Photosensitive resin composition and method for producing cured relief pattern

Abstract

To provide a negative photosensitive resin composition that exhibits higher resolution in forming a relief pattern on copper, hardly forms voids on copper during high-temperature storage, and exhibits an excellent elongation even when being stored under high temperature and high humidity.SOLUTION: The negative photosensitive resin composition comprises: a polyimide precursor comprising a structural unit represented by the general formula (I-1); a nitrogen-containing compound of a specific structure; and a photoinitiator. In the formula, at least one of R1 and R2 is a group including two or more polymerizable groups selected from the group consisting of acid polymerizable groups, base polymerizable groups and radical polymerizable groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a method for producing a cured relief pattern from the photosensitive resin composition, and the like. [Background technology]

[0002] Polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used conventionally as insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, interlayer insulating films, etc. Among these polyimide resins, those provided in the form of photosensitive polyimide precursors can easily form heat-resistant relief pattern films by applying the precursor, exposing it to light, developing it, and subjecting it to a thermal imidization treatment that involves curing. This allows for a significant reduction in the number of processes compared to conventional non-photosensitive polyimide resins.

[0003] Meanwhile, in recent years, the methods for mounting semiconductor devices on printed wiring boards have been changing in order to improve integration density and computing performance, as well as to reduce chip size. Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures in which a polyimide coating directly contacts solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable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. When forming such bump structures, the polyimide coating must have high heat resistance and chemical resistance.

[0004] Furthermore, as semiconductor devices become increasingly miniaturized, the problem of wiring delays has become apparent. As a means of improving the wiring resistance of semiconductor devices, the gold or aluminum wiring that has been used until now has been replaced by copper or copper alloy wiring, which has lower resistance. Another method that has been adopted is to prevent wiring delays by improving the insulation between wiring. In recent years, semiconductor devices are often constructed using low-dielectric-constant materials as highly insulating materials. However, low-dielectric-constant materials tend to be brittle and easily broken. In semiconductor devices constructed using low-dielectric-constant materials, there is a problem that when the semiconductor chip is mounted on a substrate after a solder reflow process, for example, the low-dielectric-constant material portion is destroyed due to contraction caused by temperature changes.

[0005] As a means for solving this problem, for example, Patent Document 1 discloses the use of a photosensitive polyimide precursor in which a portion of the photosensitive group having a terminal ethylene bond and 4 or more carbon atoms is substituted with a hydrocarbon group having 1 to 3 carbon atoms.

[0006] Incidentally, Patent Document 2 discloses a thermal base generator that can be incorporated into a photosensitive resin composition.

[0007] Patent Document 3 proposes flip-chip mounting, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped over and mounted directly on a printed circuit board. Chemical resistance is required for the resin layer during the metal rewiring layer formation process in flip-chip mounting, but with conventional resin compositions, the film thickness changes after immersion in a chemical solution, making it difficult to form a pattern as designed.

[0008] Patent Document 4 proposes a semiconductor chip packaging technology called fan-out wafer-level packaging (FOWLP), in which a preprocessed wafer is diced to produce individual chips, the individual chips are reassembled on a support, sealed with a mold resin, and a rewiring layer is formed after the support is peeled off. As package packaging technologies become more diverse, the types of support materials are becoming more diverse and the rewiring layers are becoming more multi-layered. Therefore, if the desired resolution cannot be obtained when stacking the rewiring layers, the layers are peeled off using a chemical solution and then stacked again. However, the chemical solution can damage the underlying film, reducing the film thickness and reducing the adhesion of the rewiring layer to the copper pillars.

[0009] Patent Document 5 also describes a fanout semiconductor device. In the manufacturing process of a fanout semiconductor device, a photosensitive polyimide resin thermally cured at the lowest possible temperature is insufficiently imidized, resulting in insufficient film properties as an interlayer insulating film. On the other hand, when a fanout semiconductor device is manufactured through a thermal curing process to completely imidize the photosensitive polyimide resin, the yield of the semiconductor device deteriorates due to thermal damage in the thermal curing process. Furthermore, in the above manufacturing process, the cured relief pattern obtained using a photosensitive resin composition leaves room for improvement in terms of suppression of Cu voids, adhesion between the interlayer insulating film in the rewiring layer and the encapsulant, imidization rate, chemical resistance, resolution on the mold resin, and the like. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 6-80776 [Patent Document 2] International Publication No. 2017 / 038598 [Patent Document 3] Japanese Patent Application Laid-Open No. 2001-338947 [Patent Document 4] Japanese Patent Application Laid-Open No. 2005-167191 [Patent Document 5] Japanese Patent Application Laid-Open No. 2011-129767 Summary of the Invention [Problem to be solved by the invention]

[0011] However, the polyimide precursor described in Patent Document 1 has a problem in that the resolution is insufficient when forming a relief pattern on copper. Furthermore, semiconductor devices having a polyimide layer obtained from the polyimide precursor described in Patent Document 1 have a problem in that voids are formed on the copper, which is thought to be caused by copper migration when stored at high temperatures. Furthermore, polyimide films obtained from the precursor described in Patent Document 1 have a problem in that the elongation of the film decreases when stored at high temperatures and high humidity.

[0012] Therefore, an object of the present invention is to provide a negative-type photosensitive resin composition that exhibits high resolution when a relief pattern is formed on copper, is less likely to form voids on copper when stored at high temperatures, and exhibits excellent elongation even when stored under high-temperature and high-humidity conditions, and a method for producing a cured relief pattern using the negative-type photosensitive resin composition. [Means for solving the problem]

[0013] The present inventors have found that the above-mentioned problems can be solved by combining a polyimide precursor having a side chain with a specific structure with a photopolymerization initiator, and have thus completed the present invention. That is, a first aspect of the present invention is as follows. [1] (A) the following general formula (I-1): [ka] In formula (I-1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R1 and R2 is a group containing two or more polymerizable groups selected from the group consisting of acid-polymerizable groups, base-polymerizable groups, and radical-polymerizable groups. 100 parts by mass of a polyimide precursor containing a structural unit represented by the formula: (B) Photopolymerization initiator: 0.1 parts by mass to 20 parts by mass A negative photosensitive resin composition comprising: [2] In the polyimide precursor (A), at least one of R1 and R2 is represented by the following general formula (I-R1): [ka] {In formula (I-R1), R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, Z is a trivalent or tetravalent organic group having 1 to 10 carbon atoms, and when Z is trivalent, m1 is 2, and when Z is tetravalent, m1 is 3.} Item 2. The negative photosensitive resin composition according to item 1, comprising a group represented by the formula: [3] Item 3. The negative photosensitive resin composition according to item 2, wherein the proportion of monovalent organic groups represented by general formula (I-R1) relative to all of R1 and R2 in the polyimide precursor (A) is 50 mol % or more. [4] In the polyimide precursor (A), at least one of R1 and R2 is represented by the following general formula (I-R2) or (I-R3): [ka] In formula (I-R2), R6 and R7 each independently represent a hydrogen atom or a methyl group. [ka] {In formula (I-R3), R8, R9, and R 10 are each independently a hydrogen atom or a methyl group. Item 2. The negative photosensitive resin composition according to item 1, comprising a group represented by the formula: [5] Item 5. The negative photosensitive resin composition according to Item 4, wherein the total proportion of the monovalent organic groups represented by the general formulas (I-R2) and (I-R3) relative to all of R1 and R2 in the polyimide precursor (A) is 50 mol % or more. [6] The structural unit represented by the general formula (I-1) in the polyimide precursor (A) is represented by the following general formula (I-1-1): [ka] In formula (I-1-1), R1 and R2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R1 and R2 is a group containing two or more polymerizable groups selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group. 6. The negative photosensitive resin composition according to any one of items 1 to 5, comprising a structural unit represented by the following formula: [7] In the polyimide precursor (A), at least one of R1 and R2 is represented by the following general formula (I-R1): [ka] {In formula (I-R1), R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, Z is a trivalent or tetravalent organic group having 1 to 10 carbon atoms, and when Z is trivalent, m1 is 2, and when Z is tetravalent, m1 is 3.} Item 7. The negative photosensitive resin composition according to item 6, comprising a group represented by the formula: [8] 8. The negative photosensitive resin composition according to item 7, wherein the proportion of monovalent organic groups represented by general formula (I-R1) to all of R1 and R2 in the polyimide precursor (A) is 50 mol % or more. [9] In the polyimide precursor (A), at least one of R1 and R2 is represented by the following general formula (I-R2) or (I-R3): [ka] In formula (I-R2), R6 and R7 each independently represent a hydrogen atom or a methyl group. [ka] {In formula (I-R3), R8, R9, and R 10 are each independently a hydrogen atom or a methyl group. Item 7. The negative photosensitive resin composition according to item 6, comprising a group represented by the formula:

[10] Item 10. The negative photosensitive resin composition according to Item 9, wherein the total proportion of the monovalent organic groups represented by the general formulas (I-R2) and (I-R3) relative to all of R1 and R2 in the polyimide precursor (A) is 50 mol % or more.

[11] (A) The structural unit represented by the above general formula (I-1) in the polyimide precursor is represented by the following general formula (I-1-2): [ka] In formula (I-1-2), R1 and R2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R1 and R2 is a group containing two or more polymerizable groups selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group. 6. The negative photosensitive resin composition according to any one of items 1 to 5, comprising a structural unit represented by the following formula:

[12] In the polyimide precursor (A), at least one of R1 and R2 is represented by the following general formula (I-R1): [ka] {In formula (I-R1), R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, Z is a trivalent or tetravalent organic group having 1 to 10 carbon atoms, and when Z is trivalent, m1 is 2, and when Z is tetravalent, m1 is 3.} Item 12. The negative photosensitive resin composition according to item 11, comprising a group represented by:

[13] Item 13. The negative photosensitive resin composition according to item 12, wherein the proportion of monovalent organic groups represented by general formula (I-R1) relative to all of R1 and R2 in the polyimide precursor (A) is 50 mol % or more.

[14] In the polyimide precursor (A), at least one of R1 and R2 is represented by the following general formula (I-R2) or (I-R3): [ka] In formula (I-R2), R6 and R7 each independently represent a hydrogen atom or a methyl group. [ka] {In formula (I-R3), R8, R9, and R 10 are each independently a hydrogen atom or a methyl group. Item 12. The negative photosensitive resin composition according to item 11, comprising a group represented by:

[15] Item 15. The negative photosensitive resin composition according to Item 14, wherein the total proportion of monovalent organic groups represented by the general formulas (I-R2) and (I-R3) relative to all of R1 and R2 in the polyimide precursor (A) is 50 mol % or more.

[16] (A) The structural unit represented by the general formula (I-1) in the polyimide precursor is represented by the following general formula (I-1-3): [ka] In formula (I-1-3), R1 and R2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R1 and R2 is a group containing two or more polymerizable groups selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group. 6. The negative photosensitive resin composition according to any one of items 1 to 5, comprising a structural unit represented by the following formula:

[17] In the polyimide precursor (A), at least one of R1 and R2 is represented by the following general formula (I-R1): [ka] {In formula (I-R1), R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, Z is a trivalent or tetravalent organic group having 1 to 10 carbon atoms, and when Z is trivalent, m1 is 2, and when Z is tetravalent, m1 is 3.} Item 17. The negative photosensitive resin composition according to item 16, comprising a group represented by the formula:

[18] Item 18. The negative photosensitive resin composition according to Item 17, wherein the proportion of monovalent organic groups represented by the general formula (I-R1) to all of R1 and R2 in the polyimide precursor (A) is 50 mol % or more.

[19] In the polyimide precursor (A), at least one of R1 and R2 is represented by the following general formula (I-R2) or (I-R3): [ka] In formula (I-R2), R6 and R7 each independently represent a hydrogen atom or a methyl group. [ka] {In formula (I-R3), R8, R9, and R 10 are each independently a hydrogen atom or a methyl group. Item 17. The negative photosensitive resin composition according to item 16, comprising a group represented by the formula:

[20] Item 20. The negative photosensitive resin composition according to Item 19, wherein the total proportion of the monovalent organic groups represented by the general formulas (I-R2) and (I-R3) relative to all of R1 and R2 in the polyimide precursor (A) is 50 mol % or more. [twenty one] 21. The negative photosensitive resin composition according to any one of items 1 to 20, further comprising 0.01 to 5 parts by mass of a rust inhibitor (C). [twenty two] 22. The negative photosensitive resin composition according to any one of items 1 to 21, further comprising 0.5 to 20 parts by mass of (D) a thermal base generator. [twenty three] 23. A method for producing a polyimide, comprising a step of curing the negative photosensitive resin composition according to any one of items 1 to 22 to form a polyimide. [twenty four] The following steps: (1) A step of applying the negative photosensitive resin composition according to any one of items 1 to 22 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising:

[0014] The second aspect of the present invention is as follows. [twenty five] (A) the following general formula (II-1): [ka] In formula (II-1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R1 and R2 is a group represented by the following general formula (II-2): [ka] (In formula (II-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.) and a group represented by the following general formula (II-3): [ka] In formula (II-3), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R6 and R7 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R6 and R7 is a group represented by the following general formula (II-4): [ka] (In formula (II-4), Z is a monovalent organic group containing a base having at least one nitrogen atom, or a base protected with a protecting group that can be removed by an acid, a base, or heat.) It is a group represented by the following formula: 100 parts by mass of a polyimide precursor having a structure represented by the formula: (B) Photopolymerization initiator: 0.1 to 20 parts by mass A photosensitive resin composition comprising:

[26] Item 26. The photosensitive resin composition according to item 25, wherein Z in general formula (II-4) has an aromatic tertiary amine structure in which one or more aromatic rings are directly bonded to a nitrogen atom.

[27] Item 26. The photosensitive resin composition according to item 25, wherein Z in the general formula (II-4) is a monovalent organic group containing an amine protected with a tert-butoxycarbonyl (boc) group or a 9-fluorenylmethyloxycarbonyl (Fmoc) group.

[28] Item 26. The photosensitive resin composition according to item 25, wherein Z in the general formula (II-4) is a monovalent organic group containing a base protected by a tert-butoxycarbonyl (boc) group.

[29] Item 26. The photosensitive resin composition according to item 25, wherein Z in the general formula (II-4) is a monovalent organic group containing an amine protected with a 9-fluorenylmethyloxycarbonyl (Fmoc) group.

[30] 30. The photosensitive resin composition according to any one of items 25 to 29, wherein the proportion of the monovalent organic group represented by the general formula (II-4) relative to all of R1, R2, R6, and R7 in the general formulas (II-1) and (II-3) of the polyimide precursor (A) is 1 mol % to 50 mol %.

[31] 31. The photosensitive resin composition according to any one of items 25 to 30, wherein the proportion of the monovalent organic group represented by the general formula (II-4) relative to all of R1, R2, R6, and R7 in the general formulas (II-1) and (II-3) of the polyimide precursor (A) is 2.5 mol % to 25 mol %.

[32] The polyimide precursor (A) is a polyimide precursor represented by the following general formula (II-5): [ka] In formula (II-5), n2 is an integer of 2 to 150, R6 and R7 are each independently a hydrogen atom or a monovalent organic group, and at least one of R6 and R7 is a group represented by the following general formula (II-4): [ka] (In formula (II-4), Z is a monovalent organic group containing a base having at least one nitrogen atom, or a base protected with a protecting group that can be removed by an acid, a base, or heat.) It is a group represented by the following formula: 32. The photosensitive resin composition according to any one of items 25 to 31, comprising a resin having a structural unit represented by the following formula:

[33] The (A) polyimide precursor is represented by the following general formula (II-6): [ka] In formula (II-6), n3 represents an integer of 2 to 150, R6 and R7 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R6 and R7 represents a group represented by the following general formula (II-4): [ka] (In formula (II-4), Z is a monovalent organic group containing a base having at least one nitrogen atom, or a base protected with a protecting group that can be removed by an acid, a base, or heat.) It is a group represented by the following formula: 33. The photosensitive resin composition according to any one of items 25 to 32, comprising a resin having a structural unit represented by the following formula:

[34] 34. The photosensitive resin composition according to any one of items 25 to 33, wherein the photosensitive resin composition is a negative type.

[35] The following steps: (1) A step of applying the photosensitive resin composition according to any one of items 25 to 34 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; 2. A method for producing a cured relief pattern comprising:

[36] 35. A method for producing a polyimide, comprising a step of converting the photosensitive resin composition according to any one of items 25 to 34 into a polyimide.

[0015] The third aspect of the present invention is as follows.

[37] A cured film containing polyimide, When IR spectrum was measured using the ATR (Attenuated Total Reflection) method, -1 Nearby peaks and 1720cm -1 Ratio of peaks around (2950cm -1 Nearby peak: 1720cm -1 A cured film characterized in that the peak (peak near the peak) is 0.05 to 0.35.

[38] Item 38. The cured film according to item 37, wherein the ratio of the peaks is 0.1 to 0.25.

[39] Furthermore, 1380cm -1 Nearby peaks and 1500cm -1 Ratio of peaks around (1380cm -1 Nearby peaks: 1500cm -1 Item 39. The cured film according to item 37 or 38, wherein the peak (peak near the peak) is 0.1 to 2.1.

[40] Item 39. The cured film according to any one of items 37 to 39, wherein the 5% weight loss temperature of the cured film is 280°C or higher and 350°C or lower.

[41] 41. The cured film according to any one of items 37 to 40, wherein the polyimide comprises a structure represented by the following general formula (III-A): [ka] {In general formula (III-A), 1 is a tetravalent organic group, and Y 1 is a divalent organic group, and m is an integer of 1 or more.

[42] The X of the polyimide 1 but The following formulas (III-C1) to (III-C3): [ka] [ka] [ka] or The Y of the polyimide 1 but The following formulas (III-D1) to (III-D3): [ka] (In general formula (III-D1), R 10 ~R 13 are hydrogen atoms or C1 to C4 monovalent aliphatic groups, and may be different from each other or the same.) [ka] [ka] (In general formula (III-D3), R 14 ~R 21 are hydrogen atoms, halogen atoms, or C1 to C4 monovalent organic groups, and may be different from each other or the same.) Item 42. The cured film according to item 41, comprising at least one structural skeleton selected from:

[43] The X of the polyimide 1 Item 43. The cured film according to item 42, comprising the structural skeleton of formula (III-C1).

[44] The X of the polyimide 1 Item 44. The cured film according to item 42 or 43, comprising the structural skeleton of formula (III-C2).

[45] The X of the polyimide 1 45. The cured film according to any one of items 42 to 44, comprising the structural skeleton of formula (III-C3).

[46] The Y of the polyimide 1 46. ​​The cured film according to any one of items 42 to 45, comprising the structural skeleton of formula (III-D1).

[47] The Y of the polyimide 1 47. The cured film according to any one of items 42 to 46, comprising the structural skeleton of formula (III-D2).

[48] The Y of the polyimide 1 48. The cured film according to any one of items 42 to 47, comprising the structural skeleton of formula (III-D3).

[49] The X of the polyimide 1 contains the structural skeleton of the formula (III-C1), and the Y 1 49. The cured film according to any one of items 42 to 48, comprising the structural skeleton of formula (III-D2).

[50] The X of the polyimide 1 contains the structural skeleton of the formula (III-C2), and the Y 1 49. The cured film according to any one of items 42 to 49, comprising the structural skeleton of formula (III-D2).

[51] The X of the polyimide 1 contains the structural skeleton of (III-C3), and the Y of the polyimide 1 The cured film according to any one of items 42 to 50, comprising the structural skeleton of (III-D2).

[52] The X of the polyimide 1 contains the structural skeleton of the formula (III-C1), and the Y 1 52. The cured film according to any one of items 42 to 51, comprising the structural skeleton of formula (III-D3).

[53] The X of the polyimide 1 contains the structural skeleton of the formula (III-C2), and the Y 1 53. The cured film according to any one of items 42 to 52, comprising the structural skeleton of formula (III-D3).

[54] The X of the polyimide 1 contains the structural skeleton of the formula (III-C3), and the Y 153. The cured film according to any one of items 42 to 52, comprising the structural skeleton of formula (III-D3).

[55] the polyimide includes a first polyimide and a second polyimide; The X of the first polyimide 1 contains the structural skeleton of the formula (III-C1), and the Y 1 contains the structural skeleton of formula (III-D2), The X of the second polyimide 1 contains the structural skeleton of the formula (III-C3), and the Y 1 contains the structural skeleton of formula (III-D2), 52. The cured film according to any one of items 42 to 51.

[56] the polyimide includes a first polyimide and a second polyimide; The X of the first polyimide 1 contains the structural skeleton of the formula (III-C2), and the Y 1 contains the structural skeleton of formula (III-D2), The X of the second polyimide 1 contains the structural skeleton of the formula (III-C3), and the Y 1 contains the structural skeleton of formula (III-D2), 52. The cured film according to any one of items 42 to 51.

[57] A photosensitive resin composition comprising: (A) a polyimide precursor; (B) a photopolymerization initiator; (C) a crosslinking agent; and (D) an organic solvent, (1) forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition onto the substrate; (2) The photosensitive resin layer is exposed to 1000 mJ / cm 2 exposing the film to an exposure dose of (3) developing the exposed photosensitive resin layer to form a relief pattern; moreover, (4) forming a hardened relief pattern by heat-treating the relief pattern at 200°C for 2 hours in a nitrogen atmosphere; The cured film obtained through the above steps was subjected to IR spectrum measurement using the ATR method. -1 Nearby peaks and 1720cm -1 Ratio of peaks around (2950cm -1 Nearby peak: 1720cm -1 A photosensitive resin composition characterized in that the peak (peak near the peak) is 0.05 to 0.35.

[58] Item 58. The photosensitive resin composition according to Item 57, further comprising (E) a thermal base generator.

[59] Item 58. The photosensitive resin composition according to Item 57, wherein the ratio of the peaks is 0.1 to 0.25.

[60] Furthermore, 1380cm -1 Nearby peaks and 1500cm -1 Ratio of peaks around (1380cm -1 Nearby peaks: 1500cm -1 Item 59. The photosensitive resin composition according to item 57 or 58, wherein the peak (peak near the peak) is 0.4 to 2.1.

[61] 59. The photosensitive resin composition according to any one of items 57 to 59, wherein the 5% weight loss temperature of the cured film is 280° C. or higher and 350° C. or lower.

[62] 62. The photosensitive resin composition according to any one of items 57 to 61, wherein the (C) crosslinking agent comprises tetraethylene glycol dimethacrylate.

[63] 62. The photosensitive resin composition according to any one of items 57 to 61, wherein the (C) crosslinking agent is a mixture of a compound containing two methacryl groups and / or acrylic groups in the molecule and a compound containing three or more methacryl groups and / or acrylic groups in the molecule.

[64] The polyimide precursor (A) is a polyimide precursor represented by the following general formula (III-1): [ka] In the formula, X is a tetravalent organic group, Y is a divalent organic group, n1 is an integer of 2 to 150, R1 and R2 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a group represented by the following general formula (III-2): [ka] (wherein 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), Or the following general formula (III-3): [ka] (wherein R6, R7, and R8 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m2 represents an integer of 2 to 10.) 64. The photosensitive resin composition according to any one of items 57 to 63, wherein the polyamic acid, polyamic acid ester, or polyamic acid salt is represented by the following formula:

[65] Item 65. The photosensitive resin composition according to item 64, wherein in the general formula (III-1), X contains a tetravalent group represented by the following general formula (III-4) or (III-5): [ka] {In the formula, a1 represents an integer of 0 to 2, and R9 represents a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 10 carbon atoms. When there are multiple R9s, they may be the same or different.} [ka] {wherein n2 is an integer of 0 to 5, and X n1 is a single bond or a divalent organic group, and X n1 If there are multiple n1 may be the same or different. X1 is a single bond or a divalent organic group, and X1 or X n1At least one of a6 and a8 is an organic group selected from a single bond, an oxycarbonyl group, an oxycarbonylmethylene group, a carbonylamino group, a carbonyl group, and a sulfonyl group. a6 and a8 are each independently an integer of 0 to 3, and a7 is an integer of 0 to 4. R 14 , R 15 , and R 16 each independently represents a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 10 carbon atoms; a7 or R 15 If there are multiple occurrences, they may be the same or different.

[66] Item 65. The photosensitive resin composition according to item 64, wherein in the general formula (III-1), Y contains a divalent group represented by the following general formula (III-6): [ka] wherein n3 is an integer of 0 to 5, and Y n2 Y is an organic group having 1 to 10 carbon atoms which may contain a fluorine atom and does not contain any heteroatoms other than fluorine, an oxygen atom, or a sulfur atom. n2 When a plurality of R are present, they may be the same or different. a9 and a10 each independently represent an integer of 0 to 4. 17 and R 18 a10, R each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 10 carbon atoms. 17 , or R 18 When there are multiple, they may be the same or different.

[67] Item 65. The photosensitive resin composition according to Item 64, wherein X of the polyimide precursor includes a structural skeleton represented by any one of the following formulas (III-C1) to (III-C3), or Y of the polyimide precursor includes a structural skeleton represented by any one of the following formulas (III-D1) to (III-D3). [ka] [ka] [ka] [ka] (In general formula (III-D1), R 10 ~R 13 are hydrogen atoms or C1 to C4 monovalent aliphatic groups, and may be different from each other or the same.) [ka] [ka] (In general formula (III-D3), R 14 ~R 21 are hydrogen atoms, halogen atoms, or C1 to C4 monovalent organic groups, and may be different from each other or the same.)

[68] Item 68. The photosensitive resin composition according to Item 67, wherein the polyimide precursor has a structural skeleton represented by formula (III-C1).

[69] Item 69. The photosensitive resin composition according to Item 67 or 68, wherein the polyimide precursor has a structural skeleton represented by formula (III-C2).

[70] 69. The photosensitive resin composition according to any one of items 67 to 69, wherein the polyimide precursor has a structural skeleton represented by formula (III-C3) in which X is a group having a structural skeleton represented by formula (III-C3).

[71] 71. The photosensitive resin composition according to any one of items 67 to 70, wherein the polyimide precursor has a structural skeleton represented by formula (III-D1) in which Y is a group having a structural skeleton represented by formula (III-D1).

[72] 72. The photosensitive resin composition according to any one of items 67 to 71, wherein in the polyimide precursor, Y includes a structural skeleton represented by formula (III-D2).

[73] 73. The photosensitive resin composition according to any one of items 67 to 72, wherein the polyimide precursor has a structural skeleton represented by formula (III-D3) in which Y is a group having a structural skeleton represented by formula (III-D3).

[74] The polyimide precursor is 74. The photosensitive resin composition according to any one of items 67 to 73, wherein X comprises the structural skeleton of formula (III-C1) and Y comprises the structural skeleton of formula (III-D2).

[75] The polyimide precursor is 75. The photosensitive resin composition according to any one of items 67 to 74, wherein X comprises the structural skeleton of formula (III-C2) and Y comprises the structural skeleton of formula (III-D2).

[76] The polyimide precursor is 76. The photosensitive resin composition according to any one of items 67 to 75, wherein X comprises the structural skeleton of formula (III-C3) and Y comprises the structural skeleton of formula (III-D2).

[77] the polyimide precursor includes a first polyimide precursor and a second polyimide precursor; In the first polyimide precursor, X includes a structural skeleton represented by formula (III-C1) and Y includes a structural skeleton represented by formula (III-D2), 77. The photosensitive resin composition according to any one of items 67 to 76, wherein, in the second polyimide precursor, X includes a structural skeleton of formula (III-C3) and Y includes a structural skeleton of formula (III-D2).

[78] the polyimide precursor includes a first polyimide precursor and a second polyimide precursor; In the first polyimide precursor, X includes a structural skeleton represented by formula (III-C2) and Y includes a structural skeleton represented by formula (III-D2), 78. The photosensitive resin composition according to any one of items 67 to 77, wherein, in the second polyimide precursor, X includes a structural skeleton of formula (III-C3) and Y includes a structural skeleton of formula (III-D2).

[79] A semiconductor chip; a sealing material that covers the semiconductor chip; a rewiring layer having an area larger than that of the semiconductor chip in a plan view, The interlayer insulating film of the rewiring layer has a wavelength of 2950 cm when IR spectrum measurement is performed by the ATR method. -1 Nearby peaks and 1720cm -1 Ratio of peaks around (2950cm -1 Nearby peak: 1720cm -1 A semiconductor device comprising a cured film having a peak in the vicinity of the peak (peak near the peak) of 0.05 to 0.35.

[80] 80. The semiconductor device according to item 79, wherein the sealing material is in direct contact with the interlayer insulating film.

[81] Item 81. The semiconductor device according to item 79 or 80, wherein the encapsulant comprises an epoxy resin.

[82] 82. The semiconductor device according to any one of items 79 to 81, wherein the redistribution layer includes, when viewed in cross section of the redistribution layer, a first interlayer insulating film layer, a second interlayer insulating film layer, and an intermediate layer that is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer and is provided between the first interlayer insulating film layer and the second interlayer insulating film layer.

[83] 83. The semiconductor device according to any one of items 79 to 82, wherein the semiconductor device is a fan-out wafer level chip size package type semiconductor device.

[84] a step of covering the semiconductor chip with an encapsulant; forming a rewiring layer having an area larger than that of the semiconductor chip in a plan view and including an interlayer insulating film; The interlayer insulating film had a thickness of 2950 cm when IR spectrum was measured by the ATR method. -1 Nearby peaks and 1720cm -1 Ratio of peaks around (2950cm -1 Nearby peak: 1720cm -1 A method for manufacturing a semiconductor device, comprising using a cured film having a peak in the vicinity of 0.05 to 0.35.

[0016] The fourth aspect of the present invention is as follows.

[85] The following steps: (1) forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition onto the substrate; (2) a step of exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) a first heat-curing step in which the relief pattern is heat-treated at a temperature in the range of 150°C to 200°C for 0 to 240 minutes to form a semi-cured relief pattern; and (5) a second heat-curing step of heat-treating the semi-cured relief pattern at a temperature in the range of 200 to 260°C, which is higher than that in the first heat-curing step, for 10 minutes or less to form a cured relief pattern; A method for producing a multilayer cured relief pattern, further comprising again performing the steps (1) to (5) in the above order.

[86] Item 86. The method for producing a multilayer cured relief pattern according to Item 85, wherein steps (1) to (5) are repeated in the order mentioned above 3 to 8 times.

[87] Item 86. The method for producing a multilayer cured relief pattern according to Item 85, wherein the temperature range of the first thermal curing step is 150°C to 180°C.

[88] Item 86. The method for producing a multilayer cured relief pattern according to Item 85, wherein the temperature range of the first thermal curing step is 150°C to 170°C.

[89] Item 86. The method for producing a multilayer cured relief pattern according to Item 85, wherein the temperature range of the first thermal curing step is 150°C to 160°C.

[90] Item 86. The method for producing a multilayer cured relief pattern according to Item 85, wherein the temperature range of the first thermal curing step is 150°C.

[91] Item 86. The method for producing a multilayer cured relief pattern according to Item 85, wherein the maximum temperature of the second thermal curing step is 260°C or less.

[92] Item 86. The method for producing a multilayer cured relief pattern according to Item 85, wherein the maximum temperature of the second thermal curing step is 240° C. or less.

[93] Item 93. The method for producing a multilayer cured relief pattern according to any one of Items 85 to 92, wherein in the second thermal curing step, the heating time at the maximum temperature is 5 minutes or less.

[94] Item 94. The method for producing a multilayer cured relief pattern according to any one of Items 85 to 93, wherein in the second thermal curing step, the heating time at the maximum temperature is 1 minute or less.

[95] Item 95. The method for producing a multilayer cured relief pattern according to any one of Items 85 to 94, wherein the substrate is a substrate composed of a semiconductor chip and an encapsulant that covers the semiconductor chip.

[96] Item 96. The method for producing a multilayer cured relief pattern according to any one of Items 85 to 95, wherein the photosensitive resin composition is a photosensitive polyimide resin composition.

[97] The resin of the photosensitive polyimide resin composition is represented by the following general formula (IV-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 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 4 carbon atoms, or a group represented by the following general formula (IV-2): [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.) or a monovalent organic group represented by the following general formula (IV-3): [ka] (In the formula, R6, R7, and R8 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m2 represents an integer of 2 to 10.) It is an ammonium ion represented by the formula: Item 97. The method for producing a multilayer cured relief pattern according to Item 96, wherein the polyimide precursor has a structure represented by the formula:

[98] Item 98. The method for producing a multilayer cured relief pattern according to Item 97, wherein in the general formula (IV-1), X1 is a tetravalent organic group having an aromatic group, and Y1 is a divalent organic group having an aromatic group.

[99] Item 98. The method for producing a multilayer cured relief pattern according to Item 97, wherein in the general formula (IV-1), X1 is a tetravalent group represented by the following formula (IV-7): [ka]

[0100] Item 98. The method for producing a multilayer cured relief pattern according to Item 97, wherein in the general formula (IV-1), Y1 is a divalent group represented by the following formula (IV-11): [ka]

[0101] Item 98. The method for producing a multilayer cured relief pattern according to Item 97, wherein in the general formula (IV-1), X1 is a tetravalent group represented by the following formula (IV-7), and Y1 is a divalent group represented by the following formula (IV-11): [ka] [ka]

[0102] Item 98. The method for producing a multilayer cured relief pattern according to Item 97, wherein in the general formula (IV-1), X1 is a tetravalent group represented by the following formula (IV-5): [ka]

[0103] Item 98. The method for producing a multilayer cured relief pattern according to Item 97, wherein in the general formula (IV-1), X1 is a tetravalent group represented by the following formula (IV-5), and Y1 is a divalent group represented by the following formula (IV-11): [ka] [ka]

[0017] A fifth aspect of the present invention is as follows.

[0104] (A) polyimide precursor: 100 parts by mass, (B) a compound represented by at least one of the following general formulas (V-1) and (V-3) to (V-6): 0.1 to 50 parts by mass, (C) Photosensitizer: 0.1 to 50 parts by mass A photosensitive resin composition comprising: [ka] In formula (V-1), A represents a nitrogen atom or a carbon atom, R1 represents an electron-withdrawing group, R2 represents a monovalent organic group having 1 to 6 carbon atoms, and a plurality of R1 and / or R2 may form a ring structure, and R3 represents a group represented by the following general formula (V-2): [ka] (In formula (V-2), R4 and R5 each independently represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms.) wherein m1 is an integer of 1 to 2, m2 is an integer of 0 to 3, and m3 is an integer of 0 to 2; when A is a carbon atom, m3 is 1 or 2, and 1≦m1+m2+m3≦6. [ka] [ka] [ka] [ka] {In formulas (V-3) to (V-6), X represents a nitrogen atom, a sulfur atom, or an oxygen atom; each R1 is independently an electron-withdrawing group; each R2 is independently a monovalent organic group having 1 to 6 carbon atoms, and a plurality of R2 may form a ring structure; m1 is an integer of 1 to 2, m2 is an integer of 0 to 3, 1≦m1+m2≦6; and T represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.}

[0105] Item 105. The photosensitive resin composition according to item 104, wherein the compound (B) is at least one selected from the group consisting of the following general formulae (V-7) and (V-8): [ka] [ka] {In formulas (V-7) and (V-8), R1, R2, m1, and m2 are as defined in at least one of general formulas (V-1) and (V-3) to (V-6) above.}

[0106] Item 104. The photosensitive resin composition according to Item 104 or 105, wherein in at least one of the general formulae (V-1) and (V-3) to (V-6), R1 is at least one selected from the group consisting of a nitro group, a fluoro group, a chloro group, a bromo group, a cyano group, a sulfonyl group, a halogenated alkyl group having 1 to 8 carbon atoms, and a monovalent organic group having 1 to 4 carbon atoms and containing a carbonyl group.

[0107] Item 104. The photosensitive resin composition according to Item 104 or 105, wherein in at least one of the general formulae (V-1) and (V-3) to (V-6), R1 is at least one selected from the group consisting of an amide group, a carboxyl group, a phthalimide group, a formyl group, and an ester group having 1 to 3 carbon atoms.

[0108] 108. The photosensitive resin composition according to any one of items 104 to 107, wherein the (A) polyimide precursor is represented by the following general formula (V-9): [ka] In formula (V-9), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R5 and R6 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R5 and R6 is a group represented by the following general formula (V-10): [ka] {In formula (V-10), R7, R8, and R9 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m4 represents an integer of 2 to 10.}

[0109] Item 109. The photosensitive resin composition according to item 108, wherein in general formula (V-9), X1 includes at least one selected from the following general formulas (V-11), (V-12), and (V-13): [ka] [ka] [ka]

[0110] Item 109. The photosensitive resin composition according to item 108, wherein in general formula (V-9), Y1 is at least one selected from the group consisting of the following general formulas (V-14) and (V-15): [ka] [ka]

[0111] 111. The photosensitive resin composition according to any one of items 108 to 110, wherein the (A) polyimide precursor contains a structure represented by the following general formula (V-16): [ka] {In formula (V-16), n1 represents an integer of 2 to 150, and R5 and R6 are as defined in general formula (V-9) above.}

[0112] 111. The photosensitive resin composition according to any one of items 108 to 110, wherein the (A) polyimide precursor contains a structure represented by the following general formula (V-17): [ka] {In formula (V-17), n1 represents an integer of 2 to 150, and R5 and R6 are as defined in general formula (V-9) above.}

[0113] 111. The photosensitive resin composition according to any one of items 108 to 110, wherein the (A) polyimide precursor simultaneously contains a polyimide precursor having a structure represented by the following general formula (V-16) and a polyimide precursor having a structure represented by the following general formula (V-17): [ka] {In formula (V-16), n1 represents an integer of 2 to 150, and R5 and R6 are as defined in general formula (V-9) above.} [ka] {In formula (V-17), n1 represents an integer of 2 to 150, and R5 and R6 are as defined in general formula (V-9) above.}

[0114] 114. The photosensitive resin composition according to any one of items 104 to 113, wherein the (C) photosensitizer is a photoradical generator, and the photosensitive resin composition is negative.

[0115] Further, (D) a thermal base generator: 0.1 to 50 parts by mass 115. The photosensitive resin composition according to any one of items 104 to 114, comprising:

[0116] A method for producing a polyimide, comprising curing the photosensitive resin composition according to any one of items 104 to 115.

[0117] The following steps: (1) A step of applying the photosensitive resin composition according to any one of items 104 to 115 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; 2. A method for producing a cured relief pattern comprising: [Effects of the Invention]

[0018] According to the present invention, there are provided a negative photosensitive resin composition that exhibits high resolution when forming a relief pattern on copper, is less likely to form voids on copper when stored at high temperatures, and exhibits excellent elongation even when stored under high-temperature and high-humidity conditions, and a method for producing a cured relief pattern using the photosensitive resin composition. [Brief explanation of the drawings]

[0019] [Figure 1] 1 is a schematic cross-sectional view of a semiconductor device according to an embodiment of the present invention; [Figure 2] 1 is a schematic plan view of a semiconductor device according to an embodiment of the present invention; [Figure 3] 1 is a diagram illustrating an example of a manufacturing process of the semiconductor device according to the present embodiment. [Figure 4] This is a comparison diagram between flip-chip BGA and fan-out type WLCSP. DETAILED DESCRIPTION OF THE INVENTION

[0020] Hereinafter, an embodiment of the present invention (hereinafter abbreviated as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist of the present invention. Throughout this specification, structures represented by the same symbol in general formulae may be the same or different when present in a molecule, and when multiple components represented by the same symbol in the drawings are present, they may be the same or different.

[0021] A first aspect of this embodiment will be described. <Negative-type photosensitive resin composition> The negative photosensitive resin composition according to this embodiment is (A) 100 parts by mass of a polyimide precursor containing a structural unit represented by the following general formula (I-1), and (B) Photopolymerization initiator: 0.1 parts by mass to 20 parts by mass Includes: [ka] In formula (I-1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R1 and R2 is a group containing two or more polymerizable groups selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group.

[0022] From the viewpoint of obtaining high sensitivity and high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor and 0.1 to 20 parts by mass of (B) photopolymerization initiator based on 100 parts by mass of (A) polyimide precursor.

[0023] (A) Polyimide precursor The polyimide precursor (A) in this embodiment is a resin component contained in the negative photosensitive resin composition, and is converted into a polyimide by subjecting it to a thermal cyclization treatment.

[0024] The polyimide precursor is preferably a polyimide precursor having a structure represented by the above general formula (I-1).

[0025] In general formula (I-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 or an alicyclic aliphatic group in which the -COOR1 group, the -COOR2 group, and the -CONH- group are located at the ortho positions relative to each other. Examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, and specific examples thereof include those represented by the following general formulae (X1-1) and (X1-2): [ka] [ka] In formulae (X1-1) and (X1-2), R6 represents a hydrogen atom, a fluorine atom, or a C1 to C 10 and hydrocarbon groups of C1 to C 10 wherein 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.} Examples of the X1 group include, but are not limited to, groups having a structure represented by each of the following formulae: X1-1 and X1-2. The structure of X1 may be one type or a combination of two or more types. X1 groups having a structure represented by each of the above formulae (X1-1) and (X1-2) are particularly preferred in that they achieve both heat resistance and photosensitive properties, and the structures represented by each of the above formulae (X1-1) are more preferred.

[0026] As the X1 group, among the structures represented by the above formula (X1-1), particularly, those represented by the following formula: [ka] {In the formula, R6 and m have the same meanings as R6 and m in the above formula (X1-1), respectively.} The structures represented by the following formulas are preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0027] In the above general formula (I-1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, in order to achieve both heat resistance and photosensitive properties, and examples thereof include the following formulae (Y1-1) and (Y1-2): [ka] [ka] wherein R6 is a hydrogen atom, a fluorine atom, or a C1 to C 10 and hydrocarbon groups of C1 to C 10 and n is an integer selected from 0 to 4.} Examples include, but are not limited to, structures represented by the formulas (Y1-1) and (Y1-2). The structure of Y1 may be one type or a combination of two or more types. Y1 groups having structures represented by the formulas (Y1-1) and (Y1-2) above are particularly preferred in that they achieve both heat resistance and photosensitive properties, and structures represented by the formulas (Y1-1) above are more preferred.

[0028] As the Y1 group, among the structures represented by the above formula (Y1-1), particularly, those represented by the following formula: [ka] {In the formula, R6 and n have the same meanings as R6 and n in the above formula (Y1-1), respectively.} The structures represented by the following formulas are preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0029] At least one of R1 and R2 in the general formula (I-1) is preferably a group containing two or more polymerizable groups selected from the group consisting of acid-polymerizable groups, base-polymerizable groups, and radical-polymerizable groups. Here, the acid-polymerizable group, base-polymerizable group, and radical-polymerizable group refer to groups that can be polymerized by the action of an acid, a base, or a radical, respectively.

[0030] The number of polymerizable groups that at least one of R1 and R2 has is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. As the polymerizable group contained in at least one of R1 and R2, from the viewpoint of sensitivity, it is desirable that at least one of R1 and R2 contains a group represented by the following general formula (I-R1). [ka] {In formula (I-R1), R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, Z is a trivalent or tetravalent organic group having 1 to 10 carbon atoms, and when Z is trivalent, m1 is 2, and when Z is tetravalent, m1 is 3.}

[0031] The proportion of the monovalent organic group represented by the general formula (I-R1) to all of R1 and R2 in the polyimide precursor (A) is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, particularly preferably 90 mol % or more or 95 mol % or more, and may be 100%, from the viewpoint of improving resolution during exposure.

[0032] Furthermore, from the viewpoint of resolution, it is desirable that at least one of R1 and R2 contains a group represented by the following general formula (I-R2) or (I-R3). [ka] {In formula (I-R2), R6 and R7 each independently represent a hydrogen atom or a methyl group} [ka] {In formula (I-R3), R8, R9, and R 10 are each independently a hydrogen atom or a methyl group.

[0033] In the polyimide precursor (A), the total proportion of the monovalent organic groups represented by the general formulas (I-R2) and (I-R3) relative to all of R1 and R2 is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, particularly preferably 90 mol % or more or 95% or more, and may be 100%, from the viewpoint of improving resolution during exposure.

[0034] The negative-type photosensitive resin composition of the present embodiment provides a polyimide film that has excellent resolution on copper and void formation suppression properties, and further has high elongation even after storage under high temperature and high humidity conditions, due to the polyimide precursor containing a side chain with a specific structure. Without being bound by theory, it is believed that the reason for the improved resolution on copper is that an increase in the number of polymerizable groups contained in one resin molecule forms a strong cross-linked structure between resins during exposure, thereby suppressing swelling due to the developer during development. Furthermore, the reason for the excellent void formation suppression is thought to be that some of the relatively low-polarity acrylate / methacrylate polymerization products that are crosslinked by photoreaction remain in the film even after thermal curing, thereby suppressing copper migration. The same is true for maintaining elongation after storage under high temperature and humidity conditions; it is thought that the presence of some of the acrylate / methacrylate polymerization product remaining in the film makes it possible to prevent water from penetrating into the film, allowing the film to maintain high elongation even after storage, just as it did before storage.

[0035] In one embodiment, the structural unit represented by the general formula (I-1) in the polyimide precursor (A) is represented by the following general formula (I-1-1): [ka] {In formula (I-1-1), R1, R2, and n1 are defined as in general formula (I-1) above.} It is preferable that the copolymer contains a structural unit represented by the following formula:

[0036] In general formula (I-1-1), from the viewpoint of sensitivity, at least one of R1 and R2 preferably contains a monovalent organic group represented by general formula (I-R1) above, and from the viewpoint of resolution, more preferably contains a group represented by general formula (I-R2) or (I-R3) above. The structural unit represented by the general formula (I-1) in the polyimide precursor (A) containing the structural unit represented by the general formula (I-1-1) particularly enhances the chemical resistance of the resulting polyimide film, and is also preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, and copper adhesion.

[0037] In one embodiment, the structural unit represented by the general formula (I-1) in the polyimide precursor (A) is represented by the following general formula (I-1-2): [ka] {In the formula, R1, R2, and n1 are defined as in the above general formula (I-1).} It is preferable that the copolymer contains a structural unit represented by the following formula:

[0038] In general formula (I-1-2), from the viewpoint of sensitivity, at least one of R1 and R2 preferably contains a monovalent organic group represented by general formula (I-R1) above, and from the viewpoint of resolution, more preferably contains a group represented by general formula (I-R2) or (I-R3) above. The structural unit represented by the general formula (I-1) in the polyimide precursor (A) containing the structural unit represented by the general formula (I-1-2) particularly enhances the chemical resistance of the resulting polyimide film, and is also preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, and copper adhesion.

[0039] In one embodiment, the structural unit represented by the general formula (I-1) in the polyimide precursor (A) is represented by the following general formula (I-1-3): [ka] {In the formula, R1, R2, and n1 are defined as in the above general formula (I-1).} It is preferable that the copolymer contains a structural unit represented by the following formula:

[0040] In general formula (I-1-3), from the viewpoint of sensitivity, at least one of R1 and R2 preferably contains a monovalent organic group represented by general formula (I-R1) above, and from the viewpoint of resolution, more preferably contains a group represented by general formula (I-R2) or (I-R3) above. The structural unit represented by the general formula (I-1) in the polyimide precursor (A) containing the structural unit represented by the general formula (I-1-3) further enhances the effect of improving resolution, and is also preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0041] (A) Preparation of polyimide precursor (A) To prepare a polyimide precursor, first, the tetracarboxylic acid dianhydride containing the tetravalent organic group X1; an alcohol having two or more polymerizable groups selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group, and optionally other alcohols; is reacted to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester). Next, a partially esterified tetracarboxylic acid (acid / ester form) and a diamine containing the divalent organic group Y1; By subjecting the above to amide polycondensation, the polyimide precursor (A) specified in this embodiment can be obtained.

[0042] (Preparation of Acid / Ester Forms) In this embodiment, the tetracarboxylic acid dianhydride containing a tetravalent organic group X1 that is suitably used to prepare the polyimide precursor (A) is a tetracarboxylic acid dianhydride represented by the following formula: [ka] {wherein X1 is as defined in general formula (I-1) above.} Preferably, X1 is a compound represented by the following formula: It is more preferable that X1 is selected from the structures represented by the above general formulas (X1-1) and (X1-2), and it is even more preferable that X1 is a structure represented by the above general formula (X1-1).

[0043] Particularly preferred examples of the tetracarboxylic dianhydride include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride (also known as oxydiphthalic dianhydride, abbreviated as "ODPA"), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (abbreviated as "BPDA"), diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-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. Particularly preferred examples include, but are not limited to, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0044] In this embodiment, examples of alcohols having two or more polymerizable groups selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group that are suitably used to prepare the polyimide precursor (A) include glycerol diacrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, glycerol dimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate.

[0045] In this embodiment, other alcohols that can be optionally used to prepare the (A) polyimide precursor include alcohols having one photopolymerizable unsaturated double bond and alcohols having no polymerizable group.

[0046] Examples of the alcohol having one photopolymerizable unsaturated double bond 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, and 2-hydroxy-3-cyclohexyloxypropyl acrylate. acrylate, 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, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.

[0047] Examples of alcohols having no polymerizable group include 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.

[0048] As the (A) polyimide precursor, a non-photosensitive polyimide precursor prepared using only the above-mentioned alcohol having no polymerizable group may be used in combination with the photosensitive polyimide precursor of the present invention. In this case, from the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor blended is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

[0049] The above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohol are dissolved and mixed in the presence of a suitable basic catalyst such as pyridine, preferably in a solvent as described below, preferably at a temperature of 20 to 50°C, preferably for 4 to 10 hours with stirring, whereby an esterification reaction of the acid anhydride group of the tetracarboxylic dianhydride proceeds, and the desired acid / ester form can be obtained.

[0050] (Preparation of Polyimide Precursor) To the above acid / ester compound (typically in the form of a solution dissolved in a solvent described below), 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, is added and mixed under ice cooling to convert the acid / ester compound into a polyacid anhydride, and then a diamine containing a divalent organic group Y1 preferably used in this embodiment, dissolved or dispersed in a separate solvent, is added dropwise to the resulting mixture to cause amide polycondensation, thereby obtaining the desired polyimide precursor. Alternatively, the acid moiety of the acid / ester compound can be converted into an acid chloride using thionyl chloride or the like, and then the acid chloride can be reacted with a diamine in the presence of a base such as pyridine to obtain the desired polyimide precursor.

[0051] The diamine containing the divalent organic group Y1 preferably used in this embodiment is a diamine represented by the formula: H2N-Y1-NH2 {wherein Y1 is as defined in general formula (I-1) above.} It is more preferable that Y1 is a structure represented by each of the above general formulae (Y1-1) and (Y1-2).

[0052] More preferred diamines include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (also known as 4,4'-oxydianiline, abbreviated as "ODA"), 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, 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]sulfone, bis[4-(3- 4,4-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)hexafluoropropane, 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, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,Examples of the diaminodiphenylmethane include, but are not limited to, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl. These may be used alone or in combination of two or more.

[0053] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as needed, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion exchange resin, a cation exchange resin, or both, swollen with an appropriate organic solvent to remove ionic impurities.

[0054] The molecular weight of the polyimide precursor (A), 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 recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrenes. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent standard sample "STANDARD SM-105" manufactured by Showa Denko K.K.

[0055] (B) Photopolymerization initiator The photopolymerization initiator (B) used in this embodiment will be described. The photopolymerization initiator is preferably a photoradical polymerization initiator or a photoacid generator.

[0056] Examples of the photoradical polymerization initiator include benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone compounds such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl compounds such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin compounds such as benzoin and benzoin methyl ether; and 1-phenyl Examples of suitable oxime compounds include 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-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-arylglycine compounds such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazole compounds; and titanocene compounds.

[0057] A preferred example of the photoacid generator is α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide.

[0058] The (B) photopolymerization initiator preferably used in this embodiment is not limited to the above examples. Among the above photopolymerization initiators, photoradical polymerization initiators are more preferred, and oxime compounds are even more preferred in terms of photosensitivity.

[0059] The blending amount of the (B) photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor. The blending amount is preferably 0.1 part by mass or more from the viewpoint of photosensitivity or patterning ability, and is preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

[0060] (C) Rust inhibitor When the photosensitive resin composition of the present embodiment is used to form a cured film on a substrate made of copper or a copper alloy, the negative photosensitive resin composition may optionally contain a rust inhibitor to suppress discoloration of the copper. Examples of the rust inhibitor include an azole compound and a purine compound.

[0061] Examples of the azole compound 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, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and 2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole. benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, 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.

[0062] Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0063] Specific examples of purine compounds 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, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 2-hydroxy ... 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9 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 the like, and derivatives thereof.

[0064] When the photosensitive resin composition contains (C) a rust inhibitor, the blending amount is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of (A) polyimide precursor, more preferably 0.03 to 10 parts by mass from the viewpoint of photosensitivity characteristics, and even more preferably 0.05 to 5 parts by mass, and may be, for example, 0.01 to 5 parts by mass. When the blending amount of (C) a rust inhibitor relative to 100 parts by mass of (A) polyimide precursor is 0.01 part by mass or more, when the photosensitive resin composition of this embodiment is formed on copper or a copper alloy, discoloration of the copper or copper alloy surface is suppressed, while when the blending amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0065] (D) Thermal base generator The negative photosensitive resin composition of this embodiment may contain (D) a thermal base generator. A base generator is a compound that generates a base upon heating. By containing a thermal base generator, it is possible to further promote imidization of the photosensitive resin composition.

[0066] The thermal base generator is not particularly limited in type, and examples thereof include an amine compound protected by a tert-butoxycarbonyl group, the thermal base generators disclosed in WO 2017 / 038598, etc. However, the thermal base generator is not limited to these, and other known thermal base generators can also be used.

[0067] 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, 2-amino-1,3-propanediol, 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)-1-propanol, 4-amino-2-methyl-1-but ...4-amino-2-methyl-1-butanol, 4-amino-2-methyl-1-butanol, 4-amino-2-methyl-1-butanol, 4-amino-2-methyl-1-but (isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, 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-butanol bis(3-aminopropyl)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, diethylene glycol bis(3-aminopropyl) ether, and compounds in which the amino group of an amino acid or a derivative thereof is protected with a tert-butoxycarbonyl group, but are not limited to these.

[0068] The blending amount of the (D) thermal base generator is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, and even more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor. The blending amount is preferably 0.1 parts by mass or more from the viewpoint of the imidization-accelerating effect, and is preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative-type photosensitive resin composition.

[0069] The negative-type photosensitive resin composition of this embodiment may further contain components other than the above components (A) to (D). Examples of the components other than components (A) to (D) include, but are not limited to, solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, adhesion aids, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors.

[0070] solvent Examples of the solvent include amides, sulfoxides, urea and derivatives thereof, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. Specific examples of the solvent that can be used include 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, propylene 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, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, and mesitylene. Among these, from the viewpoints of resin solubility, resin composition stability, and adhesion to substrates, one or more selected from the group consisting of 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, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

[0071] Among these solvents, those that completely dissolve the (A) polyimide precursor are particularly preferred, and suitable examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma-butyrolactone.

[0072] In the photosensitive resin composition of the present embodiment, the amount of the solvent used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor.

[0073] Hindered phenol compounds To inhibit discoloration on copper surfaces, the negative photosensitive resin composition may optionally contain a hindered phenol compound.Examples of the hindered phenol compound include 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), alcohol), 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, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3 H,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-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -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-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 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, Examples of the hydroxybenzoates include, but are not limited to, 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-2,4,6-(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 and the like are particularly preferred.

[0074] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity. When the amount of the hindered phenol compound relative to 100 parts by mass of the (A) polyimide precursor is 0.1 part by mass or more, for example, when the photosensitive resin composition of this embodiment 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.

[0075] Organotitanium Compounds The negative photosensitive resin composition of the present embodiment may contain an organotitanium compound. By containing an organotitanium compound in the negative photosensitive resin composition, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0076] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the negative photosensitive resin composition and produce good cured patterns. 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(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -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.

[0077] Among them, 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. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0078] When an organotitanium compound is added, the amount added 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. When the amount added is 0.05 part by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance, while when the amount added is 10 parts by mass or less, the photosensitive resin composition has excellent storage stability.

[0079] Adhesion aid In order to improve the adhesion between a film formed using the negative photosensitive resin composition of this embodiment and a substrate, the negative photosensitive resin composition may optionally contain an adhesion aid. As the adhesion promoter, an aluminum-based adhesion promoter, a silane coupling agent, or the like can be used.

[0080] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0081] Examples of silane coupling agents include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3- (triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]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)propyl succinic anhydride, 3-mercaptopropyltrimethoxysilane (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-Mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltrippropoxysilane, 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, N-(3-ethoxydimethoxysilylethyl) 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), aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2),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(methoxyethoxy) Silane), 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] [propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane arylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol,In addition to n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like, the following formula (S-1): [ka] Examples of silane coupling agents include, but are not limited to, silane coupling agents having the structures represented by the following formulas:

[0082] Among these adhesion aids, it is more preferable to use a silane coupling agent in terms of adhesive strength. Among the above-mentioned silane coupling agents, from the viewpoint of storage stability, it is preferable to use one or more silane coupling agents selected from the group consisting of phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and silane coupling agents having a structure represented by each of the above formula (S1).

[0083] When the photosensitive resin composition contains an adhesion promoter, the amount of the adhesion promoter is preferably in the range of 0.01 to 25 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the (A) polyimide precursor. 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.

[0084] sensitizer The negative photosensitive resin composition of this embodiment may optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizer include 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.

[0085] When the photosensitive 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.

[0086] Photopolymerizable unsaturated monomers The negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, and examples thereof include, but are not limited to, the following: Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of ethylene glycol; Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of polyethylene glycol; Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of propylene glycol; Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of polypropylene glycol; Monoacrylates, diacrylates, triacrylates, monomethacrylates, dimethacrylates, and trimethacrylates of glycerol; Diacrylates and dimethacrylates of cyclohexane; Diacrylates and dimethacrylates of 1,4-butanediol; Diacrylate and dimethacrylate of 1,6-hexanediol; Neopentyl glycol diacrylate and dimethacrylate; Monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of bisphenol A; Benzene trimethacrylate; Isobornyl acrylate and isobornyl methacrylate; Acrylamide and its derivatives; methacrylamide and its derivatives; Trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; Diacrylates, triacrylates, tetraacrylates, dimethacrylates, trimethacrylates, and tetramethacrylates of pentaerythritol; and Examples of compounds include ethylene oxide adducts and propylene oxide adducts of these compounds.

[0087] When the photosensitive resin composition contains the above-mentioned photopolymerizable unsaturated monomer for improving the resolution of the relief pattern, the amount of the photopolymerizable unsaturated monomer blended is preferably 1 to 50 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0088] Thermal polymerization inhibitor The negative photosensitive resin composition of this embodiment may optionally contain a thermal polymerization inhibitor in order to improve the stability of viscosity and photosensitivity, particularly when stored in the form of a solution containing a solvent. Examples of the thermal polymerization inhibitor that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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.

[0089] <Method for producing cured relief pattern> The method for producing a cured relief pattern of this embodiment includes the steps of: (1) a step of applying the negative photosensitive resin composition of the present embodiment described above onto a substrate to form a photosensitive resin layer on the substrate (a resin layer forming step); (2) a step of exposing the photosensitive resin layer to light (exposure step); (3) developing the exposed photosensitive resin layer to form a relief pattern (relief pattern forming step); (4) a step of heat-treating the relief pattern to form a cured relief pattern (a step of forming a cured relief pattern); Includes:

[0090] (1) Resin layer formation process In this step, the negative photosensitive resin composition of this embodiment is applied to a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0091] If necessary, the coating film containing the photosensitive resin composition can be dried. Drying methods include air drying, heat drying using an oven or a hot plate, and vacuum drying. Specifically, in the case of air drying or heat drying, drying can be carried out at 20°C to 150°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on a substrate.

[0092] (2) Exposure process In this step, the photosensitive resin layer formed above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern. This exposure causes the polymerizable groups of the polyimide precursor (A) contained in the negative photosensitive resin composition to crosslink due to the action of the photopolymerization initiator (B). This crosslinking makes the exposed area insoluble in the developer described below, enabling the formation of a relief pattern.

[0093] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) or pre-development baking, or both, may be performed at any combination of temperature and time, as necessary. The baking conditions are preferably a temperature of 40°C to 120°C and a time of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition of this embodiment.

[0094] (3) Relief pattern formation process In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The developing method for developing the exposed (irradiated) photosensitive resin layer can be any method selected from conventionally known photoresist developing methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. 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.

[0095] The developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition of this embodiment, or a combination of the good solvent and a poor solvent. Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative photosensitive resin composition. Two or more solvents, for example, several types, can also be used in combination.

[0096] (4) Hardened relief pattern formation process In this step, the relief pattern obtained by the above development is heat-treated to dissolve the photosensitive component and imidize the (A) polyimide precursor, 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 200°C or lower, more preferably 180°C or lower. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may also be used.

[0097] The photosensitive resin layer after exposure has a crosslinked structure formed by crosslinking of the polymerizable groups of the (A) polyimide precursor. However, this crosslinked structure is eliminated from the polymer during heating in the cured relief pattern formation step, and the amide acid structure generated by this elimination undergoes ring closure to form an imide ring structure, which is thought to result in the formation of a cured relief pattern made of polyimide.

[0098] <Polyimide> Therefore, it is believed that the cured relief pattern formed from the above photosensitive resin composition contains a polyimide having a structure represented by the following general formula (I-2). [ka] {In general formula (I-2), X 1 and Y 1 respectively represent X in general formula (I-1). 1 and Y 1 is the same as Preferred X in formula (I-1) 1 , Y 1 For the same reason, the following is also preferred for the polyimide of general formula (I-2). Another aspect of the present invention is a method for producing a polyimide, which includes a step of curing the above-described negative-type photosensitive resin composition to form a polyimide.

[0099] <Semiconductor device> This embodiment also provides a semiconductor device having a cured relief pattern obtained from the above-described photosensitive resin composition. More specifically, a semiconductor device is provided having a substrate that is a semiconductor element and a cured relief pattern. The cured relief pattern may be produced by the above-described method for producing a cured relief pattern using the above-described photosensitive resin composition. This embodiment can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the method for manufacturing a cured relief pattern of this embodiment as part of its steps. In this case, the cured relief pattern formed by the method for manufacturing a cured relief pattern of this embodiment can be formed as a surface protective film for a semiconductor device, 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 can be manufactured by combining this method with a known method for manufacturing a semiconductor device.

[0100] <Display device> This embodiment provides a display device comprising a display element and a cured film disposed on the display element, the cured film having the cured relief pattern described above. The cured relief pattern may be laminated directly on the display element, or may be laminated via another layer. The cured film can be used, for example, as a surface protection film, insulating film, or planarizing film for a TFT liquid crystal display element or a color filter element; a protrusion for an MVA-type liquid crystal display device; or a partition wall for a cathode of an organic EL element.

[0101] The negative photosensitive resin composition of this embodiment is useful not only for application to the semiconductor device described above, but also for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[0102] A second aspect of this embodiment will be described. In the second embodiment, the photosensitive resin composition includes (A) a polyimide precursor and (B) a photopolymerization initiator. If desired, the photosensitive resin composition may include other components. Each component will be described below in turn.

[0103] Whether the photosensitive resin composition is negative or positive can be selected depending on the desired application, and from the viewpoint of the physical properties of the (A) polyimide precursor described below, the photosensitive resin composition is preferably negative.

[0104] (A) Polyimide precursor In this embodiment, the polyimide precursor (A) is a resin component contained in the photosensitive resin composition, and is represented by the following general formula (II-1): [ka] In formula (II-1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R1 and R2 is a group represented by the following general formula (II-2): [ka] (In formula (II-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 a group represented by the following formula: and the structure represented by the following general formula (II-3): [ka] In formula (II-3), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R6 and R7 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R6 and R7 is a group represented by the following general formula (II-4): [ka] (In formula (II-4), Z is a monovalent organic group containing a base having at least one nitrogen atom, or a base protected with a protecting group that can be removed by an acid, a base, or heat.) It is a group represented by the following formula: It is a polyamide containing a structure represented by the following formula:

[0105] In the general formula (II-4), the group represented by Z is preferably a monovalent organic group having an aromatic amine structure in which one or more aromatic rings are directly bonded to a nitrogen atom from the viewpoint of storage stability, and more preferably a monovalent organic group having an aromatic tertiary amine structure from the viewpoint of imidization rate and chemical resistance.

[0106] As the group represented by Z, a monovalent organic group having an aromatic tertiary amine structure may be mentioned, for example, a group represented by the following general formula (II-7): [ka] Examples of the group include a group represented by the following formula:

[0107] In one embodiment, the group represented by Z in the above general formula (II-4) is preferably a monovalent organic group containing an amine protected with a tert-butoxycarbonyl (boc) group or a 9-fluorenylmethyloxycarbonyl (Fmoc) group, and from the viewpoints of the imidization rate during low-temperature curing and chemical resistance, a monovalent organic group containing an amine protected with a tert-butoxycarbonyl (boc) group is particularly preferred.

[0108] Examples of the monovalent organic group containing an amine protected with a tert-butoxycarbonyl (boc) group or a 9-fluorenylmethyloxycarbonyl (Fmoc) group include a group represented by the following general formula (II-8): [ka] Examples of the group include a group represented by the following formula:

[0109] The proportion of the monovalent organic group represented by the general formula (II-4) to all of R1 and R2 of the precursor represented by the general formula (II-1) contained in the (A) polyimide precursor is preferably 1 mol % to 50 mol % from the viewpoint of achieving both a high imidization rate and photosensitivity, and more preferably 2.5 mol % to 25 mol % from the viewpoint of high chemical resistance and sensitivity.

[0110] In the (A) polyimide precursor, R6 and / or R7 contain a monovalent organic group containing a base having at least one nitrogen atom or a base protected by a protecting group that can be removed by acid, base, or heat, thereby creating a chemical structure similar to that of an imidization accelerator in the vicinity of the polymer chain. This is believed to improve imidization promotion compared to when the additive is used. Furthermore, when an imidization accelerator with a low boiling point is used as an additive, it volatilizes before promoting imidization during the thermal curing process, and therefore does not achieve the imidization promotion effect. However, as shown in this embodiment, when a group having an imidization promotion effect is introduced into the side chain of the resin, it remains in the film until the imidization reaction occurs. After the imidization reaction, the released group having an imidization promotion effect quickly volatilizes, resulting in an imidization-effect film with excellent thermal properties and chemical resistance.

[0111] In the above general formulas (II-1) and (II-3), 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 photosensitive resin composition, it is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

[0112] In the above general formulas (II-1) and (II-3), 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 or an alicyclic aliphatic group in which the -COOR1 group, the -COOR2 group, and the -CONH- group are located at the ortho positions relative to each other. 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 (II-20): [ka] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, 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.} Examples of suitable X1 groups include, but are not limited to, groups having a structure represented by the following formula: In addition, the structure of X1 may be one type or a combination of two or more types. X1 groups having a structure represented by the above formula (II-20) are particularly preferred in that they achieve both heat resistance and photosensitive properties.

[0113] In the above general formulas (II-1) and (II-3), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, in order to achieve both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (II-21): [ka] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4.} Examples include, but are not limited to, structures represented by the following formula: In addition, the structure of Y1 may be one type or a combination of two or more types. The Y1 group having the structure represented by formula (II-21) above is particularly preferred in that it achieves both heat resistance and photosensitive properties.

[0114] As the Y1 group, among the structures represented by the above formula (II-21), particularly, those represented by the following formula: [ka] The structure represented by the following formula is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0115] In the general formula (II-2), R3 is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitivity. Also, m1 is an integer of 2 to 10, preferably 2 to 4, from the viewpoint of photosensitivity.

[0116] In one embodiment, the polyimide precursor (A) is represented by the following general formula (II-5): [ka] In formula (II-5), n2 is an integer of 2 to 150, R6 and R7 are each independently a hydrogen atom or a monovalent organic group, and at least one of R6 and R7 is a group represented by the following general formula (II-4): [ka] (In formula (II-4), Z is a monovalent organic group containing a base having at least one nitrogen atom, or a base protected with a protecting group that can be removed by an acid, a base, or heat.) It is a group represented by the following formula: It is preferable that the resin contains a resin having a structural unit represented by the following formula: In general formula (II-5), the other of R6 and R7 is more preferably a monovalent organic group represented by general formula (II-2). When (A) polyimide precursor contains a polyimide precursor represented by general formula (II-5), the effect of particularly improving resolution is enhanced.

[0117] In one embodiment, the polyimide precursor (A) is represented by the following general formula (II-6): [ka] In formula (II-6), n3 represents an integer of 2 to 150, R6 and R7 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R6 and R7 represents a group represented by the following general formula (II-4): [ka] (In formula (II-4), Z is a monovalent organic group containing a base having at least one nitrogen atom, or a base protected with a protecting group that can be removed by an acid, a base, or heat.) It is a group represented by the following formula: It is preferable that the resin contains a resin having a structural unit represented by the following formula: In the general formula (II-6), at least one of R6 and R7 is preferably a monovalent organic group represented by the general formula (II-2). When the polyimide precursor (A) contains a polyimide precursor represented by the general formula (II-6) in addition to the polyimide precursor represented by the general formula (II-5), the effect of improving resolution is further improved.

[0118] In one embodiment, the polyimide precursor (A) is represented by the following general formula (II-9): [ka] {wherein R6, R7, and n1 are as defined above.} It is preferable that the polyimide precursor has a structural unit represented by the following formula: In general formula (II-9), at least one of R6 and R7 is preferably a monovalent organic group represented by general formula (II-4). (A) Polyimide precursor containing a polyimide precursor represented by general formula (II-9) in addition to a polyimide precursor represented by general formula (II-5) further enhances the effect of improving resolution.

[0119] [(A) Method for preparing polyimide precursor] The polyimide precursors of this embodiment containing the structures represented by general formula (II-1) and general formula (II-3) can be obtained, for example, by reacting a tetracarboxylic acid dianhydride containing the tetravalent organic group X1 having 6 to 40 carbon atoms with (a) an alcohol formed by bonding a monovalent organic group represented by general formula (II-2) and a hydroxyl group, an alcohol formed by bonding a monovalent organic group represented by general formula (II-4) and a hydroxyl group, and, if desired, (a) an alcohol other than the group represented by general formula (II-2) or (II-4) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester), and then polycondensing the resulting tetracarboxylic acid with a diamine containing the divalent organic group Y1 having 6 to 40 carbon atoms.

[0120] (Preparation of Acid / Ester Forms) In this embodiment, examples of tetracarboxylic dianhydrides containing a tetravalent organic group X1 having 6 to 40 carbon atoms include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. These may be used alone or in combination of two or more.

[0121] (a) Examples of alcohols other than the group represented by general formula (II-2) above include aliphatic alcohols having 5 to 30 carbon atoms and aromatic alcohols having 6 to 30 carbon atoms, such as 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.

[0122] The content of the component (a) in the polyimide precursor is preferably 50 mol % or more relative to the total content of R1, R2, R6, and R7. When the content of the component (a) exceeds 50 mol %, it is possible to obtain desired photosensitive properties, which is preferable. The content of the component (a) in the photosensitive resin composition is preferably 75 mol % or more relative to the total content of R1, R2, R6, and R7.

[0123] The above tetracarboxylic dianhydride and the above alcohol are stirred, dissolved, and mixed in a reaction solvent in the presence of a basic catalyst such as pyridine at a reaction temperature of 20 to 50°C for 4 to 10 hours, whereby the half-esterification reaction of the acid dianhydride proceeds, and the desired acid / ester form can be obtained.

[0124] The reaction solvent is preferably one that dissolves the acid / ester compound and the polyimide precursor, which is a polycondensation product of the acid / ester compound and a diamine, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. These may be used alone or in combination as needed.

[0125] (Preparation of Polyimide Precursor) A known 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, is added to and mixed with the acid / ester compound (typically a solution in the reaction solvent) under ice cooling to convert the acid / ester compound into a polyacid anhydride, and then a diamine containing a divalent organic group Y1 having 6 to 40 carbon atoms dissolved or dispersed in a separate solvent is added dropwise to the acid / ester compound to cause polycondensation, thereby obtaining a polyimide precursor that can be used in the embodiment.

[0126] Examples of diamines containing a divalent organic group Y1 having 6 to 40 carbon atoms include 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, 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]sulfone, bis[4-(3-aminophenoxy)phen 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)hexafluoropropane, 2,2-bis[4-(4-aminophenyl) 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, 9,9-bis(4-aminophenyl)fluorene, and compounds in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,Examples of the diaminodiphenylmethane include, but are not limited to, 4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

[0127] In an embodiment, in order to improve the adhesion between the photosensitive resin layer formed on a substrate by applying the negative photosensitive resin composition onto the substrate and various substrates, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized during the preparation of the polyimide precursor (A).

[0128] After the polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as needed, and then a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof is added to the reaction solution to precipitate the polymer component. The polymer is then purified by repeated redissolution and reprecipitation procedures, and vacuum dried to isolate a polyimide precursor that can be used in the embodiments. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0129] The molecular weight of the (A) polyimide precursor, 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, and particularly preferably 20,000 to 40,000. A weight average molecular weight of 8,000 or more is preferred because it provides good mechanical properties, while a weight average molecular weight of 150,000 or less is preferred because it provides good dispersibility in the developer and good resolution performance of the relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0130] The (B) photopolymerization initiator and other components can be the same as those in the first embodiment, including, for example, a solvent, a resin component other than the (A) polyimide precursor, a sensitizer, a monomer having a photopolymerizable unsaturated bond, an adhesion promoter, a thermal polymerization inhibitor, an azole compound, a hindered phenol compound, and an organic titanium compound.

[0131] In this embodiment, by introducing a compound having a similar structure to the imidization accelerator (a basic compound) into the polymer side chain, a higher imidization rate can be obtained than when the compound is used as an additive, and a negative-type photosensitive resin composition that has both storage stability and chemical resistance can be realized.

[0132] The photosensitive resin composition according to this embodiment contains a polyimide precursor, a photopolymerization initiator, and a solvent. The photosensitive resin composition according to the present embodiment has a viscosity change rate of within 5% compared to the initial viscosity when stored at a temperature of 23° C. and a humidity of 50% Rh for 4 weeks. Furthermore, when the photosensitive resin composition according to this embodiment is heated at 170°C for 2 hours to obtain a cured coating film, the imidization rate of the cured coating film is preferably 70% or more, and more preferably 85% or more. As described above, the photosensitive resin composition according to this embodiment has a high imidization rate and exhibits both storage stability and chemical resistance.

[0133] <Polyimide> The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (II-10). [ka] {In general formula (II-10), X 1 and Y 1 are the same as X1 and Y1 in general formula (II-1), and m is a positive integer. For the same reason, the preferred X1 and Y1 in general formula (II-1) are also preferred in the polyimide of general formula (II-10). The number m of repeating units in general formula (II-10) is not particularly limited, but may be an integer of 2 to 150. Another aspect of the present invention is a method for producing a polyimide, which includes a step of converting the above-described photosensitive resin composition into a polyimide. The method for producing a cured relief pattern, the semiconductor device, and the display device can also be used in the same manner as in the first embodiment.

[0134] A third embodiment of the present invention will now be described. In the following description, the drawings may be referenced. The cured film according to the present embodiment is a photosensitive resin composition containing (A) a polyimide precursor, which is coated, exposed, developed, and cured by the method described below, and then subjected to IR spectrum measurement by the ATR (Attenuated Total Reflection) method. The cured film has a peak at 2950 cm -1 Nearby peaks and 1720cm -1 Ratio of peaks around 2950 cm -1 Nearby peak: 1720cm-1 The peak in the vicinity of the peak) is not limited as long as it is 0.05 to 0.35. In this embodiment, the IR spectrum measurement by the ATR method was carried out by the method described in the examples below.

[0135] The cured film typically contains (A) a polyimide precursor and / or a polyimide, (B) a polymerization initiator, (C) a crosslinking agent, and (D) an organic solvent, and may also contain (E) a thermal base generator, if necessary. Such a hardened film is used, for example, as an interlayer insulating film for a redistribution layer in a semiconductor device including a semiconductor chip, a sealing material covering the semiconductor chip, and a redistribution layer having an area larger than that of the semiconductor chip in a planar view. Each of the components will be explained below.

[0136] [(A) Polyimide precursor] The polyimide precursor (A) according to this embodiment will be described. The polyimide precursor (A) according to the present embodiment is not limited as long as it can form a cured relief pattern by the action of the photopolymerization initiator (B) and the cured film can have the above-mentioned range. The polyimide precursor (A) according to the present embodiment preferably contains, as a main component, at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. Here, "main component" means that the resin accounts for 60% by mass or more, preferably 80% by mass or more, of the total resin. Furthermore, the polyimide precursor may contain other resins as needed.

[0137] From the viewpoint of the heat resistance and mechanical properties of the film obtained after heat treatment, the weight-average molecular weight of the (A) polyimide precursor is preferably 1,000 or more, more preferably 5,000 or more, as determined by gel permeation chromatography in terms of polystyrene. The upper limit is preferably 100,000 or less. From the viewpoint of solubility in a developer, the weight-average molecular weight is more preferably 50,000 or less.

[0138] In the resin composition according to the present embodiment, the polyimide precursor (A) that is preferable from the viewpoint of heat resistance and photosensitivity is represented by the following general formula (III-1): [ka] In the formula, X is a tetravalent organic group, Y is a divalent organic group, n1 is an integer of 2 to 150, R1 and R2 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a group represented by the following general formula (III-2): [ka] (wherein 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), or a monovalent organic group represented by the following general formula (III-3): [ka] (wherein R6, R7, and R8 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m2 represents an integer of 2 to 10.) The structure is expressed as follows. Among these groups R1 and R2, the structure represented by general formula (III-2) is preferred from the viewpoint of the electrical properties of the resulting cured film.

[0139] In the polyimide precursor, in general formula (III-1), X preferably contains a tetravalent group represented by the following general formula (III-4) or (III-5). [ka] {In the formula, a1 represents an integer of 0 to 2, and R9 represents a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 10 carbon atoms. When there are multiple R9s, they may be the same or different.} [ka] {wherein n2 is an integer of 0 to 5, and X n1 is a single bond or a divalent organic group, and X n1 If there are multiple n1 may be the same or different. X1 is a single bond or a divalent organic group, and X1 or X n1 At least one of a6 and a8 is an organic group selected from a single bond, an oxycarbonyl group, an oxycarbonylmethylene group, a carbonylamino group, a carbonyl group, and a sulfonyl group. a6 and a8 are each independently an integer of 0 to 3, and a7 is an integer of 0 to 4. R 14 , R 15 , and R 16 each independently represents a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 10 carbon atoms; a7 or R 15 If there are multiple occurrences, they may be the same or different.

[0140] In the general formula (III-1), the tetravalent organic group represented by X is preferably an organic group having 6 to 40 carbon atoms, and more preferably a tetravalent aromatic group in which one of the -COOR1 group and the -CONH- group is bonded to the same aromatic ring and both are in the ortho position relative to each other, or an alicyclic aliphatic group. In the former case, the aromatic ring to which the -COOR1 group is bonded and the aromatic ring to which the -COOR2 group is bonded may be the same aromatic ring or different aromatic rings. In this context, the aromatic ring is preferably a benzene ring.

[0141] The tetravalent organic group represented by X is more preferably a group represented by the following formula: [ka] Examples of the structure include, but are not limited to, the structure of X. The structure of X may be one type or a combination of two or more types.

[0142] In particular, in the photosensitive resin composition of the present invention, the tetravalent organic group represented by X in the general formula (III-1) is preferably any of the following (III-C1) to (III-C3): [ka] [ka] [ka] It is more preferable that the composition contains at least one selected from the following: The polyimide precursor having such a structure provides the resulting polyimide with a corresponding structural backbone, which improves heat resistance and photosensitivity, and the resulting cured film (cured relief pattern) exhibits good chemical resistance and adhesion to copper pillars, thereby preventing deterioration of the epoxy resin used as the molding resin (sealant) and reducing its adhesion.

[0143] In the general formula (III-1), the divalent organic group represented by Y is preferably an aromatic group having 6 to 40 carbon atoms, for example, a group represented by the following formula: [ka]

[0144] [ka] {wherein A is a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), or a butyl group (-C4H9).} Examples include, but are not limited to, structures represented by the following formulas. Furthermore, the structure of Y may be one type or a combination of two or more types.

[0145] In the general formula (III-2), R3 is preferably a hydrogen atom or a methyl group, and R4 and R5 are each preferably a hydrogen atom from the viewpoint of photosensitivity. m1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, from the viewpoint of photosensitivity.

[0146] In the polyimide precursor, in general formula (III-1), Y preferably contains a divalent group represented by the following general formula (III-6). [ka] wherein n3 is an integer of 0 to 5, and Y n2 Y is an organic group having 1 to 10 carbon atoms which may contain a fluorine atom and does not contain any heteroatoms other than fluorine, an oxygen atom, or a sulfur atom. n2 When a plurality of R are present, they may be the same or different. a9 and a10 each independently represent an integer of 0 to 4. 17 and R 18 a10, R each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 10 carbon atoms. 17 , or R 18 When there are multiple, they may be the same or different.

[0147] In particular, in the photosensitive resin composition of the present invention, the polyimide precursor is represented by the general formula (III-1), and the divalent organic group represented by Y is one of the following (III-D1) to (III-D3): [ka] (In general formula (III-D1), R 10 ~R 13 are hydrogen atoms or C1 to C4 monovalent aliphatic groups, and may be different from each other or the same.) [ka] [ka] (In general formula (III-D3), R 14 ~R 21 are hydrogen atoms, halogen atoms, or C1 to C4 monovalent organic groups, and may be different from each other or the same.) It is more preferable that the composition contains at least one selected from the following: When the polyimide precursor has such a structure, the heat resistance and photosensitivity are further improved, and the resulting cured film exhibits good chemical resistance and good adhesion to copper pillars, thereby suppressing deterioration of the epoxy resin used as the molding resin and a decrease in adhesion.

[0148] In the photosensitive resin composition of the present invention, it is more preferable that X in the polyimide precursor contains a structural skeleton of formula (III-C1) and Y contains a structural skeleton of formula (III-D2). Furthermore, in the polyimide precursor, X more preferably contains a structural skeleton of formula (III-C2) and Y more preferably contains a structural skeleton of formula (III-D2). Furthermore, in the polyimide precursor, X more preferably contains a structural skeleton of formula (III-C3) and Y more preferably contains a structural skeleton of formula (III-D2). In the photosensitive resin composition of the present invention, it is more preferable that X in the polyimide precursor includes a structural skeleton represented by formula (III-C1) and Y includes a structural skeleton represented by formula (III-D3). Furthermore, it is more preferable that the polyimide precursor has X containing a structural skeleton of formula (III-C2) and Y containing a structural skeleton of formula (III-D3). Furthermore, in the polyimide precursor, X more preferably contains a structural skeleton of formula (III-C3), and Y more preferably contains a structural skeleton of formula (III-D3). The polyimide precursor precursor has such a structure, which further improves heat resistance and photosensitivity, and the resulting cured film exhibits good chemical resistance and good adhesion to copper pillars, thereby more reliably suppressing deterioration of the epoxy resin used as the molding resin and loss of adhesion.

[0149] In the photosensitive resin composition of the present invention, the polyimide precursor comprises a first polyimide precursor and a second polyimide precursor. It is particularly preferred that, in the first polyimide precursor, X comprises a structural skeleton of formula (III-C1) and Y comprises a structural skeleton of formula (III-D2), and that, in the second polyimide precursor, X comprises a structural skeleton of formula (III-C3) and Y comprises a structural skeleton of formula (III-D2). The polyimide precursor particularly preferably includes a first polyimide precursor and a second polyimide precursor, and the first polyimide precursor preferably includes X having a structural skeleton represented by formula (III-C2) and Y having a structural skeleton represented by formula (III-D2), and the second polyimide precursor preferably includes X having a structural skeleton represented by formula (III-C3) and Y having a structural skeleton represented by formula (III-D2). The polyimide precursor having such a structure has particularly improved heat resistance and photosensitivity, and the resulting cured film exhibits good chemical resistance and good adhesion to copper pillars, making it possible to particularly reliably suppress deterioration of the epoxy resin used as the molding resin and a decrease in adhesion.

[0150] [(A) Method for preparing polyimide precursor] The ester-bonded polyimide precursor is prepared, for example, by first reacting a tetracarboxylic dianhydride having the desired tetravalent organic group X with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester). The acid / ester is then subjected to amide polycondensation with a diamine having a divalent organic group Y. Saturated aliphatic alcohols may be used in combination with the alcohol having the photopolymerizable group.

[0151] (Preparation of Acid / Ester Forms) In the present invention, examples of tetracarboxylic dianhydrides having a tetravalent organic group X that are suitable for preparing an ester-bonded polyimide precursor include, but are not limited to, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-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. These may be used alone or in combination.

[0152] In the present invention, examples of alcohols having a photopolymerizable group that are preferably used to prepare an ester bond type polyimide precursor 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, and 2-hydroxy-3-t-butoxypropyl acrylate. acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 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, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.

[0153] The saturated aliphatic alcohols that can be optionally used together with the alcohols having a photopolymerizable group are preferably saturated aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

[0154] The tetracarboxylic dianhydride suitable for the present invention and the alcohol are mixed and stirred preferably in the presence of a basic catalyst such as pyridine, preferably in an appropriate reaction solvent, at a temperature of 20 to 50°C for 4 to 10 hours, whereby the esterification reaction of the acid anhydride proceeds, and the desired acid / ester can be obtained.

[0155] The reaction solvent is preferably one that completely dissolves the raw material tetracarboxylic dianhydride and alcohols, as well as the resulting acid / ester. More preferably, it is a solvent that completely dissolves the polyimide precursor, which is an amide polycondensation product of the acid / ester and diamine. Examples of such solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. Specific examples of these solvents include: Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate; Lactones include, for example, γ-butyrolactone; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; Halogenated hydrocarbons, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, etc.; Examples of hydrocarbons include hexane, heptane, benzene, toluene, and xylene. These may be used alone or in combination of two or more, as required.

[0156] (Preparation of Polyimide Precursor) The acid / ester compound (typically in solution in the reaction solvent) is mixed with an appropriate dehydration condensation agent, preferably under ice cooling, to convert the acid / ester compound into a polyanhydride. A diamine having a divalent organic group Y, which is suitable for use in the present invention, dissolved or dispersed in a separate solvent is then added dropwise to the acid / ester compound, and the two are subjected to amide polycondensation to obtain the desired polyimide precursor. Diaminosiloxanes may be used in combination with the diamine having a divalent organic group Y. Examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. In this manner, the intermediate polyanhydride is obtained.

[0157] In the present invention, examples of diamines having a divalent organic group Y that can be suitably used in the reaction with the polyacid anhydride obtained as described above include 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 ... ,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 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,

[0158] 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-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-aminophen 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)hexafluoropropane, 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, 9,9-bis(4-aminophenyl)fluorene, etc.; and those in which some of the hydrogen atoms on the benzene ring are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen atom, or the like; and mixtures thereof.

[0159] Specific examples of the substitution products include 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-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. The diamines are not limited to the above examples.

[0160] For the purpose of improving adhesion between a coating film formed from the photosensitive resin composition of the present invention and various substrates, diaminosiloxanes are used in combination with the diamines containing the divalent organic group Y when preparing (A) the photosensitive polyimide precursor. Specific examples of such diaminosiloxanes include 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane.

[0161] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off, if necessary. Then, a suitable poor solvent (e.g., water, aliphatic lower alcohol, or a mixture thereof) is added to the solution containing the polymer component to precipitate the polymer component. The polymer is further purified, if necessary, by repeated redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0162] From the viewpoint of the heat resistance and mechanical properties of the film obtained after heat treatment, the weight-average molecular weight of the ester-bonded polyimide precursor is preferably 1,000 or more, as measured by gel permeation chromatography in terms of polystyrene. It is more preferably 5,000 or more. The upper limit is preferably 100,000 or less. From the viewpoint of solubility in the developer, the weight-average molecular weight is more preferably 50,000 or less. Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the developing solvent for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0163] [Polyimide] The structure of the polyimide obtained by curing the polyimide precursor composition is represented by the following general formula (III-A). [ka] X in general formula (III-A) 1 , Y 1 , m corresponds to X, Y, n1 in the general formula (III-1), 1 is a tetravalent organic group, and Y 1 is a divalent organic group, and m is an integer of 1 or greater. For the same reason, preferred X, Y, and n1 in the general formula (III-1) are X in the general formula (III-A). 1 , Y 1 , m is also preferred.

[0164] [(B) Photopolymerization initiator] Next, the component (B) according to the present embodiment will be described. The (B) photopolymerization initiator is preferably one that generates radicals by absorbing and decomposing light of a specific wavelength. The amount of the (B) photopolymerization initiator in the photosensitive resin composition is 1 to 50 parts by mass per 100 parts by mass of the (A) polyimide precursor. When the amount is 1 part by mass or more, photosensitivity or patterning ability is exhibited, and when the amount is 50 parts by mass or less, the physical properties of the photosensitive resin layer after curing are improved.

[0165] In the case of a photopolymerization initiator, the generated radicals undergo a chain transfer reaction with the main chain skeleton of the (A) polyimide precursor (resin) or a radical polymerization reaction with a (meth)acrylate group introduced into the (A) polyimide precursor (resin), thereby curing the (A) polyimide precursor (resin).

[0166] (B) 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; and 1-phenyl-1,2-butanedione-2-(o-methoxyphenyl)-2-methyl ... Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as 1-phenyl-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; and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.

[0167] Among the above oxime photopolymerization initiators, from the viewpoint of adhesiveness, those having a structure represented by the following general formula (III-7) are more preferred, and those having a structure represented by any of the following formulas (III-8) to (III-11) are most preferred. [ka] (wherein Z is a sulfur or oxygen atom, and R 41 represents a methyl group, a phenyl group, or a divalent organic group, and R42 ~R 44 each independently represents a hydrogen atom or a monovalent organic group. [ka] [ka] [ka] [ka]

[0168] [(C) Crosslinking agent] The crosslinking agent (C) according to this embodiment may be a monomer having a photopolymerizable unsaturated bond. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, particularly, but not limited to, mono- or di(meth)acrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; Mono- or di(meth)acrylates of propylene glycol or polypropylene glycol; Mono-, di- or tri(meth)acrylates of glycerol; Cyclohexane di(meth)acrylate; Diacrylate and dimethacrylate of 1,4-butanediol, di(meth)acrylate of 1,6-hexanediol;

[0169] Neopentyl glycol di(meth)acrylate; Mono- or di(meth)acrylate of bisphenol A; Benzene trimethacrylate; Isobornyl (meth)acrylate; Acrylamide and its derivatives; methacrylamide and its derivatives; Trimethylolpropane tri(meth)acrylate; Di- or tri(meth)acrylates of glycerol; Di-, tri-, or tetra(meth)acrylates of pentaerythritol; and compounds such as ethylene oxide or propylene oxide adducts of these compounds.

[0170] Here, the peak value of the IR spectrum measurement of the cured film of this embodiment can be adjusted by appropriately selecting the type and amount of the crosslinking agent (C) in the photosensitive resin composition. Specifically, by increasing the amount of the crosslinking agent containing an alkyl group in one molecule, the peak value of 2950 cm -1 The higher the alkyl group content in one molecule of the crosslinking agent, the higher the peak intensity around 2950 cm. -1 The peak intensity around 1720 cm-1 is derived from the carbonyl group in the polyimide precursor and polyimide, and the peak intensity can be changed by increasing or decreasing the content of carbonyl groups per unit consisting of acid dianhydride and diamine.

[0171] It is preferable that the (C) crosslinking agent contains tetraethylene glycol dimethacrylate, and it is more preferable that the (C) crosslinking agent is a mixture of a compound containing two methacryl groups and / or two acrylic groups in the molecule and a compound containing three or more methacryl groups and / or two acrylic groups in the molecule.

[0172] The content of the crosslinking agent according to the present embodiment is preferably 1 to 100 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, more preferably 5 to 80 parts by mass from the viewpoint of chemical resistance, and particularly preferably 10 to 60 parts by mass from the viewpoint of suppressing peeling of the copper pillar.

[0173] [(D) Organic solvent] The organic solvent according to the present embodiment is not limited as long as it can dissolve the (A) polyimide precursor, (B) photopolymerization initiator, (C) crosslinking agent, etc. Specific examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, and N-cyclohexyl-2-pyrrolidone, which can be used alone or in combination of two or more.

[0174] (E) Thermal base generator The photosensitive resin composition according to the present embodiment may contain a thermal base generator (E) as needed. The thermal base generator according to the present embodiment is not limited as long as it is a compound capable of generating a base upon heating, and examples thereof include an acidic compound capable of generating a base upon heating to 40°C or higher, or an ammonium salt having an anion with a pKa1 of 0 to 4 and an ammonium cation. Here, pKa1 indicates the logarithmic representation of the first proton dissociation constant (Ka) of a polyvalent acid. By including such a compound, for example, the cyclization reaction of the polyimide precursor can be carried out at a low temperature, and a composition with excellent stability can be provided. In particular, since the photosensitive resin composition according to the present embodiment includes a large amount of crosslinking agents, it tends to be difficult to cyclize the polyimide precursor at a low temperature. Therefore, by adding a thermal base generator, the imidization rate can be controlled. Examples of such compounds include those in which primary, secondary, and tertiary amines are protected with a protecting group that can be deprotected by heat. Examples of such protecting groups include a tert-butoxycarbonyl group and an Fmoc group, but the present invention is not limited to these. Here, the Fmoc group refers to a 9-fluorenylmethyloxycarbonyl group. It is more preferable that one or more amino groups are protected with a tert-butoxycarbonyl group.

[0175] The molecular weight of the protected amine is preferably 250 to 600. If the molecular weight is 250 or more, the base-protected compound remains in the film even after thermal curing, and the Cu void suppression effect can be exerted. The molecular weight is preferably 300 or more, and more preferably 340 or more. On the other hand, from the viewpoint of obtaining high resolution, the molecular weight is preferably 600 or less, more preferably 550 or less, more preferably 450 or less, and more preferably 400 or less. As such a compound, for example, compounds represented by the following formula (AM-1) and / or (AM-2) are preferably used. [ka] [ka]

[0176] [(F) Other ingredients] The photosensitive resin composition according to this embodiment may further contain components other than the above components (A) to (E). For example, a thermal crosslinking agent that crosslinks when heated, a resin other than the (A) polyimide precursor, a sensitizer, an adhesion promoter, a thermal polymerization inhibitor, a copper discoloration inhibitor, and the like can be added. The thermal crosslinking agent optionally used in the present embodiment may be any compound having multiple functional groups in the molecule, such as an acrylic group, a methacrylic group, an epoxy group, a methylol group, an allyl group, a vinyl group, or a maleimide group.

[0177] The blending amount of the thermal crosslinking agent is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, per 100 parts by mass of the (A) resin.

[0178] The photosensitive resin composition according to the present embodiment may further contain a resin component other than the polyimide precursor (A). Examples of the resin component that can be contained include polyimide, polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The amount of these resin components to be added is preferably in the range of 0.01 to 20 parts by mass per 100 parts by mass of the polyimide precursor (A).

[0179] The photosensitive resin composition according to the present embodiment may optionally contain a sensitizer in order to improve photosensitivity. Examples of the sensitizer include 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, p-dimethylaminocinnamylideneindanone, 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,

[0180] 3,3'-Carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-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, dimethylamino Examples include isoamyl benzoate, 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, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. These can be used alone or in combination of two or more.

[0181] When the photosensitive 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.

[0182] In order to improve the adhesion between a film formed from the photosensitive resin composition according to this embodiment and a substrate, an adhesion promoter can be optionally blended into the photosensitive resin composition. Examples of the adhesion promoter 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, and N-[3-(triethoxysilyl)propyl]phthalate. Examples of suitable adhesives include silane coupling agents such as amido acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane, and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0183] Among these adhesion aids, it is more preferable to use a silane coupling agent in terms of adhesive strength. When the photosensitive resin composition contains an adhesion aid, the blending amount is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0184] When the photosensitive resin composition according to the present embodiment is in a solution state containing a solvent, a thermal polymerization inhibitor can be optionally blended into the photosensitive resin composition to improve the stability of its viscosity and photosensitivity during storage. Examples of the thermal polymerization inhibitor 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.

[0185] When the thermal polymerization inhibitor is added to the photosensitive resin composition, the amount of the thermal polymerization inhibitor added is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the (A) photosensitive polyimide precursor.

[0186] When the substrate to which the resin composition according to the present embodiment is applied is made of, for example, copper or a copper alloy, an azole compound can be optionally blended to suppress discoloration of the copper surface. Examples of the azole compound 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, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and the like. Examples of the benzotriazole include 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, 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, and 1-methyl-1H-tetrazole. Particularly preferred is at least one selected from tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in a mixture of two or more.

[0187] When the photosensitive resin composition according to the present embodiment contains the azole compound, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound relative to 100 parts by mass of the (A) polyimide precursor is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition according to the present embodiment is formed on copper or a copper alloy. On the other hand, when the blending amount is 10 parts by mass or less, the excellent photosensitivity of the photosensitive resin composition is maintained.

[0188] In order to suppress discoloration of the copper surface, a hindered phenol compound can be optionally blended in place of or together with the azole compound. Examples of the hindered phenol compound include 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],

[0189] 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, 1,3,5-tris(3-hydroxy-2,6-dimethyl- 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,

[0190] 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-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -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-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 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,

[0191] Examples of the hydroxybenzoates include, but are not limited to, 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-2,4,6-(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.

[0192] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, and from the viewpoint of photosensitivity, more preferably 0.5 to 10 parts by mass. When the amount of the hindered phenol compound relative to 100 parts by mass of the (A) polyimide precursor is 0.1 part by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented. On the other hand, when the amount is 20 parts by mass or less, the excellent photosensitivity of the photosensitive resin composition is maintained.

[0193] The method for producing a cured film of the present embodiment includes: (1) a step of forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition onto the substrate; (2) a step of applying a photosensitive resin composition to the photosensitive resin layer at 10 to 1200 mJ / cm 2 More preferably, the exposure dose is 10 to 1000 mJ / cm 2 More preferably, the exposure dose is 30 to 500 mJ / cm 2 (3) developing the photosensitive resin layer after the exposure to form a relief pattern; and (4) heat-treating the relief pattern at 200°C in a nitrogen atmosphere to form a hardened relief pattern. This will be explained in detail below. A typical embodiment of each step will be described below.

[0194] (1)Coating process In this step, the photosensitive resin composition according to the present embodiment is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. Substrates include, for example: Metal substrates made of silicon, aluminum, copper, copper alloys, etc.; Resin substrates such as epoxy, polyimide, and polybenzoxazole; a substrate in which a metal circuit is formed on the resin substrate; A substrate made of multiple layers of metal or metal and resin. etc. can be used.

[0195] As the application method, a method that has conventionally been used for applying a photosensitive resin composition, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or a method of spray application using a spray coater, can be used.

[0196] If necessary, the photosensitive resin composition film can be dried. Drying methods include air drying, heat drying using an oven or a hot plate, vacuum drying, and the like. The coating film is preferably dried under conditions that do not cause imidization of the (A) polyimide precursor (polyamic acid ester) in the photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be performed under conditions of 20°C to 140°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the substrate.

[0197] (2) Exposure process In this step, the photosensitive resin layer formed above is exposed to light. Examples of the exposure device that can be used include a contact aligner, a mirror projection device, and a stepper. The exposure can be performed directly or through a photomask or reticle having a pattern. The light used for exposure is, for example, an ultraviolet light source. The exposure dose is not limited as long as a pattern can be formed, but is preferably 10 to 1200 mJ / cm 2 , or 10 to 1000 mJ / cm 2 The range is preferably used, and 20 to 800 mJ / cm 2 Preferably, 30 to 500 mJ / cm 2 , or 50 to 600 mJ / cm 2 is more preferred.

[0198] After the exposure, post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as needed for the purpose of improving photosensitivity, etc. The baking conditions are preferably in the range of a temperature of 40 to 120°C and a time of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition of the present embodiment.

[0199] (3)Developing process In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The developing method for developing the exposed (irradiated) photosensitive resin layer can be selected from conventionally known photoresist developing methods. Examples include the rotary spray method, the puddle method, and the immersion method accompanied by ultrasonic treatment. Furthermore, after development, post-development baking may be performed at any desired temperature and time combination, as needed, for the purpose of adjusting the shape of the relief pattern, etc. The post-development baking temperature can be, for example, 80 to 130°C, and the time can be, for example, 0.5 to 10 minutes.

[0200] The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. Preferred good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative photosensitive resin composition. Furthermore, two or more types of each solvent, for example, several types, can also be used in combination.

[0201] (4)Heating process In this step, the relief pattern obtained by the above development is heated to dissolve the photosensitive component and also imidize the (A) polyimide precursor, thereby converting it into a cured relief pattern made of polyimide. Various methods can be selected for heat curing, such as using a hot plate, an oven, or a temperature-programmable heating oven, etc. The atmospheric gas used during heat curing may be air or an inert gas such as nitrogen or argon.

[0202] The heating temperature is not particularly limited, but a low heating temperature is preferable from the viewpoint of preventing effects on other components. 250°C or less is preferable, 230°C or less is more preferable, 200°C or less is more preferable, and 180°C or less is particularly preferable. From the viewpoint of preventing effects on other components, the heating time is preferably 1 hour to 4 hours, more preferably 1 hour 30 minutes to 3 hours, and even more preferably 2 hours. In this manner, a cured relief pattern can be produced.

[0203] In this embodiment, the pattern obtained by exposing and developing the photosensitive resin composition is referred to as a relief pattern, and the relief pattern obtained by heat curing is referred to as a cured relief pattern. This cured relief pattern is a cured film, and is used, for example, as an interlayer insulating film 6 of a semiconductor device, which will be described later. The cured film thus obtained contains a polyimide, and the polyimide has, for example, the structure of the above-mentioned general formula (III-A).

[0204] The cured film thus obtained has a viscosity of 2950 cm -1 Nearby peaks and 1720cm -1 Ratio of peaks around (2950cm -1 Nearby peak: 1720cm -1 The peak ratio (peak near the peak) is not limited as long as it is 0.05 to 0.35. If the peak ratio is 0.05 or more, chemical resistance tends to be good, and if it is 0.35 or less, adhesion to the copper pillar tends to be good. The peak ratio is preferably 0.07 to 0.32, and more preferably 0.1 to 0.25. When the cured film is used as the interlayer insulating film 6 of a semiconductor device described later, if the peak ratio is within the range of 0.05 to 0.35, the adhesion between the interlayer insulating film 6 in the rewiring layer 4 and the sealing material 3 will be excellent. Furthermore, from the viewpoint of chemical resistance, adhesion to copper pillars, and adhesion to sealing materials, -1 Nearby peaks and 1500cm -1 Ratio of peaks around (1380cm -1 Nearby peaks: 1500cm -1It is more preferable that the peak (peak near the peak) is 0.1 to 2.1, or 0.4 to 2.1. From the same viewpoint, the 5% weight loss temperature of the cured film is preferably 280°C or higher and 350°C or lower.

[0205] Here, the peak ratio represents the rate at which the polyimide precursor has closed its ring to form a polyimide in the cured film (hereinafter referred to as the imidization rate), and the peak intensity can be controlled by controlling the imidization rate of the cured film. The imidization rate can be controlled by adjusting the amount of an imidization accelerator such as a base generator. Examples of base generators include amine compounds protected by a tert-butoxycarbonyl group and the thermal base generators disclosed in International Publication No. 2017 / 038598. However, the base generators are not limited to these, and other known base generators can also be used.

[0206] 2950cm -1 The peak in this area is, for example, 2900 to 3000 cm -1 The peak is in the range. 1720cm -1 For example, the peak in the vicinity is 1680-1750 cm -1 The peak is in the range. 1380cm -1 For example, the peak in the vicinity is 1350-1450 cm -1 The peak is in the range. 1500cm -1 For example, the peak in the vicinity is 1460-1550 cm -1 The peak is in the range. If there are multiple peaks within a range, the peak with the greatest intensity within the range is taken as the peak near that range.

[0207] Furthermore, the semiconductor device and the manufacturing method thereof will be described in detail below with reference to the drawings.

[0208] (Semiconductor Devices) The present invention also provides a semiconductor device comprising the above-described cured film (cured relief pattern) of the present invention. As shown in FIG. 1, a semiconductor device (semiconductor IC) 1 is composed of a semiconductor chip 2, a sealing material (mold resin) 3 that covers the semiconductor chip 2, and a rewiring layer 4 that is in close contact with the semiconductor chip 2 and the sealing material 3.

[0209] As shown in FIG. 1, the sealing material 3 covers the surface of the semiconductor chip 2 and is formed with an area larger than the region of the semiconductor chip 2 in a plan view (as viewed from the arrow A).

[0210] The redistribution layer 4 is composed of a plurality of wires 5 electrically connected to a plurality of terminals 2a provided on the semiconductor chip 2, and an interlayer insulating film 6 filling the spaces between the wires 5. The plurality of terminals 2a provided on the semiconductor chip 2 are electrically connected to the wires 5 in the redistribution layer 4. One end of the wire 5 is connected to the terminal 2a, and the other end is connected to an external connection terminal 7. The entire surface of the wire 5 between the terminal 2a and the external connection terminal 7 is covered with the interlayer insulating film 6.

[0211] As shown in FIG. 1, in a plan view (as viewed from the arrow A), the redistribution layer 4 is formed to be larger than the semiconductor chip 2. The semiconductor device 1 shown in FIG. 1 is a fan-out wafer-level chip size package (WLCSP) type semiconductor device. In a fan-out type semiconductor device, the interlayer insulating film 6 in the redistribution layer 4 is in close contact with not only the semiconductor chip 2 but also the encapsulant 3. The semiconductor chip 2 is made of a semiconductor such as silicon, and has a circuit formed therein.

[0212] (Rewiring layer) The rewiring layer 4 is mainly composed of wiring 5 and an interlayer insulating film 6 that covers the periphery of the wiring 5. From the viewpoint of preventing unintended conduction with the wiring 5, the interlayer insulating film 6 is preferably a highly insulating material.

[0213] Here, as described above, the "rewiring layer 4" in this embodiment is a thin-film layer having wiring 5 and interlayer insulating layer 6, and does not include an interposer or a printed wiring board. Since the semiconductor device (semiconductor IC) 1 uses the rewiring layer 4, it is thinner than a semiconductor device that uses an interposer such as a flip-chip BGA, as shown in FIG.

[0214] In this embodiment, the thickness of the redistribution layer 4 can be approximately 3 to 30 μm. The thickness of the redistribution layer 4 may be 1 μm or more, 5 μm or more, or 10 μm or more. The thickness of the redistribution layer 4 may be 40 μm or less, 30 μm or less, or 20 μm or less.

[0215] When the semiconductor device 1 is viewed from above (as viewed from the arrow A), it appears as shown in the following Figure 2. Note that the sealing material 3 is omitted.

[0216] The semiconductor device 1 shown in FIG. 2 is configured so that the area S1 of the redistribution layer 4 is larger than the area S2 of the semiconductor chip 2. While the area S1 of the redistribution layer 4 is not particularly limited, from the viewpoint of increasing the number of external connection terminals, the area S1 of the redistribution layer 4 is preferably 1.05 times or more, more preferably 1.1 times or more, more preferably 1.2 times or more, and particularly preferably 1.3 times or more, the area S2 of the semiconductor chip 2. While there is no particular upper limit, the area S1 of the redistribution layer 4 may be 50 times or less, 25 times or less, 10 times or less, or 5 times or less the area S2 of the semiconductor chip 2. Note that in FIG. 2, the area S1 of the redistribution layer 4 also includes the area of ​​the portion of the redistribution layer 4 covered by the semiconductor chip 2.

[0217] Furthermore, the external shapes of the semiconductor chip 2 and the redistribution layer 4 may be the same or different. In Fig. 2, the external shapes of the semiconductor chip 2 and the redistribution layer 4 are both similar rectangular shapes, but the shapes may be other than rectangular.

[0218] The redistribution layer 4 may be a single layer or may be a multi-layer consisting of two or more layers. The redistribution layer 4 includes wires 5 and an interlayer insulating film 6 filling the spaces between the wires 5, but the redistribution layer 4 may include a layer consisting only of the interlayer insulating film 6 or a layer consisting only of the wires 5.

[0219] The wiring 5 is not particularly limited as long as it is made of a highly conductive material, but copper is generally used.

[0220] (Sealing material) There are no particular limitations on the material of the sealing material 3, but epoxy resin is preferred from the viewpoints of heat resistance and adhesion to the interlayer insulating film.

[0221] 1, the encapsulant 3 is preferably in direct contact with the semiconductor chip 2 and the rewiring layer 4, and more preferably in direct contact with the interlayer insulating film 6. This effectively improves the encapsulation from the surface of the semiconductor chip 2 to the surface of the rewiring layer 4.

[0222] The sealing material 3 may be a single layer or may have a structure in which multiple layers are laminated. When the sealing material 3 has a laminated structure, it may be a laminated structure of the same type of material or a laminated structure of different materials.

[0223] (Interlayer insulating film) The interlayer insulating film 6 is made of a cured film obtained by curing the above-mentioned photosensitive resin composition. In this embodiment, when the interlayer insulating film 6 was subjected to IR spectrum measurement by the ATR method, the -1 Nearby peaks and 1720cm -1 Ratio of peaks around (2950cm -1 Nearby peak: 1720cm -1 It is characterized by the peak (peak near the center) being 0.05 to 0.35.

[0224] In this embodiment, the reason why an IR spectrum peak ratio of 0.05 to 0.35 results in excellent adhesion to the encapsulant is unclear, but the inventors believe it to be as follows: Typically, the epoxy resin used as the encapsulant and the polyimide resin used as the cured film have different linear expansion coefficients, which causes residual stress during the cooling process after heating. Peeling occurs when this residual stress exceeds a certain level. Here, it is believed that if alkyl groups derived from a crosslinking agent or polymer side chains are present in the cured product, the linear expansion coefficient of the cured product becomes similar to that of the epoxy resin, or the Young's modulus during thermal history decreases, thereby reducing the residual stress and improving adhesion.

[0225] The peak value of the IR spectrum measurement of the interlayer insulating film of this embodiment can be adjusted by appropriately selecting the type and amount of the (C) crosslinking agent in the photosensitive resin composition. It can also be adjusted by introducing a hydrocarbon group into the main chain or side chain of a resin such as a polyimide precursor. For example, by introducing an alkyl group into the main chain or side chain, the peak value of 2950 cm -1 This can increase the peak intensity around 2950 cm in the IR spectrum. Specific examples include the introduction of 2-hydroxyethyl methacrylate into the side chain of the polyimide precursor, or the use of the aforementioned photopolymerizable monomer with an unsaturated bond. (C) The amount of crosslinking agent is adjusted to increase the peak intensity around 2950 cm in the IR spectrum. -1 Nearby peaks and 1720cm -1 Ratio of peaks around (2950cm -1 Nearby peak: 1720cm -1 The amount of the polyimide precursor (peak near the peak) is not limited as long as it is 0.05 to 0.35, but for example, it is preferably 1 to 100 parts by mass relative to 100 parts by mass of the polyimide precursor (A), more preferably 5 to 80 parts by mass from the viewpoint of chemical resistance, and particularly preferably 10 to 60 parts by mass from the viewpoint of suppressing peeling of the copper pillar.

[0226] The interlayer insulating film 6 in the redistribution layer 4 may have multiple layers. That is, when viewed in cross section of the redistribution layer 4, the redistribution layer 4 may include a first interlayer insulating film layer, a second interlayer insulating film layer, and an intermediate layer that is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer and is provided between the first interlayer insulating film layer and the second interlayer insulating film layer. The intermediate layer is, for example, a wiring 5.

[0227] The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same peak ratio or different peak ratios. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions, different peak ratios, or different film thicknesses, it is possible to impart different properties to each interlayer insulating film layer, which is preferable.

[0228] When the interlayer insulating film 6 is multi-layered, it is sufficient that at least one of the multiple layers has an i-line transmittance of 80% or less, but it is preferable that the i-line transmittance of the interlayer insulating film layer (first interlayer insulating film layer) in contact with the sealing material 3 is 80% or less. If the i-line transmittance of the interlayer insulating film layer in contact with the sealing material 3 is 80% or less, i-line can be efficiently absorbed when forming an interlayer insulating film layer that is not in contact with the sealing material 3, and deterioration of the sealing material can be prevented.

[0229] (Method of manufacturing a semiconductor device) The method for manufacturing the semiconductor device according to this embodiment will be described with reference to FIG. The method for manufacturing a semiconductor device includes the steps of covering a semiconductor chip with a sealing material and forming a rewiring layer that is larger in area than the semiconductor chip in a plan view and includes an interlayer insulating film. In FIG. 3A, a pre-processed wafer 10 is prepared. Then, in FIG. 3B, the pre-processed wafer 10 is diced to form a plurality of semiconductor chips 2. The semiconductor chips 2 may be purchased. The semiconductor chips 2 thus prepared are attached to a support 11 at predetermined intervals, as shown in FIG. 3C.

[0230] Next, molding resin 12 is applied from above semiconductor chip 2 to above support 11, and mold sealing is performed as shown in FIG. 3D. Next, support 11 is peeled off, and molding resin 12 is inverted (see FIG. 3E). As shown in FIG. 3E, semiconductor chip 2 and molding resin 12 appear to be on approximately the same plane. Next, in the step shown in FIG. 3F, photosensitive resin composition 13 is applied onto semiconductor chip 2 and molding resin 12. Then, the applied photosensitive resin composition 13 is exposed and developed to form a relief pattern (relief pattern forming step). Note that photosensitive resin composition 13 may be either positive or negative. Furthermore, the relief pattern is heated to form a cured relief pattern (interlayer insulating film forming step). Furthermore, wiring is formed in areas where the cured relief pattern is not to be formed (wiring forming step).

[0231] In this embodiment, the relief pattern forming step, interlayer insulating film forming step, and wiring forming step are combined together to form a rewiring layer forming step for forming a rewiring layer connected to the semiconductor chip 2.

[0232] The interlayer insulating film in the rewiring layer may be multi-layered, and therefore the rewiring layer forming step may include a plurality of relief pattern forming steps, a plurality of interlayer insulating film forming steps, and a plurality of wiring forming steps.

[0233] 3G, a plurality of external connection terminals 7 corresponding to each semiconductor chip 2 are formed (bump formation), and the semiconductor chips 2 are diced apart. This allows a semiconductor device (semiconductor IC) 1 to be obtained, as shown in FIG. 3H. In this embodiment, a plurality of fan-out type semiconductor devices 1 can be obtained by the manufacturing method shown in FIG.

[0234] In this embodiment, the interlayer insulating film formed through the above process was measured for IR spectrum by the ATR method. -1 Nearby peaks and 1720cm -1 Ratio of peaks around (2950cm -1 Nearby peak: 1720cm -1A cured film having a peak (peak near the peak) of 0.05 to 0.35 can be obtained. This allows the interlayer insulating film to exhibit good chemical resistance and good adhesion to the copper pillars, and can prevent deterioration of the epoxy resin used as the molding resin and a decrease in adhesion.

[0235] In the above description, the cured film (cured relief pattern) is used as an interlayer insulating film of a rewiring layer of a semiconductor device, but the present invention is not limited to this. For example, the cured film can also be used as a surface protective 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.

[0236] A fourth aspect of the present embodiment will be described with reference to the drawings.

[0237] (Semiconductor Devices) As shown in FIG. 1, a semiconductor device (semiconductor IC) 1 is composed of a semiconductor chip 2, a sealing material (mold resin) 3 that covers the semiconductor chip 2, and a rewiring layer 4 that is in close contact with the semiconductor chip 2 and the sealing material 3.

[0238] As shown in FIG. 1, the sealing material 3 covers the surface of the semiconductor chip 2 and is formed with an area larger than the region of the semiconductor chip 2 in a plan view (as viewed from the arrow A).

[0239] The redistribution layer 4 is composed of a plurality of wires 5 electrically connected to a plurality of terminals 2a provided on the semiconductor chip 2, and an interlayer insulating film 6 filling the spaces between the wires 5. The plurality of terminals 2a provided on the semiconductor chip 2 are electrically connected to the wires 5 in the redistribution layer 4. One end of the wire 5 is connected to the terminal 2a, and the other end is connected to an external connection terminal 7. The entire surface of the wire 5 between the terminal 2a and the external connection terminal 7 is covered with the interlayer insulating film 6.

[0240] As shown in FIG. 1, in a plan view (as viewed from the arrow A), the redistribution layer 4 is formed to be larger than the semiconductor chip 2. The semiconductor device 1 shown in FIG. 1 is a fan-out wafer-level chip size package (WLCSP) type semiconductor device. In a fan-out type semiconductor device, the interlayer insulating film 6 in the redistribution layer 4 is in close contact with not only the semiconductor chip 2 but also the encapsulant 3. The semiconductor chip 2 is made of a semiconductor such as silicon, and has a circuit formed therein.

[0241] (Rewiring layer) The rewiring layer 4 is mainly composed of wiring 5 and an interlayer insulating film 6 that covers the periphery of the wiring 5. From the viewpoint of preventing unintended conduction with the wiring 5, the interlayer insulating film 6 is preferably a highly insulating material.

[0242] Here, as described above, the "rewiring layer 4" in this embodiment is a thin-film layer having wiring 5 and interlayer insulating layer 6, and does not include an interposer or a printed wiring board. Since the semiconductor device (semiconductor IC) 1 uses the rewiring layer 4, it is thinner than a semiconductor device that uses an interposer such as a flip-chip BGA, as shown in FIG.

[0243] In this embodiment, the thickness of the redistribution layer 4 can be approximately 3 to 30 μm. The thickness of the redistribution layer 4 may be 1 μm or more, 5 μm or more, or 10 μm or more. The thickness of the redistribution layer 4 may be 40 μm or less, 30 μm or less, or 20 μm or less.

[0244] When the semiconductor device 1 is viewed from above (as viewed from the arrow A), it appears as shown in the following Figure 2. Note that the sealing material 3 is omitted.

[0245] The semiconductor device 1 shown in FIG. 2 is configured so that the area S1 of the redistribution layer 4 is larger than the area S2 of the semiconductor chip 2. While the area S1 of the redistribution layer 4 is not particularly limited, from the viewpoint of increasing the number of external connection terminals, the area S1 of the redistribution layer 4 is preferably 1.05 times or more, more preferably 1.1 times or more, more preferably 1.2 times or more, and particularly preferably 1.3 times or more, the area S2 of the semiconductor chip 2. While there is no particular upper limit, the area S1 of the redistribution layer 4 may be 50 times or less, 25 times or less, 10 times or less, or 5 times or less the area S2 of the semiconductor chip 2. Note that in FIG. 2, the area S1 of the redistribution layer 4 also includes the area of ​​the portion of the redistribution layer 4 covered by the semiconductor chip 2.

[0246] Furthermore, the external shapes of the semiconductor chip 2 and the redistribution layer 4 may be the same or different. In Fig. 2, the external shapes of the semiconductor chip 2 and the redistribution layer 4 are both similar rectangular shapes, but the shapes may be other than rectangular.

[0247] The redistribution layer 4 has two or more layers, may have four or more layers, or may have eight or more layers. The redistribution layer 4 includes wires 5 and an interlayer insulating film 6 filling the spaces between the wires 5, but the redistribution layer 4 may include a layer consisting only of the interlayer insulating film 6 or a layer consisting only of the wires 5.

[0248] The wiring 5 is not particularly limited as long as it is made of a highly conductive material, but copper is generally used.

[0249] (Sealing material) There are no particular limitations on the material of the sealing material 3, but epoxy resin is preferred from the viewpoints of heat resistance and adhesion to the interlayer insulating film.

[0250] 1, the encapsulant 3 is preferably in direct contact with the semiconductor chip 2 and the rewiring layer 4. This effectively improves the encapsulation from the surface of the semiconductor chip 2 to the surface of the rewiring layer 4.

[0251] The sealing material 3 may be a single layer or may have a structure in which multiple layers are laminated. When the sealing material 3 has a laminated structure, it may be a laminated structure of the same type of material or a laminated structure of different materials.

[0252] (Interlayer insulating film) In the manufacturing process of a fanout semiconductor device, a photosensitive resin composition is applied to a chip encapsulation structure composed of a semiconductor chip 2 and an encapsulant 3 to form a redistribution layer 4. The photosensitive resin composition is then exposed to light including i-rays. The photosensitive resin composition is then developed and cured to selectively form areas with and without the cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6. Furthermore, wiring 5 is formed in the areas without the cured product of the photosensitive resin composition. Typically, the redistribution layer 4 is often multilayered. That is, a photosensitive resin composition is further applied, exposed, developed, and cured on the interlayer insulating film 6 and wiring 5, and wiring is formed. Various chemical solutions are used in the process of forming the interlayer insulating film 6 and the process of forming the wiring 5.

[0253] The interlayer insulating film 6 in the redistribution layer 4 may have multiple layers. That is, when viewed in cross section of the redistribution layer 4, the redistribution layer 4 may include a first interlayer insulating film layer, a second interlayer insulating film layer, and an intermediate layer that is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer and is provided between the first interlayer insulating film layer and the second interlayer insulating film layer. The intermediate layer is, for example, a wiring 5.

[0254] The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions, different refractive index differences, or different film thicknesses, it is possible to impart different properties to each interlayer insulating film layer, which is preferable.

[0255] (Composition of interlayer insulating film) The composition of the interlayer insulating film 6 is not particularly limited, but it is preferable that the film contains at least one compound selected from, for example, polyimide, polybenzoxazole, or a polymer having a phenolic hydroxyl group.

[0256] (Resin composition for forming interlayer insulating film) The resin composition used to form the interlayer insulating film 6 is not particularly limited as long as it is a photosensitive resin composition, but is preferably a photosensitive resin composition containing at least one compound selected from a polyimide precursor, a polybenzoxazole precursor, or a polymer having a phenolic hydroxyl group. The resin composition used to form the interlayer insulating film 6 may be in the form of a liquid or a film. Furthermore, the resin composition used to form the interlayer insulating film 6 may be either a negative-type photosensitive resin composition or a positive-type photosensitive resin composition.

[0257] In this embodiment, the pattern obtained after exposing and developing the photosensitive resin composition is referred to as a relief pattern, and the relief pattern that is heat-cured is referred to as a cured relief pattern. This cured relief pattern becomes the interlayer insulating film 6. The interlayer insulating film 6 may be formed from a multilayer cured relief pattern. In this embodiment, the multilayer cured relief pattern (interlayer insulating film 6) is manufactured by the following method.

[0258] <Method for manufacturing a multilayer cured relief pattern> The method for producing a multi-layer cured relief pattern comprises the following steps: (1) forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition onto the substrate; (2) a step of exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) a first heat-curing step in which the relief pattern is heat-treated at a temperature in the range of 150°C to 200°C for 0 to 240 minutes to form a semi-cured relief pattern; and (5) a second heat-curing step of heat-treating the semi-cured relief pattern at a temperature in the range of 200 to 260°C, which is higher than that in the first heat-curing step, for 10 minutes or less to form a cured relief pattern; Furthermore, the steps (1) to (5) are performed again in order. This allows the interlayer insulating film 6 to have a multilayer structure (multilayer cured relief pattern). It is preferable to repeat the steps (1) to (5) in the above order 3 to 8 times. The substrate is, for example, a substrate composed of a semiconductor chip and a sealing material covering the semiconductor chip.

[0259] According to the manufacturing method of the present invention, it is possible to achieve both a curing reaction that provides sufficient film properties for the photosensitive resin as an interlayer insulating film and suppress a decrease in the yield of fan-out semiconductor devices due to thermal damage. That is, by suppressing thermal damage to the semiconductor chip and encapsulating resin due to heat during thermal curing, the curing reaction of the photosensitive resin composition proceeds smoothly, thereby increasing the proportion of resin in the polymer and achieving sufficient film properties and chemical resistance. The steps (1) to (5) will be described in detail later.

[0260] Hereinafter, as the photosensitive resin composition constituting the interlayer insulating film 6, polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group will be described in order.

[0261] <Polyimide precursor composition> (A) Photosensitive resin Examples of the photosensitive resin used in the polyimide precursor composition include polyamide, polyamic acid ester, etc. For example, the polyamic acid ester may be a polyamic acid ester containing a repeating unit represented by the following general formula (IV-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 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 4 carbon atoms, or a group represented by the following general formula (IV-2): [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.) or a monovalent organic group represented by the following general formula (IV-3): [ka] (In the formula, R6, R7, and R8 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m2 represents an integer of 2 to 10.) It is an ammonium ion represented by the formula: It has a structure represented by the following formula:

[0262] A plurality of polyamic acid esters represented by general formula (IV-1) may be mixed together, or a polyamic acid ester obtained by copolymerizing polyamic acid esters represented by general formula (IV-1) with each other may be used.

[0263] In general formula (IV-1), X1 is not particularly limited, but from the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3, X1 is preferably a tetravalent organic group containing an aromatic group. Specifically, X1 is preferably a tetravalent organic group containing at least one structure represented by the following formulas (IV-4) to (IV-6). [ka] [ka] [ka] (In general formula (IV-6), R9 is any one of an oxygen atom, a sulfur atom, and a divalent organic group.)

[0264] In the general formula (IV-6), R9 is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom. R9 may contain a hydroxyl group.

[0265] From the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3, X1 in the general formula (IV-1) is particularly preferably a tetravalent organic group containing a structure represented by the following formula (IV-7).

[0266] [ka]

[0267] In general formula (IV-1), X1 is preferably a tetravalent organic group containing a structure represented by the following formula (IV-7) or formula (IV-5). [ka] [ka]

[0268] X1 is more preferably a tetravalent organic group containing a structure represented by the following formula (IV-5). [ka]

[0269] Although there are no particular limitations on Y1, Y1 is preferably a divalent organic group containing an aromatic group from the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3. Specifically, Y1 is preferably a divalent organic group containing at least one structure represented by the following general formulas (IV-8) to (IV-10). [ka] (In the formula, R 10 , R 11 , R 12 and R 13are hydrogen atoms or monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different. [ka] (In the formula, R 14 ~R 21 are hydrogen atoms, halogen atoms, or monovalent organic groups having 1 to 5 carbon atoms, and may be different from each other or the same.) [ka] (In the formula, R 22 is a divalent organic group, and R 23 ~R 30 are hydrogen atoms, halogen atoms, or monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different.

[0270] R in general formula (IV-10) 22 is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom.

[0271] From the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3, Y1 in general formula (IV-1) is particularly preferably a divalent organic group containing a structure represented by the following formula (IV-11). [ka]

[0272] Specifically, in the photosensitive polyimide resin composition of general formula (IV-1), X1 is more preferably a group represented by the following formula (IV-7), and Y1 is more preferably a group represented by the following formula (IV-11). [ka] [ka]

[0273] In the photosensitive polyimide resin composition, in general formula (IV-1), X1 is more preferably a group represented by the following formula (IV-5), and Y1 is more preferably a group represented by the following formula (IV-11). [ka] [ka]

[0274] In the polyamic acid ester, X1 in the repeating unit is derived from the tetracarboxylic dianhydride used as a raw material, and Y1 is derived from the diamine used as a raw material.

[0275] Examples of tetracarboxylic dianhydrides used as raw materials include, but are not limited to, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-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. These may be used alone or in combination.

[0276] Examples of diamines used as raw materials include 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, and 3,3'-diaminodiphenyl. sulfone, 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-amino phenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-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, 9,1 Examples of suitable amines include 0-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 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. These amines may also be substituted with some of the hydrogen atoms on the benzene ring. These amines may be used alone or in combination.

[0277] In the synthesis of the polyamic acid ester (A), a method can be preferably used in which a tetracarboxylic acid diester obtained by an esterification reaction of a tetracarboxylic acid dianhydride, which will be described later, is directly subjected to a condensation reaction with a diamine.

[0278] The alcohol used in the esterification reaction of the tetracarboxylic dianhydride is an alcohol having an olefinic double bond. Specific examples include, but are not limited to, 2-hydroxyethyl methacrylate, 2-methacryloyloxyethyl alcohol, glycerin diacrylate, and glycerin dimethacrylate. These alcohols can be used alone or in combination.

[0279] A specific synthesis method for the polyamic acid ester (A) used in this embodiment can be a conventionally known method. Examples of synthesis methods include the method disclosed in International Publication No. 00 / 43439. Specifically, a method can be used in which a tetracarboxylic acid diester is first converted into a tetracarboxylic acid diester diacid chloride, and then the tetracarboxylic acid diester diacid chloride and a diamine are subjected to a condensation reaction in the presence of a basic compound to produce the polyamic acid ester (A). Another example can be used in which a tetracarboxylic acid diester and a diamine are subjected to a condensation reaction in the presence of an organic dehydrating agent to produce the polyamic acid ester (A).

[0280] Examples of organic dehydrating agents include dicyclohexylcarbodiimide (DCC), diethylcarbodiimide, diisopropylcarbodiimide, ethylcyclohexylcarbodiimide, diphenylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 1-cyclohexyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride.

[0281] The weight average molecular weight of the polyamic acid ester (A) used in this embodiment is preferably 6,000 to 150,000, more preferably 7,000 to 50,000, and even more preferably 7,000 to 20,000.

[0282] (B1) Photoinitiator When the resin composition used to form the interlayer insulating film 6 is a negative photosensitive resin, a photoinitiator is added. Examples of the photoinitiator include benzophenone derivatives such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone; thioxanthone derivatives such as 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzil derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; and 2,6-di(4'-diazidobenzal)-4-methylcyclohexanoate. Examples of suitable oximes include azides such as 2,6'-di(4'-diazidobenzal)cyclohexanone and 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-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 peroxide; aromatic biimidazoles; and titanocenes. Among these, the oximes are preferred in terms of photosensitivity.

[0283] The amount of these photoinitiators added is preferably 1 to 40 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the polyamic acid ester (A). Adding 1 part by mass or more of the photoinitiator per 100 parts by mass of the polyamic acid ester (A) provides excellent photosensitivity. Adding 40 parts by mass or less provides excellent thick-film curing properties.

[0284] (B2) Photoacid generator When the resin composition used to form the interlayer insulating film 6 is a positive photosensitive resin, a photoacid generator is added. By including a photoacid generator, acid is generated in the ultraviolet-exposed area, increasing the solubility of the exposed area in an alkaline aqueous solution. This allows the resin composition to be used as a positive photosensitive resin composition.

[0285] Examples of photoacid generators include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among these, quinone diazide compounds are preferred because they exhibit excellent dissolution-inhibiting effects and can produce highly sensitive positive-type photosensitive resin compositions. Two or more photoacid generators may be contained.

[0286] (D) Solvent There are no particular limitations on the solvent as long as it can dissolve or disperse each component. Examples include N-methyl-2-pyrrolidone, γ-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide, etc. These solvents can be used in an amount of 30 to 1500 parts by mass per 100 parts by mass of the photosensitive resin (A) depending on the coating film thickness and viscosity.

[0287] (E) Other The polyimide precursor composition may contain a crosslinking agent. The crosslinking agent may be one that can crosslink the (A) photosensitive resin or that can itself form a crosslinked network when the polyimide precursor composition is exposed to light, developed, and then heat-cured. The use of a crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film (interlayer insulating film).

[0288] In addition, the layer may contain a sensitizer for improving photosensitivity, an adhesion aid for improving adhesion to the substrate, and the like.

[0289] In this embodiment, the multilayer cured relief pattern (interlayer insulating film 6) using the polyimide precursor composition is produced by the following method. <Method for manufacturing a multilayer cured relief pattern> The method for producing a multi-layer cured relief pattern comprises the following steps: (1) forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition (polyimide precursor composition) onto the substrate; (2) a step of exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) a first heat-curing step in which the relief pattern is heat-treated at a temperature in the range of 150°C to 200°C for 0 to 240 minutes to form a semi-cured relief pattern; and (5) a second heat-curing step of heat-treating the semi-cured relief pattern at a temperature in the range of 200 to 260°C, which is higher than that in the first heat-curing step, for 10 minutes or less to form a cured relief pattern; Furthermore, steps (1) to (5) are performed again in order, thereby forming the interlayer insulating film 6 into a multilayer structure (multilayer cured relief pattern). It is preferable to repeat steps (1) to (5) in the above order 3 to 8 times.

[0290] (1) A step of forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition onto the substrate. In this step, the photosensitive resin composition is applied to a substrate, and then dried as necessary to form a resin layer. The substrate is, for example, a substrate composed of a semiconductor chip 2 and an encapsulant 3 that covers the semiconductor chip. As the application method, a method that has conventionally been used for applying a photosensitive resin composition, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or a method of spray application using a spray coater, can be used.

[0291] As a method for forming a relief pattern using a photosensitive resin composition, not only can the photosensitive resin composition be applied to a substrate to form a resin layer on the substrate, but also the photosensitive resin composition can be formed into a film and the layer of the photosensitive resin composition can be laminated on a substrate to form a resin layer. Alternatively, a film of the photosensitive resin composition according to the present invention can be formed on a supporting substrate, and the supporting substrate can be removed after lamination when the film is used, or before lamination.

[0292] If necessary, the coating film made of the photosensitive resin composition can be dried. Drying methods include air drying, heat drying using an oven or a hot plate, vacuum drying, etc. Specifically, when air drying or heat drying is performed, drying can be carried out under conditions of 20°C to 140°C for 1 minute to 1 hour. As described above, a resin layer can be formed on a substrate.

[0293] (2) A step of exposing the photosensitive resin layer to light In this step, the photosensitive resin layer formed in step (1) is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern.

[0294] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as necessary for the purpose of improving photosensitivity, etc. The baking conditions preferably range from 40 to 120°C for a temperature of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition.

[0295] (3) A step of developing the exposed photosensitive resin layer to form a relief pattern. In this process, after the polyimide precursor composition is exposed to light, unnecessary portions are washed away with a developer. There are no particular limitations on the developer used, but in the case of a polyimide precursor composition that is developed with a solvent, good solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, and acetate esters, and mixed solvents of these good solvents with poor solvents such as lower alcohols, water, and aromatic hydrocarbons are used. After development, the composition is optionally rinsed with a poor solvent.

[0296] In the case of a polyimide precursor composition that is developed with an alkaline aqueous solution, preferred are aqueous solutions of compounds that exhibit alkalinity, such as an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine.

[0297] (thermal curing) After development, the polyimide precursor is heated to close the ring and form polyimide. This polyimide becomes the cured relief pattern, i.e., the interlayer insulating film 6. The higher the proportion of polyimide in the polymer, the better the film's physical properties and chemical resistance. Typically, it is desirable to heat the film at a heat curing temperature of 250°C or higher for at least one hour.

[0298] If the heat curing temperature is below 200°C, the proportion of polyimide in the polymer will be low even if the heat curing time is long, and the desired film properties and chemical resistance will not be obtained. Therefore, in the present invention, the heat curing of polyimide is performed in two stages: (4) a first heat curing step in which the relief pattern is heat-treated at a temperature range of 150°C to 200°C for 0 to 240 minutes to form a semi-cured relief pattern, and (5) a second heat curing step in which the semi-cured relief pattern is heat-treated at a temperature range of 200°C to 260°C, higher than that in the first heat curing step, for 10 minutes or less to form a cured relief pattern. This allows the proportion of polyimide in the polymer to be increased.

[0299] Furthermore, the heat applied to the semiconductor device during thermal curing can cause thermal damage to the semiconductor chip and encapsulating resin. If the interlayer insulating film 6 has two or more layers, the interlayer insulating film layers are thermally cured multiple times, significantly increasing the thermal damage. In the present invention, the time required for the second thermal curing step is short, thereby reducing the thermal damage during thermal curing.

[0300] (4) A step of forming a semi-cured relief pattern by heat-treating the relief pattern at a temperature in the range of 150°C to 200°C for 0 to 240 minutes (first heat-curing step). The heating temperature in the first thermal curing step is preferably 150°C to 200°C, more preferably 150°C to 180°C, more preferably 150°C to 170°C, more preferably 150°C to 160°C, and most preferably 150°C. If the heating temperature in the first thermal curing step is less than 150°C, additive components and solvent components may remain in the semi-cured relief pattern, which may cause bubbles to form between layers and lead to interlayer peeling when a multilayer interlayer insulating film 6 is formed. If the heating temperature is higher than 200°C, the semi-cured relief pattern may be over-cured, making it difficult for the cyclization reaction to occur in the second thermal curing step, and a sufficiently cyclized cured film may not be obtained.

[0301] The heating time in the first thermal curing step is preferably 0 to 240 minutes. If the heating time is longer than 240 minutes, the semi-cured relief pattern may be over-cured, making it difficult for the cyclization reaction to occur in the second thermal curing step, and a sufficiently cyclized cured film may not be obtained. In addition, the semiconductor chip or encapsulating resin may be damaged by heat.

[0302] (5) A step of forming a hardened relief pattern by heat-treating the semi-cured relief pattern at a temperature in the range of 200°C to 260°C, which is higher than that in the first heat-curing step, for 10 minutes or less (second heat-curing step). The heating temperature in the second heat curing step is preferably 200°C to 260°C. If the temperature is lower than 200°C, the proportion of polyimide in the polymer is low, and sufficient film properties and chemical resistance may not be obtained. If the heating temperature is higher than 260°C, the semiconductor chip and encapsulating resin may be damaged by heat. The maximum temperature in the second heat curing step is preferably 260°C or lower, and more preferably 240°C or lower.

[0303] In the second heat curing step, the heating time at the maximum temperature is preferably 10 minutes or less, more preferably 5 minutes or less, and most preferably 1 minute or less. If the heating time is longer than 10 minutes, the semiconductor chip or encapsulating resin may be damaged by heat. Furthermore, in the second heat curing step, the heating time at the maximum temperature may be 30 seconds or more. If the heating time is shorter than 30 seconds, the proportion of polyimide in the polymer may be low, and sufficient film properties and chemical resistance may not be obtained.

[0304] <Polyimide> The structure of the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (IV-12). [ka] X in general formula (IV-12) 1 , Y 1, m are the same as X1, Y1, and m in general formula (IV-1), where X1 is a tetravalent organic group containing an aromatic group, Y1 is a divalent organic group containing an aromatic group, and m is an integer of 1 or more. For the same reason, the preferred X1, Y1, and m in general formula (IV-1) are also preferred in the polyimide of general formula (IV-12).

[0305] In the case of an alkali-soluble polyimide, the polyimide may be terminated with a hydroxyl group.

[0306] <Polybenzoxazole Precursor Composition> (A) Photosensitive resin The photosensitive resin used in the polybenzoxazole precursor composition may be a poly(o-hydroxyamide) containing a repeating unit represented by the following general formula (IV-13).

[0307] [ka] (In general formula (IV-13), U and V are divalent organic groups.)

[0308] From the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3, U in formula (IV-13) is preferably a divalent organic group having 1 to 30 carbon atoms, more preferably a chain alkylene group having 1 to 15 carbon atoms (however, the hydrogen atoms of the chain alkylene may be substituted with halogen atoms), and particularly preferably a chain alkylene group having 1 to 8 carbon atoms and in which the hydrogen atoms are substituted with fluorine atoms.

[0309] Furthermore, from the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3, V in formula (IV-13) is preferably a divalent organic group containing an aromatic group, and more preferably a divalent organic group containing at least one structure represented by the following general formulas (IV-8) to (IV-10). [ka] (In the formula, R 10 , R 11 , R 12 and R 13are hydrogen atoms or monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different. [ka] (In the formula, R 14 ~R 21 are hydrogen atoms, halogen atoms, or monovalent organic groups having 1 to 5 carbon atoms, and may be different from each other or the same.) [ka] (In the formula, R 22 is a divalent organic group, and R 23 ~R 30 are hydrogen atoms, halogen atoms, or monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different.

[0310] R in general formula (IV-10) 22 is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom.

[0311] From the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3, V in formula (IV-13) is particularly preferably a divalent organic group containing the structure represented by general formula (IV-11) above.

[0312] From the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3, V in formula (IV-13) is preferably a divalent organic group having 1 to 40 carbon atoms, more preferably a divalent chain aliphatic group having 1 to 40 carbon atoms, and particularly preferably a divalent chain aliphatic group having 1 to 20 carbon atoms.

[0313] Polybenzoxazole precursors can generally be synthesized from dicarboxylic acid derivatives and hydroxyl-containing diamines. Specifically, they can be synthesized by converting the dicarboxylic acid derivatives into dihalide derivatives and then reacting them with diamines. As the dihalide derivatives, dichloride derivatives are preferred.

[0314] The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent, such as thionyl chloride, phosphoryl chloride, phosphorus oxychloride, or phosphorus pentachloride, which are commonly used in acid chloride reactions of carboxylic acids.

[0315] The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with the above-mentioned halogenating agent in a solvent, or by reacting in an excess amount of the halogenating agent and then distilling off the excess.

[0316] Examples of dicarboxylic acids used in the dicarboxylic acid derivative include isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, and hexafluoroglutaric acid. 2-Methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecane Examples of the diacid include tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosaneedioic acid, heneicosaneedioic acid, docosaneedioic acid, tricosaneedioic acid, tetracosaneedioic acid, pentacosaneedioic acid, hexacosaneedioic acid, heptacosaneedioic acid, octacosaneedioic acid, nonacosaneedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, and diglycolic acid. These may also be used in combination.

[0317] Examples of hydroxy group-containing diamines include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc. These may also be used in combination.

[0318] (B2) Photoacid generator The photoacid generator has the function of increasing the solubility of the irradiated portion in an alkaline aqueous solution. Examples of the photoacid generator include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. Among these, diazonaphthoquinone compounds are preferred because of their high sensitivity.

[0319] (C) Additives The preferred types and amounts of additives are the same as those described in the section on the polyimide precursor composition.

[0320] (D) Solvent There are no particular limitations on the solvent as long as it can dissolve or disperse each component.

[0321] (E) Other The polybenzoxazole precursor composition may contain a crosslinking agent, a sensitizer, an adhesion promoter, a thermal acid generator, and the like.

[0322] In this embodiment, the multilayer cured relief pattern (interlayer insulating film 6) using the polybenzoxazole precursor composition is produced by the following method. <Method for manufacturing a multilayer cured relief pattern> The method for producing a multi-layer cured relief pattern comprises the following steps: (1) forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition (polybenzoxazole precursor composition) onto the substrate; (2) a step of exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) a first heat-curing step in which the relief pattern is heat-treated at a temperature in the range of 150°C to 200°C for 0 to 240 minutes to form a semi-cured relief pattern; and (5) A second heat-curing step in which the semi-cured relief pattern is heat-treated at a temperature in the range of 200 to 260°C, which is higher than that in the first heat-curing step, for 10 minutes or less to form a cured relief pattern. in order, Furthermore, steps (1) to (5) are performed again in order, thereby forming the interlayer insulating film 6 into a multilayer structure (multilayer cured relief pattern). It is preferable to repeat steps (1) to (5) in the above order 3 to 8 times.

[0323] (1) A step of forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition (polybenzoxazole precursor composition) onto the substrate. In this step, the photosensitive resin composition is applied to a substrate and then dried as necessary to form a resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0324] As a method for forming a relief pattern using a photosensitive resin composition, not only can the photosensitive resin composition be applied to a substrate to form a resin layer on the substrate, but also the photosensitive resin composition can be formed into a film and the layer of the photosensitive resin composition can be laminated on a substrate to form a resin layer. Alternatively, a film of the photosensitive resin composition according to the present invention can be formed on a supporting substrate, and the supporting substrate can be removed after lamination when the film is used, or before lamination.

[0325] If necessary, the coating film made of the photosensitive resin composition can be dried by air drying, heat drying in an oven or on a hot plate, vacuum drying, or the like.

[0326] (2) A step of exposing the photosensitive resin layer to light In this step, the photosensitive resin layer formed in step (1) is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern.

[0327] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and / or pre-development baking may be carried out using any combination of temperature and time, as required.

[0328] (3) A step of developing the exposed photosensitive resin layer to form a relief pattern. After the polybenzoxazole precursor composition is exposed to light, unnecessary portions are washed away with a developer. The developer to be used is not particularly limited, but preferred examples include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide.

[0329] Although the above description has focused on positive polybenzoxazole precursor compositions, negative polybenzoxazole precursor compositions may also be used.

[0330] (thermal curing) After development, the polybenzoxazole precursor is ring-closed by heating to form polybenzoxazole. This polybenzoxazole becomes the cured relief pattern, i.e., the interlayer insulating film 6. The higher the proportion of polybenzoxazole in the polymer, the better the film's physical properties and chemical resistance. Typically, the thermal curing temperature is preferably 250°C or higher for at least 1 hour.

[0331] If the heat curing temperature is below 200°C, the proportion of polybenzoxazole in the polymer will be low even if the heat curing time is long, and the desired film properties and chemical resistance of the film will not be obtained. Therefore, in this embodiment, the thermal curing of polybenzoxazole is carried out in two stages: (4) a first thermal curing step in which the relief pattern is heated at a temperature in the range of 150°C to 200°C for 0 to 240 minutes to form a semi-cured relief pattern, and (5) a second thermal curing step in which the semi-cured relief pattern is heated at a temperature in the range of 200°C to 260°C, higher than that in the first thermal curing step, for 10 minutes or less to form a cured relief pattern. This allows the proportion of polybenzoxazole in the polymer to be increased. Furthermore, the heat applied to the semiconductor device during thermal curing can cause thermal damage to the semiconductor chip and encapsulating resin. If the interlayer insulating film 6 has two or more layers, the interlayer insulating film layers are thermally cured multiple times, significantly increasing the thermal damage. In the present invention, the time required for the second thermal curing step is short, thereby reducing the thermal damage during thermal curing.

[0332] (4) Heat-treat the relief pattern at a temperature range of 150°C to 200°C for 0 to 240 minutes. forming a semi-cured relief pattern by the above-mentioned process (first thermal curing process). The heating temperature in the first thermal curing step is preferably 150°C to 200°C, more preferably 150°C to 180°C, more preferably 150°C to 170°C, more preferably 150°C to 160°C, and most preferably 150°C. If the heating temperature in the first thermal curing step is less than 150°C, additive components and solvent components will remain in the semi-cured relief pattern, and when a multilayer interlayer insulating film 6 is formed, bubbles will form between the layers, causing interlayer peeling. If the heating temperature is higher than 200°C, the semi-cured relief pattern will be over-cured, making it difficult for the cyclization reaction to occur in the second thermal curing step, and a sufficiently cyclized cured film will not be obtained.

[0333] The heating time in the first heat curing step is preferably 0 to 240 minutes. If the heating time is longer than 240 minutes, the semi-cured relief pattern may be over-cured, making it difficult for the cyclization reaction to occur in the second heat curing step, and a sufficiently cyclized cured film may not be obtained. In addition, the semiconductor chip and encapsulating resin may be damaged by heat.

[0334] (5) A step of forming a hardened relief pattern by heat-treating the semi-cured relief pattern at a temperature in the range of 200°C to 260°C, which is higher than that in the first heat-curing step, for 10 minutes or less (second heat-curing step). The heating temperature in the second heat curing step is preferably 200°C to 260°C. If the temperature is lower than 200°C, the proportion of polybenzoxazole in the polymer is low, and sufficient film properties and chemical resistance may not be obtained. If the heating temperature is higher than 260°C, the semiconductor chip and encapsulating resin may be damaged by heat. The maximum temperature in the second heat curing step is preferably 260°C or lower, and more preferably 240°C or lower.

[0335] In the second heat curing step, the heating time at the maximum temperature is preferably 10 minutes or less, more preferably 5 minutes or less, and most preferably 1 minute or less. If the heating time is longer than 10 minutes, the semiconductor chip or encapsulating resin may be damaged by heat. If the heating time is shorter than 30 seconds, the proportion of polybenzoxazole in the polymer is low, and sufficient film properties and chemical resistance may not be achieved.

[0336] <Polybenzoxazole> The structure of the cured relief pattern formed from the polybenzoxazole precursor composition is represented by the following general formula (IV-14).

[0337] [ka]

[0338] U and V in general formula (IV-14) are the same as U and V in general formula (IV-13). For the same reason, the preferred U and V in general formula (IV-13) are also preferred in the polybenzoxazole of general formula (IV-14).

[0339] <Polymers containing phenolic hydroxyl groups> (A) Photosensitive resin These resins have phenolic hydroxyl groups in their molecules and are alkali-soluble. Specific examples include vinyl polymers containing monomer units having phenolic hydroxyl groups, such as poly(hydroxystyrene), phenolic resins, poly(hydroxyamides), poly(hydroxyphenylene) ethers, and polynaphthols. Among these, phenolic resins are preferred because of their low cost and small volumetric shrinkage during curing, and novolac-type phenolic resins are particularly preferred.

[0340] Phenolic resins are polycondensation products of phenol or its derivatives with aldehydes. The polycondensation is carried out in the presence of a catalyst such as an acid or a base. Phenolic resins obtained using an acid catalyst are specifically called novolak-type phenolic resins.

[0341] Examples of phenol derivatives include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, catechol, resorcinol, ethylresorcinol, hexylresorcinol, hydroquinone, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, pararosolic acid, biphenol, bisphenol A, bisphenol AF, bisphenol B, bisphenol F, and bisphenol S. , dihydroxydiphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,4-bis(3-hydroxyphenoxybenzene), 2,2-bis(4-hydroxy-3-methylphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2-hydroxy-5-biphenylyl)propane, dihydroxybenzoic acid, and the like.

[0342] Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxaldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, and terephthalaldehyde.

[0343] Component (A) preferably contains (a) a phenolic resin having no unsaturated hydrocarbon groups and (b) a modified phenolic resin having unsaturated hydrocarbon groups. Component (b) is more preferably further modified by reaction of the phenolic hydroxyl groups with a polybasic acid anhydride.

[0344] Furthermore, as component (b), it is preferable to use a phenolic resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms, from the viewpoint of further improving mechanical properties (elongation at break, elastic modulus, and residual stress).

[0345] (b) Modified phenolic resins having unsaturated hydrocarbon groups are generally reaction products of phenol or its derivatives with compounds having unsaturated hydrocarbon groups (preferably those having 4 to 100 carbon atoms) (hereinafter sometimes simply referred to as "unsaturated hydrocarbon group-containing compounds") (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivatives") and aldehydes, or reaction products of phenolic resins with unsaturated hydrocarbon group-containing compounds.

[0346] The phenol derivatives used here may be the same as those described above as raw materials for the phenolic resin as component (A).

[0347] The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups from the viewpoints of adhesion of the resist pattern and thermal shock resistance. Furthermore, from the viewpoints of compatibility when formed into a resin composition and flexibility of the cured film, the unsaturated hydrocarbon group-containing compound preferably has 8 to 80 carbon atoms, more preferably 10 to 60 carbon atoms.

[0348] Examples of unsaturated hydrocarbon group-containing compounds include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linolyl alcohol, oleyl alcohol, unsaturated fatty acids, and unsaturated fatty acid esters. Suitable unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, sardine acid, and docosahexaenoic acid. Among these, esters of unsaturated fatty acids having 8 to 30 carbon atoms and monohydric to trihydric alcohols having 1 to 10 carbon atoms are more preferred, and esters of unsaturated fatty acids having 8 to 30 carbon atoms and the trihydric alcohol glycerin are particularly preferred.

[0349] Esters of unsaturated fatty acids having 8 to 30 carbon atoms and glycerin are commercially available as vegetable oils. Vegetable oils include non-drying oils with an iodine value of 100 or less, semi-drying oils with an iodine value of more than 100 but less than 130, and drying oils with an iodine value of 130 or more. Examples of non-drying oils include olive oil, morning glory seed oil, cashew seed oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of drying oils include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil, and mustard oil. Processed vegetable oils obtained by processing these vegetable oils may also be used.

[0350] Among the above vegetable oils, it is preferable to use non-drying oils from the viewpoint of preventing gelation due to excessive reaction in the reaction between phenol or its derivatives or phenolic resins and vegetable oils and improving yield. On the other hand, it is preferable to use drying oils from the viewpoint of improving the adhesion, mechanical properties, and thermal shock resistance of the resist pattern. Among drying oils, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferred, and tung oil and linseed oil are more preferred, as they can more effectively and reliably exhibit the effects of the present invention.

[0351] These unsaturated hydrocarbon group-containing compounds may be used singly or in combination of two or more.

[0352] To prepare component (b), the phenol derivative is first reacted with the unsaturated hydrocarbon group-containing compound to produce an unsaturated hydrocarbon group-modified phenol derivative. The reaction is preferably carried out at 50 to 130°C. From the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio of the phenol derivative and the unsaturated hydrocarbon group-containing compound is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, of the unsaturated hydrocarbon group-containing compound per 100 parts by mass of the phenol derivative. If the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, while if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst, if necessary.

[0353] The unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction is polycondensed with an aldehyde to produce a phenolic resin modified with the unsaturated hydrocarbon group-containing compound. The aldehyde may be the same as the aldehyde used to obtain the phenolic resin described above.

[0354] The reaction between the aldehydes and the unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and conventionally known synthesis conditions for phenolic resins can be used. The reaction is preferably carried out in the presence of a catalyst such as an acid or a base, and more preferably an acid catalyst is used. Examples of acid catalysts include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.

[0355] The reaction is preferably carried out at a temperature of 100°C to 120°C. The reaction time varies depending on the type and amount of catalyst used, but is usually 1 to 50 hours. After the reaction is completed, the reaction product is dehydrated under reduced pressure at a temperature of 200°C or less to obtain a phenolic resin modified with an unsaturated hydrocarbon group-containing compound. Solvents such as toluene, xylene, and methanol can be used for the reaction.

[0356] The phenolic resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by polycondensing the above-mentioned unsaturated hydrocarbon group-modified phenol derivative with an aldehyde together with a compound other than phenol, such as m-xylene. In this case, the molar ratio of the compound other than phenol to the compound obtained by reacting the phenol derivative with the unsaturated hydrocarbon group-containing compound is preferably less than 0.5.

[0357] The component (b) can also be obtained by reacting the phenolic resin of the component (a) with a compound containing an unsaturated hydrocarbon group.

[0358] The unsaturated hydrocarbon group-containing compound to be reacted with the phenolic resin may be the same as the unsaturated hydrocarbon group-containing compound described above.

[0359] The reaction between the phenolic resin and the unsaturated hydrocarbon group-containing compound is preferably carried out at 50°C to 130°C. Furthermore, from the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio between the phenolic resin and the unsaturated hydrocarbon group-containing compound is preferably 1 to 100 parts by mass of the unsaturated hydrocarbon group-containing compound per 100 parts by mass of the phenolic resin, more preferably 2 to 70 parts by mass, and even more preferably 5 to 50 parts by mass. If the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease. If the amount is more than 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the heat resistance of the cured film tends to decrease. In this case, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst. Solvents such as toluene, xylene, methanol, and tetrahydrofuran can be used for the reaction.

[0360] The phenolic hydroxyl groups remaining in the phenolic resin modified with the unsaturated hydrocarbon group-containing compound produced by the above method are further reacted with a polybasic acid anhydride. This acid-modified phenolic resin can also be used as component (b). Acid modification with a polybasic acid anhydride introduces carboxyl groups, further improving the solubility of component (b) in an aqueous alkaline solution (developer).

[0361] The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxy groups of a polybasic acid having a plurality of carboxy groups. Examples of the polybasic acid anhydride include dibasic acid anhydrides such as phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, and trimellitic anhydride, and aromatic tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. These may be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern with a better shape can be formed.

[0362] Furthermore, the alkali-soluble resin (A) having a phenolic hydroxyl group can further contain a phenolic resin that has been acid-modified by reacting it with a polybasic acid anhydride. When component (A) contains a phenolic resin that has been acid-modified with a polybasic acid anhydride, the solubility of component (A) in an aqueous alkaline solution (developer) is further improved.

[0363] Examples of the polybasic acid anhydride include dibasic acid anhydrides such as phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, and trimellitic anhydride; and aliphatic and aromatic tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. These may be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably, for example, one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride.

[0364] (B2) Photoacid generator Examples of the photoacid generator include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, etc. Among these, diazonaphthoquinone compounds are preferred because of their high sensitivity.

[0365] (C) Additives The preferred types and amounts of additives are the same as those described in the section on the polyimide precursor composition.

[0366] (D) Solvent There are no particular limitations on the solvent as long as it can dissolve or disperse each component.

[0367] (E) Other The composition may contain a thermal crosslinking agent, a sensitizer, an adhesion promoter, a dye, a surfactant, a dissolution promoter, a crosslinking promoter, etc. Among these, by including a thermal crosslinking agent, when the photosensitive resin film after pattern formation is heated and cured, the thermal crosslinking agent component reacts with component (A) to form a crosslinked structure. This enables curing at low temperatures and prevents the film from becoming brittle or melting. Specific examples of the thermal crosslinking agent component that can be used preferably include compounds having a phenolic hydroxyl group, compounds having a hydroxymethylamino group, and compounds having an epoxy group.

[0368] In this embodiment, the multilayer cured relief pattern (interlayer insulating film 6) using a polymer having a phenolic hydroxyl group is produced by the following method. <Method for manufacturing a multilayer cured relief pattern> The method for producing a multi-layer cured relief pattern comprises the following steps: (1) forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition (a polymer having a phenolic hydroxyl group) onto the substrate; (2) a step of exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) a first heat-curing step in which the relief pattern is heat-treated at a temperature in the range of 150°C to 200°C for 0 to 240 minutes to form a semi-cured relief pattern; and (5) A second heat-curing step in which the semi-cured relief pattern is heat-treated at a temperature in the range of 200 to 260°C, which is higher than that in the first heat-curing step, for 10 minutes or less to form a cured relief pattern. in order, Furthermore, steps (1) to (5) are performed again in order, thereby forming the interlayer insulating film 6 into a multilayer structure (multilayer cured relief pattern). It is preferable to repeat steps (1) to (5) in the above order 3 to 8 times.

[0369] (1) A step of forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition (a polymer having a phenolic hydroxyl group) onto the substrate. In this step, the photosensitive resin composition is applied to a substrate and then dried as necessary to form a resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0370] As a method for forming a relief pattern using a photosensitive resin composition, not only can the photosensitive resin composition be applied to a substrate to form a resin layer on the substrate, but also the photosensitive resin composition can be formed into a film and the layer of the photosensitive resin composition can be laminated on a substrate to form a resin layer. Alternatively, a film of the photosensitive resin composition according to the present invention can be formed on a supporting substrate, and the supporting substrate can be removed after lamination when the film is used, or before lamination.

[0371] If necessary, the coating film made of the photosensitive resin composition can be dried by air drying, heat drying in an oven or on a hot plate, vacuum drying, or the like. (2) A step of exposing the photosensitive resin layer to light In this step, the photosensitive resin layer formed in step (1) is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern.

[0372] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and / or pre-development baking may be carried out using any combination of temperature and time, as required.

[0373] (3) A step of developing the exposed photosensitive resin layer to form a relief pattern. After the polymer having a phenolic hydroxyl group is exposed to light, unnecessary portions are washed away with a developer. The developer to be used is not particularly limited, but suitable examples include aqueous alkaline solutions of sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), and the like.

[0374] (thermal curing) After development, the polymers having phenolic hydroxyl groups are thermally crosslinked by heating. This thermally crosslinked product becomes the cured relief pattern, i.e., the interlayer insulating film 6. The greater the proportion of thermal crosslinking, the better the film's physical properties and chemical resistance. Typically, it is desirable to heat the film at a thermal curing temperature of 250°C or higher for at least one hour.

[0375] If the thermal curing temperature is below 200°C, the proportion of thermal crosslinking in the film will be low even if the thermal curing time is long, and the desired film properties and chemical resistance will not be obtained. Therefore, in this embodiment, the thermal crosslinking of the polymer having a phenolic hydroxyl group is performed in two stages: (4) a first thermal curing step in which the relief pattern is heat-treated at a temperature range of 150°C to 200°C for 0 to 240 minutes to form a semi-cured relief pattern, and (5) a second thermal curing step in which the semi-cured relief pattern is heat-treated at a temperature range of 200°C to 260°C, higher than that in the first thermal curing step, for 10 minutes or less to form a cured relief pattern. This allows for a high proportion of thermal crosslinking.

[0376] Furthermore, the heat applied to the semiconductor device during thermal curing can cause thermal damage to the semiconductor chip and encapsulating resin. If the interlayer insulating film 6 has two or more layers, the interlayer insulating film layers are thermally cured multiple times, significantly increasing the thermal damage. In the present invention, the time required for the second thermal curing step is short, thereby reducing the thermal damage during thermal curing.

[0377] (4) A step of forming a semi-cured relief pattern by heat-treating the relief pattern at a temperature in the range of 150°C to 200°C for 0 to 240 minutes (first heat-curing step). The heating temperature in the first thermal curing step is preferably 150°C to 200°C, more preferably 150°C to 180°C, more preferably 150°C to 170°C, more preferably 150°C to 160°C, and most preferably 150°C. If the heating temperature in the first thermal curing step is less than 150°C, additive components and solvent components may remain in the semi-cured relief pattern, which may cause bubbles to form between layers and lead to interlayer peeling when a multilayer interlayer insulating film 6 is formed. If the heating temperature is higher than 200°C, the semi-cured relief pattern may be over-cured, making it difficult for the thermal crosslinking reaction to occur in the second thermal curing step, and a sufficiently thermally crosslinked cured film may not be obtained.

[0378] The heating time in the first thermal curing step is preferably 0 to 240 minutes. If the heating time is longer than 240 minutes, the semi-cured relief pattern may be over-cured, making it difficult for the thermal crosslinking reaction to occur in the second thermal curing step, resulting in a sufficiently thermally crosslinked cured film, and the semiconductor chip or encapsulating resin may be damaged by heat.

[0379] (5) A step of forming a hardened relief pattern by heat-treating the semi-cured relief pattern at a temperature in the range of 200°C to 260°C, which is higher than that in the first heat-curing step, for 10 minutes or less (second heat-curing step). The heating temperature in the second thermal curing step is preferably 200°C to 260°C. If the temperature is lower than 200°C, the rate of thermal crosslinking reaction in the film is low, and sufficient film properties and chemical resistance may not be obtained. If the heating temperature is higher than 260°C, the semiconductor chip and encapsulating resin may be damaged by heat. The maximum temperature in the second thermal curing step is preferably 260°C or lower, and more preferably 240°C or lower.

[0380] In the second heat curing step, the heating time at the maximum temperature is preferably 10 minutes or less, more preferably 5 minutes or less, and most preferably 1 minute or less. If the heating time is longer than 10 minutes, the semiconductor chip or encapsulating resin may be damaged by heat. If the heating time is shorter than 30 seconds, the rate of thermal crosslinking in the film may be low, and sufficient film properties and chemical resistance may not be obtained.

[0381] (Method of manufacturing a semiconductor device) The method for manufacturing a semiconductor device according to this embodiment will be described with reference to FIG. 3. In FIG. 3A, a pre-processed wafer 10 is prepared. Then, in FIG. 3B, the pre-processed wafer 10 is diced to form a plurality of semiconductor chips 2. The semiconductor chips 2 may be purchased. The semiconductor chips 2 thus prepared are attached to a support 11 at predetermined intervals, as shown in FIG. 3C.

[0382] Next, molding resin 12 is applied from above semiconductor chip 2 to above support 11, and mold sealing is performed as shown in FIG. 3D. Next, support 11 is peeled off, and molding resin 12 is inverted (see FIG. 3E). As shown in FIG. 3E, semiconductor chip 2 and molding resin 12 appear to be on approximately the same plane. Next, in the step shown in FIG. 3F, photosensitive resin composition 13 is applied onto semiconductor chip 2 and molding resin 12. Then, the applied photosensitive resin composition 13 is exposed and developed to form a relief pattern (relief pattern forming step). Note that photosensitive resin composition 13 may be either positive or negative. Furthermore, the relief pattern is heated to form a cured relief pattern (interlayer insulating film forming step). Furthermore, wiring is formed in areas where the cured relief pattern is not to be formed (wiring forming step).

[0383] In this embodiment, the relief pattern forming step, interlayer insulating film forming step, and wiring forming step are combined together to form a rewiring layer forming step for forming a rewiring layer connected to the semiconductor chip 2.

[0384] The interlayer insulating film in the rewiring layer may be multi-layered, and therefore the rewiring layer forming step may include a plurality of relief pattern forming steps, a plurality of interlayer insulating film forming steps, and a plurality of wiring forming steps.

[0385] 3G, a plurality of external connection terminals 7 corresponding to each semiconductor chip 2 are formed (bump formation), and the semiconductor chips 2 are diced apart. This allows a semiconductor device (semiconductor IC) 1 to be obtained, as shown in FIG. 3H. In this embodiment, a plurality of fan-out type semiconductor devices 1 can be obtained by the manufacturing method shown in FIG.

[0386] In the present embodiment, in the interlayer insulating film forming step, it is preferable to form the interlayer insulating film from a photosensitive resin composition capable of forming at least one compound selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

[0387] A fifth aspect of the present embodiment will be described. <Photosensitive resin composition> The photosensitive resin composition according to this embodiment comprises: (A) polyimide precursor: 100 parts by mass, (B) a compound represented by at least one of the following general formulas (V-1) and (V-3) to (V-6): 0.1 to 50 parts by mass, (C) Photosensitizer: 0.1 to 50 parts by mass The photosensitive resin composition is preferably used as a negative or positive photosensitive resin composition, more preferably as a negative photosensitive resin composition. Each of the components contained in the negative photosensitive resin composition will be described below.

[0388] The polyimide precursor (A) in this embodiment is a resin component contained in the negative photosensitive resin composition, and is converted into a polyimide by subjecting it to a thermal cyclization treatment. The polyimide precursor is preferably a polyamide having a structure represented by the following general formula (V-9). [ka] In formula (V-9), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 150, and R5 and R6 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R5 and R6 is a group represented by the following general formula (V-10): [ka] {In formula (V-10), R7, R8, and R9 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m4 represents an integer of 2 to 10.}

[0389] In general formula (V-9), 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. In general formula (V-9), the tetravalent organic group 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 X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, such as those represented by the following general formula (V-20): [ka] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, 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.} Examples include, but are not limited to, groups having a structure represented by the following formula: In addition, the structure of the X1 group may be one type or a combination of two or more types. The X1 group having a structure represented by the above formula (V-20) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties. Among these, from the viewpoint of achieving both heat resistance and photosensitive properties, it is preferable that the X1 group contains at least one of the following general formulae (V-11) to (V-13). [ka] [ka] [ka]

[0390] In the above general formula (V-9), the divalent organic group 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 (V-21): [ka] {In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4.} Examples include, but are not limited to, structures represented by the following formula: In addition, the structure of Y1 may be one type or a combination of two or more types. A Y1 group having a structure represented by the above formula (V-21) is preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0391] As the Y1 group, among the structures represented by the above formula (V-21), those represented by the following formula: [ka] is more preferable from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance, and at least one selected from the group consisting of the following general formulae (V-14) and (V-15) is even more preferable. [ka] [ka]

[0392] In the general formula (V-10), R7 is preferably a hydrogen atom or a methyl group, and R8 and R9 are preferably hydrogen atoms from the viewpoint of photosensitivity. Also, m4 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitivity.

[0393] In one embodiment, the polyimide precursor (A) is represented by the following general formula (V-16): [ka] In formula (V-16), n1 is an integer of 2 to 150, and R5 and R6 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R5 and R6 is a group represented by the following general formula (V-18): [ka] {In formula (V-18), R7, R8, and R9 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m3 represents an integer of 2 to 10.} It is preferable that the polyimide precursor has a structural unit represented by the following formula: In general formula (V-16), at least one of R5 and R6 is more preferably a monovalent organic group represented by general formula (V-18) above. When (A) polyimide precursor contains a polyimide precursor represented by general formula (V-16), the effect of particularly improving resolution is enhanced.

[0394] In one embodiment, the polyimide precursor (A) is represented by the following general formula (V-17): [ka] In formula (V-17), n1 is an integer of 2 to 150, and R5 and R6 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R5 and R6 is a group represented by the following general formula (V-18): [ka] {In formula (V-18), R7, R8, and R9 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m3 represents an integer of 2 to 10.} It is preferable that the polyimide precursor has a structural unit represented by the following formula: In general formula (V-17), at least one of R5 and R6 is preferably a monovalent organic group represented by general formula (V-18). When (A) polyimide precursor contains a polyimide precursor represented by general formula (V-17) in addition to a polyimide precursor represented by general formula (V-16), or when (A) polyimide precursor contains a copolymer of a polyimide precursor represented by general formula (V-16) and a polyimide precursor represented by general formula (V-17), the effect of particularly improving resolution is further enhanced. A copolymer of a polyimide precursor represented by general formula (V-16) and a polyimide precursor represented by general formula (V-17) exhibits properties similar to a mixture of a polyimide precursor represented by general formula (V-16) and a polyimide precursor represented by general formula (V-17).

[0395] In one embodiment, the polyimide precursor (A) is represented by the following general formula (V-19): [ka] {wherein R1 and R2 correspond to R5 and R6 above, respectively, and n1 is as defined above.} It is preferable that the polyimide precursor has a structural unit represented by the following formula: In general formula (V-19), at least one of R1 and R2 is more preferably a monovalent organic group represented by general formula (V-18) above. When the polyimide precursor (A) contains a polyimide precursor represented by general formula (V-19) in addition to a polyimide precursor represented by general formula (V-16) or general formula (V-17), the effect of particularly improving resolution is further improved.

[0396] (A) Preparation of polyimide precursor (A) The polyimide precursor is obtained by first reacting a tetracarboxylic acid dianhydride containing the above-mentioned 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), and then subjecting this to amide polycondensation with a diamine containing the above-mentioned divalent organic group Y1.

[0397] (Preparation of Acid / Ester Forms) In this embodiment, examples of the tetracarboxylic acid dianhydride containing a tetravalent organic group X1 that is suitably used to prepare the polyimide precursor (A) include the tetracarboxylic acid dianhydride represented by the general formula (V-20) above, as well as, for example, 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, and diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride. Examples of suitable dianhydrides include diphenylmethane-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 include 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.

[0398] In this embodiment, examples of alcohols having a photopolymerizable unsaturated double bond that are suitably used to prepare the polyimide precursor (A) 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- Examples of the alkyl acrylate include 3-cyclohexyloxypropyl acrylate, 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.

[0399] The above-mentioned photopolymerizable alcohols having an unsaturated double bond may be partially 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.

[0400] Alternatively, a non-photosensitive polyimide precursor prepared solely from the above-mentioned alcohols having no unsaturated double bonds may be used as the polyimide precursor by mixing it with the photosensitive polyimide precursor. From the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

[0401] The above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohol are stirred, dissolved, and mixed in a solvent as described below at a temperature of 20 to 50°C for 4 to 10 hours in the presence of a basic catalyst such as pyridine, whereby the esterification reaction of the acid anhydride proceeds, and the desired acid / ester form can be obtained.

[0402] (Preparation of Polyimide Precursor) The acid / ester compound (typically a solution in a solvent described below) is mixed 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 to convert the acid / ester compound into a polyanhydride. A diamine containing a divalent organic group Y1, as preferred in this embodiment, dissolved or dispersed in a separate solvent is then added dropwise to the resulting mixture to carry out amide polycondensation, thereby obtaining the desired polyimide precursor. Alternatively, the acid moiety of the acid / ester compound can be converted 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, thereby obtaining the desired polyimide precursor.

[0403] Diamines containing a divalent organic group Y1 that are preferably used in this embodiment include diamines having a structure represented by the above general formula (V-21), 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, 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)benzene] 4,4-bis(4-aminophenoxy)phenyl)sulfone, bis[4-(3-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)propane 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 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, 9,9-bis(4-aminophenyl)fluorene, and compounds in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,Examples of the diaminobiphenyl include, but are not limited to, 2'-dimethyl-4,4'-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.

[0404] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as needed, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor.To improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0405] The molecular weight of the polyimide precursor (A), 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 recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0406] (B) Aromatic compounds The aromatic compound (B) in this embodiment may be an aromatic hydrocarbon compound or a heteroaromatic compound, and specifically, it is at least one compound selected from the following general formulae (V-1) and (V-3) to (V-6). [ka] In formula (V-1), A represents a nitrogen atom or a carbon atom, R1 represents an electron-withdrawing group, R2 represents a monovalent organic group having 1 to 6 carbon atoms, and a plurality of R1 and / or R2 may form a ring structure, and R3 represents a group represented by the following general formula (V-2): [ka] (In formula (V-2), R4 and R5 each independently represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms.) wherein m1 is an integer of 1 to 2, m2 is an integer of 0 to 3, and m3 is an integer of 0 to 2; when A is a carbon atom, m3 is 1 or 2, and 1≦m1+m2+m3≦6. [ka] [ka] [ka] [ka] {In formulas (V-3) to (V-6), each X is independently a nitrogen atom, a sulfur atom, or an oxygen atom; R1 is an electron-withdrawing group; each R2 is independently a monovalent organic group having 1 to 6 carbon atoms, and a plurality of R2 may form a ring structure; m1 is an integer of 1 to 2, m2 is an integer of 0 to 3, 1≦m1+m2≦6; and T represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.}

[0407] From the viewpoint of the imidization rate and Cu voids, the aromatic compound (B) according to the present embodiment preferably has a structure represented by the above general formula (V-1), and more preferably is at least one selected from the group consisting of the following general formulas (V-7) and (V-8). [ka] [ka] {In formulas (V-7) and (V-8), R1, R2, m1, and m2 are as defined in at least one of general formulas (V-1) and (V-3) to (V-6).}

[0408] The electron-withdrawing group according to the present embodiment is not limited as long as it is a functional group that withdraws electrons. Among these, a nitro group, a fluoro group, a chloro group, a bromo group, a cyano group, a sulfonyl group, a halogenated alkyl group having 1 to 8 carbon atoms, and a monovalent organic group having 1 to 4 carbon atoms including a carbonyl group are preferred, and an amide group, a carboxyl group, a phthalimide group, a formyl group, and an ester group having 1 to 3 carbon atoms are more preferred.

[0409] The aromatic compound represented by the general formula (V-1) above includes compounds represented by the following general formula (V-22): [ka] Examples of compounds include compounds having the following structure:

[0410] More specific examples of aromatic compounds include, but are not limited to, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, p-dimethylaminoacetophenone, 4,4'-diaminobenzanilide, 4-aminophthalimide, 4-aminobenznitrile, 4-nitro-1-naphthylamine, and 4-nitroaniline.

[0411] Examples of the compound represented by general formula (V-3) include the following. 3,6-Dichloropyridazine, 3,5-dichloropyridazine, 3,6-dibromopyridazine, 3,5-dibromopyridazine, 3,4,6-trichloropyridazine, 1,4-dichlorophthalazine, 3-chloro-6-methylpyridazine, 3,6-dichloro-4-methylpyridazine, pyridazine-4-carboxylic acid, 3-chloro-6-methoxypyridazine, 6-hydroxypyridazine-3-carboxylic acid, 3-chloro-6-phenylpyridazine, sulfamethoxypyridazine, 6-phenyl-3(H)-pyridazinone, 4,5-dibromo-3(2H)-pyridazinone

[0412] Examples of the compound represented by general formula (V-4) include the following. 5-Bromopyrimidine, 2-bromopyrimidine, 5-chloropyrimidine, 2-chloropyrimidine, 5-fluoropyrimidine, 2-fluoropyrimidine, 2-cyanopyrimidine, 5-cyanopyrimidine, 4,6-dichloropyrimidine, 5-bromo-2-fluoropyrimidine, 4,6-dibromopyrimidine, 5-bromo-2-chloropyrimidine, 2,5-dichloropyrimidine, 2,5-dibromopyrimidine, 5-bromo-2-iodopyrimidine, 5-bromo-2-methylpyrimidine, 2-chloro-5-iodopyrimidine, 2,4-dichloropyrimidine, 2- Chloro-4-methylpyrimidine, 2-chloro-5-fluoropyrimidine, 2-chloro-5-methylpyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-tributylpyrimidine, 4-chloro-2-methylpyrimidine, pyrimidine-2-sulfonyl fluoride, 4,5,6-trichloropyrimidine, 5-bromo-2-tert-butylpyrimidine, 4-chloro-2-(methylthio)pyrimidine, pyrimidine-5-carboxylic acid, 5-bromo-hydroxypyrimidine, 2-amino-5-bromopyrimidine, 5-bromo-2-methoxypyrimidine, 5-chloro-2,4,6-trifluoropyrimidine, pyrimidine-2-carboxylic acid, methyl pyrimidine-2-carboxylate, 5-nitropyrimidine, methyl 5-bromopyridine-2-carboxylate, pyrimidine-4-carboxylic acid, 2-amino-5-pyrimidine, 4-aminopyrimidine-5-carboxylate, 2-amino-4-(trifluoromethyl)pyrimidine, 5-bromo-2,4-dimethoxypyrimidine, 2-hydroxy-4-(trifluoromethyl)pyrimidine, 6-trifluoromethyl-4-pyrimidinol, ethylpyrimidine- 4-carboxylate, 4,6-dihydroxy-5-nitropyrimidine, 4,6-dimethoxy-2-(methylsulfonyl)pyrimidine, 6-hydroxy-4-pyrimidinecarboxylic acid, 4-hydroxy-2-methyl-6-(trifluoromethyl)pyrimidine, 4-amino-5-fluoro-2-methoxypyrimidine, 2-hydrazino-4-(trifluoromethyl)pyrimidine, 4-hydroxy-6-(trifluoromethyl)-4-pyrimidinol, 4-phenylpyrimidine, 5-bromo-2-(methylthio)pyrimidine-4-carboxylic acid, 4-amino-2,6-dihydroxy-5-nitrosopyrimidine, ethyl 2-amino-4-hydroxypyrimidine-5-carboxylic acid, 2-bromo-4,6-diphenylpyrimidine, 2-amino-4,6-diphenylpyrimidine,

[0413] Examples of the compound represented by general formula (V-5) include the following. Examples include 2-bromopyrazine, 2-chloropyrazine, 3-chloropyrazine-2-carboxyamide, 5-chloropyrazine-2-carboxylic acid, cyanopyrazine, and 2,5-dibromopyrazine.

[0414] Examples of the compound represented by general formula (V-6) include the following. Examples include 4-bromo-1H-imidazole, 2-bromo-4-nitroimidazole, 2-chloro-1H-imidazole, 5-chloro-1-methyl-4-nitroimidazole, and 4,5-dicyanoimidazole.

[0415] Furthermore, when R1 in the compound represented by the general formula (V-1), (V-3), or (V-4) is a monovalent organic group containing...

Claims

1. (A) polyimide precursor: 100 parts by mass, (B) a compound represented by at least one of the following general formulas (V-1) and (V-3) to (V-6); 0.1 to 50 parts by mass, (C) Photosensitizer: 0.1 to 50 parts by mass A photosensitive resin composition comprising: 【Chemistry 1】 In formula (V-1), A is a nitrogen atom or a carbon atom, and R １ is an electron-withdrawing group, R ２ is a monovalent organic group having 1 to 6 carbon atoms, and a plurality of R １ and / or R ２ may form a ring structure, and R ３ is represented by the following general formula (V-2): 【Chemistry 2】 (In formula (V-2), R ４ and R ５ are each independently a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms. The structure represented by m １ is an integer from 1 to 2, m ２ is an integer from 0 to 3, m ３ is an integer from 0 to 2, and when A is a carbon atom, m ３ is 1 or 2, and 1≦m １ +m ２ +m ３ ≦6. 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 In formulae (V-3) to (V-6), X is a nitrogen atom, a sulfur atom, or an oxygen atom; R １ are each independently an electron-withdrawing group, R ２ are each independently a monovalent organic group having 1 to 6 carbon atoms, ２ may form a ring structure, m １ is an integer from 1 to 2, m ２ is an integer of 0 to 3, and 1≦m １ +m ２ ≦6, and T represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

2. The photosensitive resin composition according to claim 1, wherein the compound (B) is at least one selected from the group consisting of the following general formulas (V-7) and (V-8): 【Chemistry 7】 【Chemistry 8】 In formulae (V-7) and (V-8), R １ , R ２ , m １ , and m ２ is as defined in at least one of the general formulae (V-1) and (V-3) to (V-6).

3. In at least one of the general formulas (V-1) and (V-3) to (V-6), １ is at least one selected from the group consisting of a nitro group, a fluoro group, a chloro group, a bromo group, a cyano group, a sulfonyl group, a halogenated alkyl group having 1 to 8 carbon atoms, and a monovalent organic group having 1 to 4 carbon atoms containing a carbonyl group.

4. In at least one of the general formulas (V-1) and (V-3) to (V-6), １ is at least one selected from the group consisting of an amide group, a carboxyl group, a phthalimide group, a formyl group, and an ester group having 1 to 3 carbon atoms.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the polyimide precursor (A) is represented by the following general formula (V-9): 【Chemistry 9】 {In formula (V-9), X １ is a tetravalent organic group having 6 to 40 carbon atoms; Y １ is a divalent organic group having 6 to 40 carbon atoms, n １ is an integer from 2 to 150; R ５ and R ６ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. ５ and R ６ At least one of the groups is a group represented by the following general formula (V-10): 【Chemistry 10】 {In formula (V-10), R ７ , R ８ and R ９ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ４ is an integer from 2 to 10.

6. In the general formula (V-9), １ The photosensitive resin composition according to claim 5, wherein the compound represented by the formula (V-11), (V-12) or (V-13) is at least one selected from the following formulae (V-11), (V-12) and (V-13): 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】

7. In the general formula (V-9), １ is at least one selected from the group consisting of the following general formulas (V-14) and (V-15): 【Chemistry 14】 【Chemistry 15】

8. The photosensitive resin composition according to any one of claims 5 to 7, wherein the polyimide precursor (A) includes a structure represented by the following general formula (V-16): 【Chemistry 16】 {In formula (V-16), n １ is an integer from 2 to 150; R ５ and R ６ is as defined in the general formula (V-9).

9. The photosensitive resin composition according to any one of claims 5 to 7, wherein the polyimide precursor (A) includes a structure represented by the following general formula (V-17): 【Chemistry 17】 {In formula (V-17), n １ is an integer from 2 to 150; R ５ and R ６ is as defined in the general formula (V-9).

10. The photosensitive resin composition according to any one of claims 5 to 7, wherein the polyimide precursor (A) simultaneously contains a polyimide precursor having a structure represented by the following general formula (V-16) and a polyimide precursor having a structure represented by the following general formula (V-17): 【Chemistry 18】 {In formula (V-16), n １ is an integer from 2 to 150; R ５ and R ６ is as defined in the general formula (V-9). 【Chemistry 19】 {In formula (V-17), n １ is an integer from 2 to 150; R ５ and R ６ is as defined in the general formula (V-9).

11. The photosensitive resin composition according to any one of claims 1 to 10, wherein the (C) photosensitizer is a photoradical generator, and the photosensitive resin composition is a negative type.

12. Further, (D) a thermal base generator: 0.1 to 50 parts by mass The photosensitive resin composition according to any one of claims 1 to 11, comprising:

13. A method for producing a polyimide, comprising curing the photosensitive resin composition according to any one of claims 1 to 12.

14. The following steps: (1) applying the photosensitive resin composition according to any one of claims 1 to 12 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat treating the relief pattern to form a hardened relief pattern; A method for producing a cured relief pattern comprising:

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