and a liquid crystal alignment film. [Example]

[0116] Examples and comparative examples will be specifically described below, but the present disclosure is not limited thereto.

[0117] (A) Example of Production of Polyimide Precursor Resin <Production Example 1> 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 3 L separable flask, followed by 135.4 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone. The mixture was stirred at room temperature, and 79.1 g of pyridine was added with stirring to obtain a reaction mixture. After the reaction ceased to generate heat, the mixture was allowed to cool to room temperature and left for 16 hours. Next, under ice cooling, a solution of 203.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by a suspension of 94.4 g of 2,2'-dimethylbiphenyl-4,4'-diamine (mTB) in 300 mL of γ-butyrolactone over 60 minutes with stirring. The reaction mixture was stirred for an additional 4 hours at room temperature, followed by the addition of 50 mL of ethyl alcohol and stirring for 1 hour. Next, 500 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain PI precursor resin A-1, a powdered polyamic acid ester. The molecular weight of PI precursor resin A-1 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 30,000.

[0118] The weight-average molecular weight (Mw) of PI precursor resin A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) under the following conditions: The column used for the measurement was a "Shodex 805M / 806M series" manufactured by Showa Denko K.K. Standard monodisperse polystyrene was selected, the developing solvent was N-methyl-2-pyrrolidone (NMP), and the detector was a "Shodex RI-930" manufactured by Showa Denko K.K.

[0119] <Production Example 2> 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 3 L separable flask, followed by 135.4 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone. The mixture was stirred at room temperature, and 158.2 g of pyridine was added with stirring to obtain a reaction mixture. After the reaction ceased to generate heat, the mixture was allowed to cool to room temperature and left for 16 hours. Next, 130.9 g of thionyl chloride was added dropwise to the ODPA-HEMA solution with stirring over 60 minutes under ice cooling to obtain an ODPA acid chloride solution. Next, a solution of 142.3 g of 2,2'-bis(trifluoromethyl)benzidine in 300 mL of NMP was added over 60 minutes under ice cooling with stirring. The reaction mixture was stirred at room temperature for another 2 hours, followed by 50 mL of ethyl alcohol and stirring for 1 hour. Next, 500 mL of γ-butyrolactone was added.

[0120] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a crude polymer precipitate. The resulting crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer. The resulting precipitate was filtered off and vacuum dried to obtain PI precursor resin A-2, a powdered polyamic acid ester. The molecular weight of PI precursor resin A-2 was measured using the same method as in Production Example 1, and the weight-average molecular weight (Mw) was found to be 28,000.

[0121] <Production Example 3> PI precursor resin A-3 was obtained by carrying out a reaction in the same manner as in Production Example 1, except that 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) was used instead of 94.4 g of 2,2'-dimethylbiphenyl-4,4'-diamine (mTB) in Production Example 1. The molecular weight of PI precursor resin A-3 was measured in the same manner as in Production Example 1, and the weight-average molecular weight (Mw) was found to be 20,000.

[0122] <Production Example 4> PI precursor resin A-4 was obtained by carrying out the reaction in the same manner as in Production Example 3, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 3, and the amount of 4,4'-diaminodiphenyl ether (DADPE) was changed to 90.1 g. The molecular weight of PI precursor resin A-4 was measured in the same manner as in Production Example 1, and the weight-average molecular weight (Mw) was found to be 30,000.

[0123] <Production Example 5> PI precursor resin A-5 was obtained by carrying out the reaction in the same manner as in Production Example 3, except that 93.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 58.8 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 3, and 87.6 g of 4,4'-diaminodiphenyl ether (DADPE) was used instead of 93.0 g. The molecular weight of PI precursor resin A-5 was measured using the same method as in Production Example 1, and the weight-average molecular weight (Mw) was found to be 20,000.

[0124] <Production Example 6> PI precursor resin A-6 was obtained by carrying out the reaction in the same manner as in Production Example 1, except that 32.72 g of pyromellitic anhydride (PMDA) and 112.78 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride were used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1, and 85.10 g of 4,4'-diaminodiphenyl ether (DADPE) was used instead of 94.4 g of 2,2'-dimethylbiphenyl-4,4'-diamine (mTB). The molecular weight of PI precursor resin A-6 was measured using the same method as in Production Example 1, and the weight-average molecular weight (Mw) was found to be 28,000.

[0125] <Production Example 7> PI precursor resin A-7 was obtained by carrying out a reaction in the same manner as in Production Example 2, except that 91.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (mTB) was used instead of 142.3 g of 2,2'-bis(trifluoromethyl)benzidine in Production Example 2. The molecular weight of PI precursor resin A-7 was measured in the same manner as in Production Example 1, and the weight-average molecular weight (Mw) was found to be 32,000.

[0126] <Production Example 8> 47.1 g of 4,4'-oxydiphthalic dianhydride (ODPA), 5.54 g of 2-hydroxyethyl methacrylate (HEMA), and a catalytic amount of 1,4-diazabicyclo[2,2,2]cutatriethylenediamine were dissolved in 380 g of NMP and stirred at 45°C for 1 hour, then cooled to 25°C. 27.4 g of 2,2'-dimethylbiphenyl-4,4'-diamine (mTB) and 145 mL of NMP were then added, stirred at 45°C for 150 minutes, and then cooled to room temperature. 59.7 g of trifluoroacetic anhydride was added dropwise to this solution and stirred for 120 minutes. After stirring, a catalytic amount of benzoquinone and 40.4 g of HEMA were added and stirred at 45°C for 20 hours. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain PI precursor resin A-8. The molecular weight of PI precursor resin A-8 was measured in the same manner as in Production Example 1, and the weight average molecular weight (Mw) was found to be 35,000.

[0127] (B) Example of synthesis of exposure ray absorber Synthesis Example 1 Synthesis of Compound B-1 with a 1,2-naphthoquinone diazide structure Into a 1 L separable flask equipped with a stirrer, a dropping funnel, and a thermometer, 30.0 g (0.707 mol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (trade name Tris-PA, manufactured by Honshu Chemical Industry Co., Ltd.) represented by the following formula (21) was placed as a hydroxy compound. [ka]

[0128] 53.56 g (0.198 mol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride, an amount equivalent to 93.3 mol% of the OH groups of the hydroxy compound, was dissolved in 300 g of acetone with stirring and then placed in a flask. The flask was then adjusted to 30°C in a thermostatic bath. Next, 20.0 g of triethylamine was dissolved in 18 g of acetone and placed in a dropping funnel. This was then added dropwise to the flask over 30 minutes. After the dropwise addition, stirring was continued for another 30 minutes, after which hydrochloric acid was added dropwise and stirred for another 30 minutes to terminate the reaction. The reaction mixture was then filtered to remove triethylamine hydrochloride. 1640 g of purified water and 30 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. The precipitate was washed with water, filtered, and then dried at 40°C under reduced pressure for 48 hours to obtain photosensitive diazonaphthoquinone (B-1).

[0129] Synthesis Example 2 Synthesis of Compound B-2 with a 1,2-Naphthoquinonediazide Structure Photosensitive diazonaphthoquinone (B-2) was obtained by carrying out reaction and purification in the same manner as in Synthesis Example 1, except that 47.82 g (0.177 mol) of 1,2-naphthoquinonediazide-4-sulfonic acid chloride was used instead of 53.56 g (0.198 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride in Synthesis Example 1.

[0130] Synthesis Example 3 Synthesis of Compound B-3 with a 1,2-Naphthoquinonediazide Structure Photosensitive diazonaphthoquinone (B-3) was obtained by carrying out reaction and purification in the same manner as in Synthesis Example 1, except that the amount of 1,2-naphthoquinone diazide-5-sulfonic acid chloride in Synthesis Example 1 was reduced from 53.56 g (0.198 mol) to 38.26 g (0.141 mol).

[0131] Synthesis Example 4 Synthesis of Compound B-4 with a 1,2-Naphthoquinonediazide Structure Into a 1 L separable flask equipped with a stirrer, a dropping funnel and a thermometer, 30 g (0.141 mol) of p-cumylphenol (manufactured by Mitsui Fine Chemicals, Inc.) represented by the following formula (20) as a hydroxy compound was placed. [ka]

[0132] 38.1 g (0.141 mol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride, an amount equivalent to 100 mol% of the OH groups of the hydroxy compound, was dissolved in 300 g of acetone with stirring and then placed in a flask. The flask was then adjusted to 30°C in a thermostatic bath. Next, 17.9 g of triethylamine was dissolved in 18 g of acetone and placed in a dropping funnel. This was then added dropwise to the flask over 30 minutes. After the dropwise addition, stirring was continued for another 30 minutes, after which hydrochloric acid was added dropwise and stirred for another 30 minutes to terminate the reaction. The reaction mixture was then filtered to remove triethylamine hydrochloride. 1640 g of purified water and 30 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. The precipitate was washed with water, filtered, and then dried at 40°C under reduced pressure for 48 hours to obtain photosensitive diazonaphthoquinone (B-4).

[0133] Synthesis Example 5 Synthesis of Compound B-5 with a 1,2-Naphthoquinonediazide Structure Photosensitive diazonaphthoquinone (B-5) was obtained by carrying out reaction and purification in the same manner as in Synthesis Example 4, except that 38.1 g (0.141 mol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride was replaced with 38.1 g (0.141 mol) of 1,2-naphthoquinone diazide-4-sulfonic acid chloride.

[0134] Synthesis Example 6 Synthesis of Compound B-6 with a 1,2-Naphthoquinonediazide Structure Into a 1 L separable flask equipped with a stirrer, a dropping funnel and a thermometer was placed 30 g (0.0474 mol) of a compound represented by the following formula (29) (trade name: Tekoc-4HBPA, manufactured by Honshu Chemical Industry Co., Ltd.) as a hydroxy compound. [ka]

[0135] 42.1 g (0.155 mol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride, an amount equivalent to 80 mol% of the OH groups of the hydroxy compound, was dissolved in 300 g of acetone with stirring and then placed in a flask. The flask was then adjusted to 30°C in a thermostatic bath. Next, 15.4 g of triethylamine was dissolved in 15 g of acetone and placed in a dropping funnel. This was then added dropwise to the flask over 30 minutes. After the dropwise addition, stirring was continued for another 30 minutes, after which hydrochloric acid was added dropwise and stirred for another 30 minutes to terminate the reaction. The reaction mixture was then filtered to remove triethylamine hydrochloride. 1640 g of purified water and 22 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. The precipitate was washed with water, filtered, and then dried at 40°C under reduced pressure for 48 hours to obtain photosensitive diazonaphthoquinone (B-6).

[0136] Synthesis Example 7 Synthesis of Compound B-7 with a 1,2-Naphthoquinonediazide Structure A 1 L separable flask equipped with a stirrer, a dropping funnel, and a thermometer was charged with 30 g (0.131 mol) of a compound represented by the following formula (30) (2,2-bis(4-hydroxyphenyl)propane) as a hydroxy compound. [ka]

[0137] 71.14 g (0.263 mol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride, an amount equivalent to 100 mol% of the OH groups of the hydroxy compound, was dissolved in 300 g of acetone with stirring and then placed in a flask. The flask was then adjusted to 30°C in a thermostatic bath. Next, 26.6 g of triethylamine was dissolved in 30 g of acetone and placed in a dropping funnel. This was then added dropwise to the flask over 30 minutes. After the dropwise addition, stirring was continued for another 30 minutes, after which hydrochloric acid was added dropwise and stirred for another 30 minutes to terminate the reaction. The reaction mixture was then filtered to remove triethylamine hydrochloride. 1640 g of purified water and 22 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. The precipitate was washed with water, filtered, and then dried at 40°C under reduced pressure for 48 hours to obtain photosensitive diazonaphthoquinone (B-7).

[0138] Synthesis Example 8 Synthesis of Compound B-8 with a 1,2-Naphthoquinonediazide Structure Photosensitive diazonaphthoquinone (B-8) was obtained by carrying out the reaction and purification in the same manner as in Synthesis Example 1, except that the amount of 1,2-naphthoquinone diazide-5-sulfonic acid chloride in Synthesis Example 1 was reduced from 53.56 g (0.198 mol) to 47.82 g (0.177 mol).

[0139] Synthesis Example 9 Synthesis of Compound B-13 with a 1,2-Naphthoquinonediazide Structure Into a 1 L separable flask equipped with a stirrer, a dropping funnel and a thermometer, 30 g (0.277 mol) of p-cresol, a compound represented by the following formula (31), was placed as a hydroxy compound. [ka]

[0140] 75.1 g (0.277 mol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride, an amount equivalent to 100 mol% of the OH groups of the hydroxy compound, was dissolved in 300 g of acetone with stirring and then placed in a flask. The flask was then adjusted to 30°C in a thermostatic bath. Next, 28.1 g of triethylamine was dissolved in 30 g of acetone and placed in a dropping funnel. This was then added dropwise to the flask over 30 minutes. After the dropwise addition, stirring was continued for another 30 minutes, after which hydrochloric acid was added dropwise and stirred for another 30 minutes to terminate the reaction. The reaction mixture was then filtered to remove triethylamine hydrochloride. 1600 g of purified water and 22 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. The precipitate was washed with water, filtered, and then dried at 40°C under reduced pressure for 48 hours to obtain photosensitive diazonaphthoquinone (B-13).

[0141] I. Examples 1 to 32 and Comparative Examples 1 to 26 <<Determination of composition ratio of polyimide precursor resin composition>> Example 1 The light beam used for exposure was specified as i-line. The resins listed in Table 4 were selected as (A) polyimide precursor resins, with an absorbance parameter Xp in the range of 0.001 to 0.20. The compounds listed in Table 4 were selected as exposure ray absorbers, with an absorbance parameter Xt in the range of 0.01 to 0.05. The compounds listed in Table 4 were selected as (C) photopolymerization initiators, with an absorbance parameter Xr in the range of 0 to 0.04. The expected thickness D of the prebaked film was set to 10 μm. α and β were determined to be the mass parts added listed in Table 4, satisfying the condition "0.7 ≦ (Xp + Xt × α + Xr × β) × D ≦ 2.2." (Xp + Xt × α + Xr × β) × D is as listed in Table 5.

[0142] Examples 2 to 32 The composition ratio of the polyimide precursor resin composition was determined in the same manner as in Example 1.

[0143] <<Preparation of Polyimide Precursor Resin Composition>> Examples 1 to 32 and Comparative Examples 1 to 26 The PI precursor resin compositions of Examples 1 to 32 and Comparative Examples 1 to 26 were prepared by dissolving (A) polyimide precursor resin, (B) exposure radiation absorber, (C) photopolymerization initiator, (E) photopolymerizable compound, (F) hindered phenol compound, and (G) polymerization inhibitor in a mixed solvent (D) of γ-butyrolactone and DMSO (weight ratio 80:20) in the amounts shown in Tables 4 and 6. The amounts shown in Tables 4 and 6 are the parts by mass of each component per 100 parts by mass of component (A). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding a small amount of the mixed solvent, and the solution was filtered through a polyethylene filter with 0.2 μm pores to obtain a resin composition. The symbols in the tables represent the following components:

[0144] As the (A) polyimide precursor resin, the following (A-1) to (A-8) were used. (A-1): The compound obtained in the above Production Example 1 (A-2): The compound obtained in Production Example 2 (A-3): The compound obtained in the above Production Example 3 (A-4): The compound obtained in Production Example 4 above (A-5): The compound obtained in the above Production Example 5 (A-6): The compound obtained in the above Production Example 6 (A-7): The compound obtained in the above Production Example 7 (A-8): The compound obtained in the above Production Example 8

[0145] (B) As the exposure ray absorber, the following (B-1) to (B-11) were used. (B-1): The diazonaphthoquinone compound obtained in Synthesis Example 1 above (B-2): The diazonaphthoquinone compound obtained in Synthesis Example 2 above (B-3): The diazonaphthoquinone compound obtained in Synthesis Example 3 above (B-4): Diazonaphthoquinone compound obtained in Synthesis Example 4 above (B-5): The diazonaphthoquinone compound obtained in Synthesis Example 5 above (B-6): Diazonaphthoquinone compound obtained in the above Synthesis Example 6 (B-7): Diazonaphthoquinone compound obtained in Synthesis Example 7 above (B-8): Diazonaphthoquinone compound obtained in the above Synthesis Example 8 (B-9): 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (trade name: Adeka STAB LA-29, manufactured by ADEKA Corporation) (B-10): 2,2',4,4'-tetrahydroxybenzophenone (trade name: SEESORB106, manufactured by Shipro Chemical Co., Ltd.) (B-11): Curcumin (Tokyo Chemical Industry Co., Ltd.) (B-12): 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (trade name: JF-77, Johoku Chemical Co., Ltd.) (B-13): Diazonaphthoquinone compound obtained in the above Synthesis Example 9

[0146] As the (C) photopolymerization initiator, the following (C-1) to (C-4) were used. (C-1): 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.) (C-2): 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (trade name: IRGACURE-OXE-01, manufactured by BASF) (C-3): 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF) (C-4): N-phenylglycine (Tokyo Chemical Industry Co., Ltd.)

[0147] As the (E) photopolymerizable compound, the following (E-1) was used. (E-1): Tetraethylene glycol dimethacrylate (Tokyo Chemical Industry Co., Ltd.)

[0148] In addition, the following ingredients were used: (F) 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (G) 2-Nitroso-1-naphthol

[0149] (H) As the nitrogen-containing heterocyclic rust inhibitor, the following (H-1) to (H-2) were used. (H-1): 8-azaadenine (Tokyo Chemical Industry Co., Ltd.) (H-2): 5-amino-1H-tetrazole (Tokyo Chemical Industry Co., Ltd.)

[0150] <<Measurement of absorbance parameters>> (A) Measurement of absorbance parameter Xp of polyimide precursor resin The absorbance (absorbance parameter Xp) of A-1 to A-8 was measured under the following measurement conditions. A-1 to A-8 were each dissolved in NMP and adjusted to 1000 mg / L to prepare measurement samples. The measurement was performed using an ultraviolet-visible spectrophotometer (UV-1800, manufactured by Shimadzu Corporation) with a 1 cm cell. The absorbance of each sample at 365 nm divided by 10 was used as Xp.

[0151] [Table 1]

[0152] (B) Measurement of the absorbance parameter Xt of the exposure radiation absorber The absorbance (absorbance parameter Xt) of B-1 to B-13 was measured under the following measurement conditions. Each of the (B) components was dissolved in NMP and adjusted to 10 mg / L to prepare a measurement sample. Measurements were performed using an ultraviolet-visible spectrophotometer (UV-1800, manufactured by Shimadzu Corporation) and a 1 cm cell. The absorbance of each sample at 365 nm divided by 10 was used as Xt.

[0153] [Table 2]

[0154] (C) Measurement of absorbance parameter Xr of photoinitiator The absorbance (absorbance parameter Xr) of C-1 to C-4 was measured under the following measurement conditions. Each of the (C) components was dissolved in NMP and adjusted to 10 mg / L to prepare a measurement sample. Measurements were performed using an ultraviolet-visible spectrophotometer (UV-1800, manufactured by Shimadzu Corporation) and a 1 cm cell. The absorbance at 365 nm of each sample divided by 10 was used as Xr.

[0155] [Table 3]

[0156] <<Production and Evaluation of Relief Pattern Films>> A 6-inch wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti layer and a 400 nm thick Cu layer, in that order, using a sputtering system (L-440S-FHL, Canon Anelva Corporation) to prepare a sputtered Cu wafer substrate. The PI precursor resin composition was spin-coated onto the 6-inch silicon wafer using a spin coater (D-SPIN60A, SOKUDO Co., Ltd.) and dried on a hot plate at 100°C for 180 seconds to produce a pre-baked film with a thickness of 10.0 μm±0.2 μm (D'). This spin-coated film was then exposed to light at 30 mJ / cm using a Prisma GHI S / N5503 projection exposure system (Ultratech Corporation) with a test pattern reticle having a 10 μm diameter circular recessed pattern and a gh-ray cut filter attached. 2 to 210 mJ / cm 2 Up to 15mJ / cm 2 The exposure was performed by varying the exposure dose in increments. Next, the coating film formed on the sputtered Cu wafer was spray-developed using cyclopentanone in a developer (D-SPIN636 model, manufactured by Dainippon Screen Co., Ltd.) and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. The development time for spray development was defined as 1.4 times the minimum time required for the resin composition in the unexposed areas to develop in the 10.0 μm spin-coated film.

[0157] <Evaluation of pattern taper shape> The cross section of the 10 μm diameter round-hole recessed pattern obtained above was machined using an FIB device (JIB-4000, manufactured by JEOL Ltd.). The cross-sectional shape of the pattern was observed, and the taper angle of the pattern relative to the substrate was determined by measuring the inclination at the midpoint of the taper. Pattern cross-sectional shapes were rated as excellent (AA) when the taper angle was 70° to 80°, fair (A) when the taper angle was 80° to 90°, and otherwise unacceptable (D). Patterns with undercuts or bridging in the cross section were also rated unacceptable. An FIB photograph of the cross-sectional shape of the pattern obtained in Example 1 is shown in Figure 1. An auxiliary line (1) indicating the inclination at the midpoint of the pattern is also shown in Figure 1. The taper angle of the pattern obtained in Example 1 relative to the substrate (auxiliary line (2)) was 82°. Patterns that failed the taper shape evaluation were not subjected to the maximum resolution evaluation and sensitivity allowance evaluation described below.

[0158] <Evaluation of highest resolution> The diameter of the round-cut recessed mold was changed as described above, and the minimum value of the mask dimension of the obtained round-cut recessed relief pattern was taken as the maximum resolution (μm), and evaluation was performed according to the following criteria. A: Patterns less than 5 μm open B: Patterns between 5 μm and 6 μm are open C: Patterns between 6 μm and 8 μm are open D: Patterns smaller than 8 μm do not open Regarding the possibility of opening the round-cut recessed relief pattern, a pattern that met both of the following criteria (I) and (II) was judged to be acceptable. (I) The area of ​​the pattern opening is at least half the area of ​​the corresponding pattern mask opening. (II) The cross section of the pattern does not have a bottomed-out edge, and no undercut, swelling, or bridging occurs.

[0159] <Evaluation of sensitivity tolerance> The range of exposure dose at which openings of 8 μm diameter were observed in the circular recessed relief pattern obtained above was evaluated according to the following criteria. A: 8μm pattern is 105mJ / cm 2 Opening with the above exposure width B: 8μm pattern is 45mJ / cm 2 More than 105mJ / cm 2 Opening with exposure width less than C: 8μm pattern is 15mJ / cm 2 More than 45mJ / cm 2 Opening with exposure width less than D: 8 μm pattern opens or does not open at pinpoint

[0160] [Table 4]

[0161] [Table 5]

[0162] [Table 6]

[0163] [Table 7]

[0164] II. Examples 33 to 49 and Comparative Examples 27 to 40 <<Determination of composition ratio of polyimide precursor resin composition>> Example 33 The light beam used for exposure was specified as i-line. Resins listed in Table 8 were selected as (A) polyimide precursor resins with an absorbance parameter Xp in the range of 0.001 to 0.20. Compounds listed in Table 8 were selected as exposure ray absorbers with an absorbance parameter Xt in the range of 0.01 to 0.05. Compounds listed in Table 8 were selected as (C) photopolymerization initiators with an absorbance parameter Xr in the range of 0 to 0.04. The expected thickness D of the prebaked film was set to 5 μm. α and β were determined to be the mass parts added listed in Table 8, satisfying the condition "0.7 ≦ (Xp + Xt × α + Xr × β) × D ≦ 2.2." (Xp + Xt × α + Xr × β) × D in this case is as listed in Table 9.

[0165] Examples 34 to 49 The composition ratio of the polyimide precursor resin composition was determined in the same manner as in Example 33.

[0166] <<Preparation of Polyimide Precursor Resin Composition>> Examples 33 to 49 and Comparative Examples 27 to 40 The PI precursor resin compositions of Examples 33 to 49 and Comparative Examples 27 to 40 were prepared by dissolving (A) polyimide precursor resin, (B) exposure radiation absorber, (C) photopolymerization initiator, (E) photopolymerizable compound, (F) hindered phenol compound, and (G) polymerization inhibitor in a mixed solvent (D) of γ-butyrolactone and DMSO (weight ratio 80:20) in the amounts shown in Tables 8 and 10. The amounts shown in Tables 8 and 10 are the parts by mass of each component per 100 parts by mass of component (A). The viscosity of the resulting solution was adjusted to approximately 15 poise by further adding a small amount of the mixed solvent, and the solution was filtered through a polyethylene filter with 0.2 μm pores to obtain a resin composition.

[0167] <<Production and Evaluation of Relief Pattern Films>> A sputtered Cu wafer substrate was prepared by sputtering a 200 nm thick Ti layer and a 400 nm thick Cu layer, in that order, onto a 6-inch wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a sputtering system (L-440S-FHL, Canon Anelva Corporation). The PI precursor resin composition was spin-coated onto the 6-inch silicon wafer using a spin coater (D-SPIN60A, SOKUDO Co., Ltd.) and dried on a hot plate at 100°C for 180 seconds to produce a coating film with a thickness of 5 μm±0.2 μm (D'). This spin-coated film was then exposed to light at 30 mJ / cm using a Prisma GHI S / N5503 projection exposure system (Ultratech Corporation) with a test pattern reticle having a 5 μm diameter circular recessed pattern and a gh-ray cut filter attached. 2 to 150 mJ / cm 2 Up to 10mJ / cm 2 The exposure was performed by varying the exposure dose in increments. Next, the coating film formed on the sputtered Cu wafer was spray-developed using cyclopentanone in a developing machine (D-SPIN636 model, manufactured by Dainippon Screen Co., Ltd.) and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. The development time for spray development was defined as 1.4 times the minimum time required for the resin composition in the unexposed areas to develop in the 5 μm spin-coated film.

[0168] <Evaluation of pattern taper shape> The cross section of the 5 μm diameter round-hole recessed pattern obtained above was milled using an FIB device (JIB-4000, manufactured by JEOL Ltd.), and the cross-sectional shape of the pattern was observed. The taper angle of the pattern relative to the substrate was determined by measuring the inclination at the midpoint of the taper. The pattern cross-sectional shape was rated as excellent (AA) if the taper angle was 70° to 80°, good (A) if it was 80° to 90°, and otherwise failed (D). Patterns with undercuts or bridging in the cross section were also considered failed. Patterns that failed the taper shape evaluation were not subjected to the maximum resolution evaluation and sensitivity tolerance evaluation described below.

[0169] <Evaluation of highest resolution> The diameter of the round-cut recessed mold was changed as described above, and the minimum value of the mask dimension of the obtained round-cut recessed relief pattern was taken as the maximum resolution (μm), and evaluation was performed according to the following criteria. A: Patterns less than 3.5 μm open B: Patterns between 3.5 μm and 4.5 μm are open C: Patterns between 4.5 μm and 6 μm are open D: Patterns smaller than 6 μm do not open Regarding the possibility of opening the round-cut recessed relief pattern, a pattern that met both of the following criteria (I) and (II) was judged to be acceptable. (I) The area of ​​the pattern opening is at least half the area of ​​the corresponding pattern mask opening. (II) The cross section of the pattern does not have a bottomed-out edge, and no undercut, swelling, or bridging occurs.

[0170] <Evaluation of sensitivity tolerance> The range of exposure dose at which openings of 5 μm diameter were observed in the circular recessed relief pattern obtained above was evaluated according to the following criteria. A: 5μm pattern is 30mJ / cm 2 Opening with the above exposure width B: 5μm pattern is 20mJ / cm 2 More than 30mJ / cm 2 Opening with exposure width less than C: 5 μm pattern is 10 mJ / cm 2 More than 20mJ / cm 2 Opening with exposure width less than D: 5 μm pattern opens or does not open at pinpoint

[0171] [Table 8]

[0172] [Table 9]

[0173] [Table 10]

[0174] [Table 11]

[0175] III. Examples 50 to 65 and Comparative Examples 41 to 44 <<Determination of composition ratio of polyimide precursor resin composition>> Examples 50 to 65 The composition ratio of the polyimide precursor resin composition was determined in the same manner as in Example 1.

[0176] <<Preparation of Polyimide Precursor Resin Composition>> Examples 50 to 65 and Comparative Examples 41 to 44 The PI precursor resin compositions of Examples 50-65 and Comparative Examples 41-44 were prepared by dissolving (A) polyimide precursor resin, (B) exposure radiation absorber, (C) photopolymerization initiator, (E) photopolymerizable compound, (F) hindered phenol compound, (G) polymerization inhibitor, and (H) nitrogen-containing heterocyclic rust inhibitor in a mixed solvent (D) of γ-butyrolactone and DMSO (80:20 weight ratio) in the amounts shown in the table. The amounts shown in the table represent parts by mass of each component relative to 100 parts by mass of component (A). The viscosity of the resulting solution was adjusted to approximately 40 poise by further adding a small amount of the mixed solvent, and the solution was filtered through a polyethylene filter with 0.2 μm pores to obtain a resin composition.

[0177] <<Production and Evaluation of Relief Pattern Films>> Using the obtained polyimide precursor resin composition, a relief pattern film was produced in the same manner as in Examples 1 to 32 and Comparative Examples 1 to 26.

[0178] <Evaluation of pattern taper shape> The tapered shape of the resulting relief pattern film was evaluated in the same manner as in Examples 1 to 32 and Comparative Examples 1 to 26.

[0179] <Evaluation of highest resolution> The resolution of the resulting relief pattern film was evaluated in the same manner as in Examples 1 to 32 and Comparative Examples 1 to 26.

[0180] <Evaluation of sensitivity tolerance> The sensitivity tolerance of the resulting relief pattern film was evaluated in the same manner as in Examples 1 to 32 and Comparative Examples 1 to 26.

[0181] <Evaluation of storage stability> After preparation of the photosensitive resin composition, the composition was stirred for three days at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%). This initial state was then considered to be the initial state, and the composition was then allowed to stand at room temperature for four weeks. The initial PI precursor resin composition was spin-coated onto a 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a spin coater (D-SPIN60A, SOKUDO Co., Ltd.) and dried on a hot plate at 100°C for 180 seconds to produce a pre-baked film with a thickness of 10.0 μm ± 0.2 μm (D'). This spin-coated film was then exposed to light at 30 mJ / cm using a Prisma GHI S / N5503 projection exposure system (Ultratech Co., Ltd.) equipped with a gh-ray cut filter and a test pattern reticle with a circular recessed 10 μm diameter pattern. 2 to 270 mJ / cm 2 Up to 20mJ / cm 2The exposure dose was varied in increments. The coating film formed on the wafer was then spray-developed using cyclopentanone in a developer (D-SPIN636, manufactured by Dainippon Screen Co., Ltd.) and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. The development time for spray development was defined as 1.4 times the minimum time required for the resin composition in the unexposed area to develop in the 10.0 μm spin-coated film. The film thickness of the relief pattern obtained in Example 50 at each exposure dose was measured. An example of the resulting sensitivity curve is shown in Figure 2. Here, the vertical axis represents the relative film thickness (normalized film thickness) calculated as (film thickness after exposure and development / film thickness before exposure) × 100 (%), and the horizontal axis represents the exposure dose. The exposure dose at the portion where the relative film thickness (normalized film thickness) is approximately 85% was defined as the sensitivity exposure dose (mJ / cm). 2 ) was defined as

[0182] The PI precursor resin composition was then left to stand at room temperature for 4 weeks, and spin-coated, exposed, and developed under the same conditions as for the initial PI precursor resin composition to produce a relief-patterned film. The normalized film thickness was calculated in the same manner. Storage stability was evaluated according to the following criteria, based on the change in relative film thickness over time at the sensitivity exposure dose determined by the initial PI precursor resin evaluation. For example, in Figure 2, the change in relative film thickness over time is 1.3%. A: The amount of change in relative film thickness over time is 0 to less than ±2%. B: The change in relative film thickness over time is ±2% or more. In Tables 13 and 15, values ​​for which the relative film thickness of the PI precursor resin composition after standing for 4 weeks was higher than that of the initial PI precursor resin composition are shown in the plus (+) column, and values ​​for which the relative film thickness was lower are shown in the minus (-) column.

[0183] [Table 12]

[0184] [Table 13]

[0185] [Table 14]

[0186] [Table 15]

[0187] IV. Examples 66 to 78 and Comparative Examples 45 to 47 <<Determination of composition ratio of polyimide precursor resin composition>> Examples 66 to 78 The composition ratio of the polyimide precursor resin composition was determined in the same manner as in Example 33.

[0188] <<Preparation of Polyimide Precursor Resin Composition>> Examples 66 to 78 and Comparative Examples 45 to 47 The PI precursor resin compositions of Examples 66-78 and Comparative Examples 45-47 were prepared by dissolving (A) polyimide precursor resin, (B) exposure radiation absorber, (C) photopolymerization initiator, (E) photopolymerizable compound, (F) hindered phenol compound, (G) polymerization inhibitor, and (H) nitrogen-containing heterocyclic rust inhibitor in a mixed solvent (D) of γ-butyrolactone and DMSO (80:20 weight ratio) in the amounts shown in the table. The amounts shown in the table represent parts by mass of each component per 100 parts by mass of component (A). The viscosity of the resulting solution was adjusted to approximately 15 poise by adding a small amount of the mixed solvent, and the solution was filtered through a polyethylene filter with 0.2 μm pores to obtain a resin composition. The symbols in the table refer to the respective components listed above.

[0189] <<Production and Evaluation of Relief Pattern Films>> Using the obtained polyimide precursor resin compositions, relief pattern films were produced in the same manner as in Examples 33 to 49 and Comparative Examples 27 to 40. <Evaluation of pattern taper shape> The tapered shape of the resulting relief pattern film was evaluated in the same manner as in Examples 33-49 and Comparative Examples 27-40.

[0190] <Evaluation of highest resolution> The resolution of the resulting relief pattern film was evaluated in the same manner as in Examples 33-49 and Comparative Examples 27-40.

[0191] <Evaluation of sensitivity tolerance> The sensitivity tolerance of the resulting relief pattern film was evaluated in the same manner as in Examples 33-49 and Comparative Examples 27-40.

[0192] <Evaluation of storage stability> After preparation of the photosensitive resin composition, the composition was stirred for three days at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%). This initial state was then considered to be the initial state, and the composition was then allowed to stand at room temperature for four weeks. The initial PI precursor resin composition was spin-coated onto a 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a spin coater (D-SPIN60A, SOKUDO Co., Ltd.) and dried on a hot plate at 100°C for 180 seconds to produce a pre-baked film with a thickness of 5.0 μm ± 0.2 μm (D'). This spin-coated film was then exposed to light at 30 mJ / cm using a Prisma GHI S / N5503 projection exposure system (Ultratech Co., Ltd.) equipped with a gh-ray cut filter and a test pattern reticle with a circular recessed 10 μm diameter pattern. 2 to 150 mJ / cm 2 Up to 10mJ / cm 2The exposure was performed by changing the exposure dose in increments. Next, the coating film formed on the wafer was spray-developed using cyclopentanone in a developing machine (D-SPIN636 model, manufactured by Dainippon Screen Co., Ltd.) and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. The development time for spray development was defined as 1.4 times the minimum time required for the resin composition in the unexposed area to develop in the 5.0 μm spin-coated film. In the obtained relief pattern, the relative film thickness (normalized film thickness) was calculated, and the exposure dose at the portion where the relative film thickness was approximately 80% was defined as the sensitivity exposure dose (mJ / cm). 2 ) was defined as

[0193] The PI precursor resin composition was then left to stand at room temperature for 4 weeks, and then spin-coated, exposed, and developed under the same conditions as for the initial PI precursor resin composition. The storage stability was evaluated according to the following criteria based on the change in relative film thickness over time at the sensitivity exposure dose. A: The amount of change in relative film thickness over time is 0 to less than ±2%. B: The change in relative film thickness over time is ±2% or more. In Tables 17 and 19, values ​​for which the relative film thickness of the PI precursor resin composition after standing for 4 weeks was higher than that of the initial PI precursor resin composition are shown in the plus (+) column, and values ​​for which the relative film thickness was lower are shown in the minus (-) column.

[0194] [Table 16]

[0195] [Table 17]

[0196] [Table 18]

[0197] [Table 19]

[0198] From the results in Tables 4 to 19, it is clear that the maximum resolution and sensitivity tolerance of the Examples are improved compared to the Comparative Examples by incorporating an exposure radiation absorber into the PI precursor resin composition. Furthermore, from Tables 12 to 19, the Examples containing both an exposure radiation absorber and a nitrogen-containing heterocyclic rust inhibitor were rated A in the storage stability test, demonstrating that the combination of the two specifically improves storage stability compared to compositions containing only one of the two. [Industrial Applicability]

[0199] According to the present disclosure, by adjusting the light transmittance of the resin composition as a whole using the light (i-line) absorption function of the exposure ray absorber, it is possible to provide a patterned cured film with excellent resolution and ease of handling, and a method for forming a cured relief pattern using the PI precursor resin composition. The present disclosure is suitable for use in the field of photosensitive materials useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. A method for producing a polyimide (PI) precursor resin composition for forming a relief pattern film, the PI precursor resin composition comprising a polyimide precursor resin, an exposure ray absorber, a photopolymerization initiator, and a solvent, the method comprising the steps of: selecting the PI precursor resin from resins having an absorbance parameter Xp of 0.001 to 0.20 for i-line, selecting the exposure ray absorber from materials having an absorbance parameter Xt of 0.01 to 0.05 for i-line, and selecting the photopolymerization initiator from materials having an absorbance parameter Xr of 0 to 0.04 for i-line; Based on the absorbance parameter Xp of the selected PI precursor resin, the absorbance parameter Xt of the selected exposure ray absorber, the absorbance parameter Xr of the selected photopolymerization initiator, and the assumed thickness D [μm] of a prebaked film obtained by coating the PI precursor resin composition and removing the solvent, the following formula: 0.7≦(Xp+Xt×α+Xr×β)×D≦2.2 determining the parts by mass α of the exposure ray absorber and the parts by mass β of the photopolymerization initiator to be added based on 100 parts by mass of the PI precursor resin so as to satisfy the following: preparing a PI precursor resin composition containing the determined PI precursor resin, the determined added weight part α of the exposure radiation absorber, the determined added weight part β of the photopolymerization initiator, and a solvent; Including, The method for producing a PI precursor resin composition, wherein the added mass part α is 0.1 mass parts or more and 20 mass parts or less per 100 mass parts of the PI precursor resin.

2. A method for producing a polyimide (PI) precursor resin composition for forming a relief pattern film, the PI precursor resin composition comprising a polyimide precursor resin, an exposure ray absorber, a photopolymerization initiator, and a solvent, the method comprising the steps of: selecting the PI precursor resin from resins having an absorbance parameter Xp of 0.001 to 0.20 for i-line, selecting the exposure ray absorber from materials having an absorbance parameter Xt of 0.01 to 0.05 for i-line, and selecting the photopolymerization initiator from materials having an absorbance parameter Xr of 0 to 0.04 for i-line; Based on the absorbance parameter Xp of the selected PI precursor resin, the absorbance parameter Xt of the selected exposure ray absorber, the absorbance parameter Xr of the selected photopolymerization initiator, and the assumed thickness D [μm] of a prebaked film obtained by coating the PI precursor resin composition and removing the solvent, the following formula: 0.7≦(Xp+Xt×α+Xr×β)×D≦2.2 determining the parts by mass α of the exposure ray absorber and the parts by mass β of the photopolymerization initiator to be added based on 100 parts by mass of the PI precursor resin so as to satisfy the following: preparing a PI precursor resin composition containing the determined PI precursor resin, the determined added weight part α of the exposure radiation absorber, the determined added weight part β of the photopolymerization initiator, and a solvent; Including, A method for producing a PI precursor resin composition, wherein the assumed thickness D is set to 1 μm or more and less than 7 μm, and the added mass parts α of the exposure ray absorber and the added mass parts β of the photopolymerization initiator are determined.

3. The PI precursor resin is represented by the following formula (1): 【Chemistry 1】 {In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, and n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom, a monovalent organic group represented by the following general formula (2), or a saturated aliphatic group having 1 to 4 carbon atoms. 【Chemistry 2】 {In the formula, R ３ , R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer from 2 to 10. The method according to claim 1 or 2, wherein the structural unit is represented by the following formula:

4. The manufacturing method according to claim 1 , wherein the assumed thickness D is set to 1 μm or more and less than 7 μm, and the added mass parts α of the exposure ray absorber and the added mass parts β of the photopolymerization initiator are determined.

5. The photopolymerization initiator is represented by the following general formula (5): 【Transformation 3】 {In the formula, R １６ , R １７ , and R １８ are each a monovalent organic group, and R １６ , and R １７ may be linked to each other to form a ring structure. The method according to any one of claims 1 to 4, wherein the compound has an oxime ester structure represented by the formula:

6. The method according to any one of claims 1 to 5, wherein the PI precursor resin composition further contains a nitrogen-containing heterocyclic rust inhibitor.

7. 7. The method according to claim 1, wherein the exposure ray absorber is a compound having a 1,2-naphthoquinone diazide structure.

8. The method according to any one of claims 1 to 7, wherein the PI precursor resin composition further contains a photopolymerizable compound.

9. Y in the formula (1) １ is expressed by the following formula (3): 【Chemistry 4】 {In the formula, R ６ ~R １３ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ６ ~R １３ At least one of is a methyl group, a trifluoromethyl group, or a methoxy group. The method according to claim 3, wherein the divalent organic group is represented by the formula:

10. Y in the formula (1) １ is expressed by the following formula (4): 【Transformation 5】 {In the formula, R １４ , R １５ are each independently a methyl group, a trifluoromethyl group, or a methoxy group. The method according to claim 3, wherein the divalent organic group is represented by the formula:

11. The exposure ray absorber is represented by the following general formulas (6) to (10): 【Transformation 6】 {In formula (6), X １ and X ２ each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms; X ３ and X ４ each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms; r1, r2, r3, and r4 each independently represent an integer of 0 to 5; at least one of r3 and r4 is an integer of 1 to 5; r1+r3=5, and r2+r4=5.} 【Transformation 7】 In formula (7), Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ５ , X ６ , X ７ and X ８ each independently represent a monovalent organic group having 1 to 30 carbon atoms; r6 is an integer of 0 or 1; r5, r7, r8, and r9 are each independently an integer of 0 to 3; r10, r11, r12, and r13 are each independently an integer of 0 to 2, and at least one of r10, r11, r12, and r13 is 1 or 2.} 【Transformation 8】 {In formula (8), r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, r14 × r15 Ls each independently represent a monovalent organic group having 1 to 20 carbon atoms, r15 Ts each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and r15 Ss each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.} 【Chemistry 9】 {In formula (9), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group.} 【Chemistry 10】 In formula (10), r17, r18, r19, and r20 each independently represent an integer of 0 to 2, and at least one of r17, r18, r19, and r20 is 1 or 2; X １０ ~X １９ each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y １ ~Y ３ each independently represents a single bond, —O—, —S—, —SO—, or —SO ２ -, -CO-, -CO ２ represents at least one divalent group selected from the group consisting of -, cyclopentylidene, cyclohexylidene, phenylene, and divalent organic groups having 1 to 20 carbon atoms.} The method according to any one of claims 1 to 10, wherein the hydroxy compound is 1,2-naphthoquinonediazide-4-sulfonic acid ester and / or 1,2-naphthoquinonediazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of:

12. 12. The method according to claim 11, wherein the exposure ray absorber is a 1,2-naphthoquinonediazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of the above formulas (6) to (10).

13. The method according to claim 7, 11, or 12, wherein the esterification rate of the exposure ray absorber is 80% or more.

14. The hydroxy compound represented by the general formula (6) is represented by the following general formula (11): 【Chemistry 11】 In formula (11), each r20 is independently an integer of 0 to 2, and X ９ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The method according to claim 11, wherein the compound is represented by the formula:

15. 1. A method for producing a relief pattern film, the method comprising: A step of producing a PI precursor resin composition containing a PI precursor resin, an exposure ray absorber, a photopolymerization initiator, and a solvent by the method according to any one of claims 1 to 14; a coating step of obtaining a coating film of the PI precursor resin composition; a drying step of removing the solvent from the coating film to obtain a photosensitive resin layer having a thickness of D′ [μm]; an exposure step of exposing the photosensitive resin layer to i-rays; a development step of developing the photosensitive resin layer after the exposure to obtain a relief pattern film; A method for producing a relief pattern film, comprising:

16. After the solvent is removed, the coating film has a thickness of D' [μm]. 0.7≦(Xp+Xt×α+Xr×β)×D'≦2.2 The method for producing a relief pattern film according to claim 15,

17. A PI precursor resin composition for forming a relief pattern film, comprising: a PI precursor resin; an exposure ray absorber in an amount of α parts by mass, a photopolymerization initiator in an amount of β parts by mass, based on 100 parts by mass of the PI precursor resin; and a solvent, an absorbance parameter Xp of the PI precursor resin for i-line; an absorbance parameter Xt of the exposure ray absorber for i-line; an absorbance parameter Xr of the photopolymerization initiator for i-line; parts by weight α of the exposure radiation absorber; The relationship with the mass parts β of the photopolymerization initiator is 0.7≦(Xp+Xt×α+Xr×β)×10≦2.2 0.001≦Xp≦0.20 0.01≦Xt≦0.05 0≦Xr≦0.04 and The photopolymerization initiator is represented by the following general formula (5): 【Chemistry 12】 {In the formula, R １６ , R １７ , and R １８ are each a monovalent organic group, and R １６ , and R １７ may be linked to each other to form a ring structure. and has an oxime ester structure represented by the formula: The PI precursor resin composition, wherein the mass parts α is 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the PI precursor resin.

18. A polyimide (PI) precursor resin composition for forming a relief pattern film, comprising: a polyimide precursor resin; an exposure ray absorber in an amount of α parts by mass, a photopolymerization initiator in an amount of β parts by mass, based on 100 parts by mass of the PI precursor resin; and a solvent, an absorbance parameter Xp of the PI precursor resin for i-line; an absorbance parameter Xt of the exposure ray absorber for i-line; an absorbance parameter Xr of the photopolymerization initiator for i-line; parts by weight α of the exposure radiation absorber; The relationship with the mass parts β of the photopolymerization initiator is 0.7≦(Xp+Xt×α+Xr×β)×5≦2.2 0.001≦Xp≦0.20 0.01≦Xt≦0.05 0≦Xr≦0.04 and The photopolymerization initiator is represented by the following general formula (5): 【Chemistry 13】 {In the formula, R １６ , R １７ , and R １８ are each a monovalent organic group, and R １６ , and R １７ may be linked to each other to form a ring structure. A PI precursor resin composition having an oxime ester structure represented by the following formula:

19. The PI precursor resin is represented by the following formula (1): 【Chemistry 14】 {In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, and n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom, a monovalent organic group represented by the following general formula (2), or a saturated aliphatic group having 1 to 4 carbon atoms. 【Chemistry 15】 {In the formula, R ３ , R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer from 2 to 10. The PI precursor resin composition according to claim 17 or 18, having a structural unit represented by the following formula:

20. The PI precursor resin composition according to any one of claims 17 to 19, further comprising a nitrogen-containing heterocyclic rust inhibitor.

21. The PI precursor resin composition according to any one of claims 17 to 20, wherein the exposure ray absorber is a compound having a 1,2-naphthoquinone diazide structure.

22. The PI precursor resin composition according to any one of claims 17 to 21, further comprising a photopolymerizable compound.

23. Y in the formula (1) １ is expressed by the following formula (3): 【Chemistry 16】 {In the formula, R ６ ~R １３ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ６ ~R １３ At least one of is a methyl group, a trifluoromethyl group, or a methoxy group. The PI precursor resin composition according to claim 19, wherein the divalent organic group is represented by the following formula:

24. Y in the formula (1) １ is expressed by the following formula (4): 【Chemistry 17】 {In the formula, R １４ , R １５ are each independently a methyl group, a trifluoromethyl group, or a methoxy group. The PI precursor resin composition according to claim 19, wherein the divalent organic group is represented by the following formula:

25. The exposure ray absorber is represented by the following general formulas (6) to (10): [Chemistry 18] {In formula (6), X １ and X ２ each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms; X ３ and X ４ each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms; r1, r2, r3, and r4 each independently represent an integer of 0 to 5; at least one of r3 and r4 is an integer of 1 to 5; r1+r3=5, and r2+r4=5.} 【Chemistry 19】 In formula (7), Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ５ , X ６ , X ７ and X ８ each independently represent a monovalent organic group having 1 to 30 carbon atoms; r6 is an integer of 0 or 1; r5, r7, r8, and r9 are each independently an integer of 0 to 3; r10, r11, r12, and r13 are each independently an integer of 0 to 2, and at least one of r10, r11, r12, and r13 is 1 or 2.} 【Chemistry 20】 {In formula (8), r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, r14 × r15 Ls each independently represent a monovalent organic group having 1 to 20 carbon atoms, r15 Ts each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and r15 Ss each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.} 【Chemistry 21】 {In formula (9), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group.} 【Chemistry 22】 In formula (10), r17, r18, r19, and r20 each independently represent an integer of 0 to 2, and at least one of r17, r18, r19, and r20 is 1 or 2; X １０ ~X １９ each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y １ ~Y ３ each independently represents a single bond, —O—, —S—, —SO—, or —SO ２ -, -CO-, -CO ２ represents at least one divalent group selected from the group consisting of -, cyclopentylidene, cyclohexylidene, phenylene, and divalent organic groups having 1 to 20 carbon atoms.} The PI precursor resin composition according to any one of claims 17 to 24, wherein the PI precursor resin composition is a 1,2-naphthoquinonediazide-4-sulfonic acid ester and / or a 1,2-naphthoquinonediazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of:

26. The PI precursor resin composition according to claim 25, wherein the exposure ray absorber is a 1,2-naphthoquinonediazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of the above formulas (6) to (10).

27. 27. The PI precursor resin composition according to claim 21, wherein the esterification rate of the exposure ray absorber is 80% or more.

28. The hydroxy compound represented by the general formula (6) is represented by the following general formula (11): 【Chemistry 23】 In formula (11), each r16 is independently an integer of 0 to 2, and X ９ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The PI precursor resin composition according to claim 25, represented by the formula:

29. A cured film of the PI precursor resin composition according to any one of claims 17 to 28.

30. A pre-baked film for forming a relief pattern film, having a thickness D' [μm] of 1≦D'≦20, the prebaked film contains a polyimide (PI) precursor resin, α parts by mass of an exposure ray absorber relative to 100 parts by mass of the PI precursor resin, and β parts by mass of a photopolymerization initiator relative to 100 parts by mass of the PI precursor resin; The PI precursor resin has an absorbance parameter Xp for i-line in the range of 0.001≦Xp≦0.20, the exposure ray absorber has an absorbance parameter Xt for i-rays in the range of 0.01≦Xt≦0.05; The photopolymerization initiator has an absorbance parameter Xr for i-line in the range of 0≦Xr≦0.04, The following formula: 0.7≦(Xp+Xt×α+Xr×β)×D'≦2.2 Fulfilling The photopolymerization initiator is represented by the following general formula (5): 【Chemistry 24】 {In the formula, R １６ , R １７ , and R １８ are each a monovalent organic group, and R １６ , and R １７ may be linked to each other to form a ring structure. and has an oxime ester structure represented by the formula: The α parts by mass is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the PI precursor resin.

31. A pre-baked film for forming a relief pattern film, having a thickness D' [μm] of 1≦D'≦20, the prebaked film contains a polyimide (PI) precursor resin, α parts by mass of an exposure ray absorber relative to 100 parts by mass of the PI precursor resin, and β parts by mass of a photopolymerization initiator relative to 100 parts by mass of the PI precursor resin; The PI precursor resin has an absorbance parameter Xp for i-line in the range of 0.001≦Xp≦0.20, the exposure ray absorber has an absorbance parameter Xt for i-rays in the range of 0.01≦Xt≦0.05; The photopolymerization initiator has an absorbance parameter Xr for i-line in the range of 0≦Xr≦0.04, The following formula: 0.7≦(Xp+Xt×α+Xr×β)×D'≦2.2 Fulfilling The photopolymerization initiator is represented by the following general formula (5): 【Chemistry 25】 {In the formula, R １６ , R １７ , and R １８ are each a monovalent organic group, and R １６ , and R １７ may be linked to each other to form a ring structure. and has an oxime ester structure represented by the formula: The prebaked film has a thickness D' [μm] of 1≦D'<7.

32. The PI precursor resin is represented by the following formula (1): 【Chemistry 26】 {In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, and n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom, a monovalent organic group represented by the following general formula (2), or a saturated aliphatic group having 1 to 4 carbon atoms. 【Chemistry 27】 {In the formula, R ３ , R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer from 2 to 10. The prebaked film according to claim 30 or 31, having a structural unit represented by the formula:

33. The prebaked film according to claim 30, wherein the thickness D' [µm] of the prebaked film is 1≦D'<7.

34. The prebaked film according to any one of claims 30 to 33, further comprising a nitrogen-containing heterocyclic rust inhibitor.

35. The prebaked film according to any one of claims 30 to 34, wherein the exposure ray absorber is a compound having a 1,2-naphthoquinone diazide structure.

36. The prebaked film according to any one of claims 30 to 35, further comprising a photopolymerizable compound.

37. Y in the formula (1) １ is expressed by the following formula (3): 【Chemistry 28】 {In the formula, R ６ ~R １３ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ６ ~R １３ At least one of is a methyl group, a trifluoromethyl group, or a methoxy group. The prebaked film according to claim 32, wherein the divalent organic group is represented by the following formula:

38. Y in the formula (1) １ is expressed by the following formula (4): 【Chemistry 29】 {In the formula, R １４ , R １５ are each independently a methyl group, a trifluoromethyl group, or a methoxy group. The prebaked film according to claim 32, wherein the divalent organic group is represented by the following formula:

39. The exposure ray absorber is represented by the following general formulas (6) to (10): 【Transformation 30】 {In formula (6), X １ and X ２ each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms; X ３ and X ４ each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms; r1, r2, r3, and r4 each independently represent an integer of 0 to 5; at least one of r3 and r4 is an integer of 1 to 5; r1+r3=5, and r2+r4=5. 【Chemistry 31】 In formula (7), Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ５ , X ６ , X ７ and X ８ each independently represent a monovalent organic group having 1 to 30 carbon atoms; r6 is an integer of 0 or 1; r5, r7, r8, and r9 are each independently an integer of 0 to 3; r10, r11, r12, and r13 are each independently an integer of 0 to 2, and at least one of r10, r11, r12, and r13 is 1 or 2.} 【Chemistry 32】 {In formula (8), r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, r14 × r15 Ls each independently represent a monovalent organic group having 1 to 20 carbon atoms, r15 Ts each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and r15 Ss each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.} 【Transformation 33】 {In formula (9), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group.} 【Transformation 34】 In formula (10), r17, r18, r19, and r20 each independently represent an integer of 0 to 2, and at least one of r17, r18, r19, and r20 is 1 or 2; X １０ ~X １９ each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y １ ~Y ３ each independently represents a single bond, —O—, —S—, —SO—, or —SO ２ -, -CO-, -CO ２ represents at least one divalent group selected from the group consisting of -, cyclopentylidene, cyclohexylidene, phenylene, and divalent organic groups having 1 to 20 carbon atoms.} The prebaked film according to any one of claims 30 to 38, wherein the prebaked film is a 1,2-naphthoquinone diazide-4-sulfonic acid ester and / or a 1,2-naphthoquinone diazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of:

40. The prebaked film according to claim 39, wherein the exposure ray absorber is a 1,2-naphthoquinonediazide-5-sulfonic acid ester of at least one hydroxy compound selected from the group consisting of the above formulas (6) to (10).

41. 41. The prebaked film according to claim 35, wherein the esterification rate of the exposure ray absorber is 80% or more.

42. The hydroxy compound represented by the general formula (6) is represented by the following general formula (11): 【Chemistry 35】 In formula (11), each r20 is independently an integer of 0 to 2, and X ９ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The pre-baked film according to claim 39, wherein the pre-baked film is represented by the formula:

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