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

Abstract

Provided is a photosensitive resin composition which has low dielectric properties and low moisture permeability, and is capable of forming a high-resolution cured relief pattern. This photosensitive resin composition contains 100 parts by mass of one or more resins selected from a polyimide and a polyimide precursor, 0.5-10 parts by mass of a photosensitizer, and 100-300 parts by mass of a solvent. The imide group concentration in a polyimide cured film obtained by heating said photosensitive resin composition at 350°C and curing the same is 12-26 wt%, and said resin contains a structure represented by general formula (14).

Description

Technical Field

[0001] The present disclosure relates to a photosensitive resin composition, a method for producing a polyimide cured film using the same, and a polyimide cured film.

Background Art

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, etc., which have excellent heat resistance, electrical properties, and mechanical properties, have been used for insulating materials of electronic components and passivation films, surface protection films, interlayer insulating films, etc. of semiconductor devices. Among these resins, those provided in the form of a photosensitive resin composition can easily form a heat-resistant relief pattern film by applying, exposing, developing, and curing the composition (imidization, benzoxazolization) or by thermal crosslinking. Such a photosensitive resin composition has the characteristic of enabling a significant shortening of the process compared to conventional non-photosensitive materials, and is used in the production of semiconductor devices.

[0003] By the way, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards by various methods according to the purpose. Conventionally, elements have generally been manufactured by the wire bonding method in which thin wires are used to connect from the external terminals (pads) of the element to the lead frame. However, as the speed of elements has increased and the operating frequency has reached GHz, the difference in the wiring length of each terminal in mounting has come to affect the operation of the element. Therefore, in the mounting of high-end application elements, it has become necessary to accurately control the length of the actual wiring, and it has become difficult to meet this requirement with wire bonding.

[0004] Therefore, a flip-chip mounting method has been proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped and directly mounted on a printed circuit board. In this flip-chip mounting method, since the wiring distance can be accurately controlled, it is adopted for high-end devices that handle high-speed signals or for mobile phones, etc., due to their small mounting size, and the demand for it has been rapidly expanding. More recently, a semiconductor chip mounting technique called fan-out wafer-level packaging (FOWLP) has been proposed, in which a wafer after the previous process is diced to manufacture individual chips, the individual chips are reconstructed on a support and encapsulated with a molding resin, and then a redistribution layer is formed after the support is peeled off (for example, see Patent Document 1). In fan-out wafer-level packaging, since the redistribution layer is formed with a thin film thickness, there are advantages that the height of the package can be reduced and high-speed transmission and cost reduction can be achieved.

[0005] In recent years, with the remarkable increase in information communication volume, it has become necessary to achieve higher communication speeds than the conventional level. There has been a shift to fifth-generation communication (5G) using frequencies of 3 GHz or higher, or to communication in the extremely high frequency bands of the quasi-millimeter wave band (20 GHz to 30 GHz) to the millimeter wave band (30 GHz or higher), where it is easier to secure a wider frequency bandwidth. High-frequency compatibility is required not only for printed circuit boards but also for semiconductor chips on which the boards are mounted. Therefore, an antenna-in-package (AiP) in which a front-end module (FEM) for transmitting and receiving radio waves and an antenna are integrated has been developed to reduce transmission loss (for example, see Patent Document 2 below). In AiP, since the wiring length is short, it is possible to suppress the transmission loss that increases in proportion to the wiring length.

[0006] Generally, as the frequency of an electrical signal increases, the transmission loss increases. To reduce the transmission loss in the high-frequency band, there are roughly two methods: a method of reducing the dielectric loss and a method of reducing the conductor loss. For the former, a photosensitive resin composition is required to have low dielectric characteristics (low dielectric tangent, low dielectric constant) (for example, see Patent Document 3). For the latter, it is necessary to reduce the roughness of the metal redistribution layer.

[0007] As an interlayer material for protecting the rewiring layer, not only low dielectric characteristics but also high adhesion between the rewired metal layer and the resin layer are required from the viewpoint of reliability. In particular, in recent years, it has been required that the temperature for heat-curing the rewiring layer be lower. As such a photosensitive resin composition, for example, Patent Document 4 can be cited.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0009] In recent years, due to the diversification of package mounting technologies, the types of substrates have become diversified, and in addition, the rewiring layers have become multilayered. Therefore, the influence of the dielectric constant and dielectric tangent (tanδ) of the insulating material used for wiring formation has become significant. When the dielectric constant and dielectric tangent are high, transmission loss increases due to an increase in dielectric loss. Since polyimide resin is excellent in insulation performance and thermomechanical properties, it has high material reliability. However, due to polar functional groups derived from imide groups, the addition of polar functional groups for photosensitization, and the influence of additives, etc., the dielectric constant and dielectric tangent are regarded as a problem because they are high. In addition, the dielectric tangent may be a problem due to its dependence on frequency in some cases, and it is considered preferable that the moisture permeability of the insulating layer be low.

[0010] The present disclosure aims to provide a photosensitive resin composition having low dielectric properties and low moisture permeability and capable of forming a cured relief pattern with high resolution, a method for producing a polyimide cured film using the same, and a polyimide cured film.

Means for Solving the Problems

[0011] Examples of embodiments of the present disclosure are listed in the following items [1] to

[19] . [1] (A) At least one resin selected from 100 parts by mass of polyimide and polyimide precursor; (B) 0.5 to 10 parts by mass of a photosensitizer; (C) 100 to 300 parts by mass of a solvent; A photosensitive resin composition comprising: in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ° C., the imide group concentration U, which is the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic dianhydride and diamine, is 12 wt% to 26 wt%, A photosensitive resin composition, wherein the resin contains a structure represented by the following general formula (14). [Chemical Formula] {In the formula, R 15 is an organic group having 1 to 5 carbon atoms, and R 16 , R 17 and R 18 are each independently a single bond that may form a ring structure, an alkyl group having 1 to 10 carbon atoms, or an organic group containing an aromatic ring having 6 to 10 carbon atoms, m9 is an integer selected from 1 to 4, and m 10 , m 11 and m 12 are each independently an integer selected from 0 to 4, Z2 is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and * represents a connection portion with the main chain of the resin.} [2] In the polyimide of the polyimide cured film obtained by heating and curing the above photosensitive resin composition at 350 ° C, the aliphatic hydrocarbon group concentration T, which is the ratio of the total molecular weight of the aliphatic hydrocarbon groups to the molecular weight of the repeating unit containing the structures derived from the tetracarboxylic dianhydride and the diamine compound, is 4 wt% to 35 wt%. The photosensitive resin composition according to Item 1. [3] The photosensitive resin composition according to Item 1 or 2, wherein the structure represented by the general formula (14) is derived from a diamine. [4] The photosensitive resin composition according to any one of Items 1 to 3, wherein the above resin is a polyimide precursor. [5] The photosensitive resin composition according to Item 4, wherein the above polyimide precursor contains a structure represented by the following general formula (4). [Chemical formula] {In the formula, 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 R4 and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R4 and R5 is a group represented by the following general formula (5).} [Chemical formula] {In the formula, R6, R7 and R8 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m2 is an integer of 2 to 10.} [6] (A) At least one resin selected from 100 parts by mass of polyimide and polyimide precursor; (B) 0.5 to 10 parts by mass of a photosensitizer; (C) 100 to 300 parts by mass of a solvent; A photosensitive resin composition comprising: When the above resin contains a polyimide precursor, the above polyimide precursor has the following general formula (4): [Chemical formula] {In the formula, 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 R4 and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R4 and R5 is a group represented by the following general formula (5).}

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] The photosensitive resin composition according to item 9, wherein at least one of the tetracarboxylic dianhydrides and at least one of the diamines constituting the resin have an aliphatic hydrocarbon group.

[11] (D) The photosensitive resin composition according to any one of items 1 to 10, further comprising a silane coupling agent.

[12] (E) The photosensitive resin composition according to any one of items 1 to 11, further comprising a radically polymerizable compound.

[13] (E) The photosensitive resin composition according to item 12, wherein the radically polymerizable compound has an alkyl group.

[14] (F) The photosensitive resin composition according to any one of items 1 to 13, further comprising a thermal crosslinking agent.

[15] (G) The photosensitive resin composition according to any one of items 1 to 14, further comprising a filler.

[16] The following steps: Coating the photosensitive resin composition according to any one of items 1 to 15 on a substrate to form a photosensitive resin layer on the substrate; Heating and drying the obtained photosensitive resin layer; Exposing the photosensitive resin layer after heating and drying; Developing the photosensitive resin layer after exposure; Heat-treating the photosensitive resin layer after development to form a polyimide cured film; A method for producing a polyimide cured film, comprising:

[17] The method for producing a polyimide cured film according to item 16, wherein the coating to development steps are performed such that a photosensitive resin layer having a film thickness of 10 μm to 15 μm is obtained in the development step, and the development time during development is 30 seconds or less.

[18] A polyimide cured film, having a dielectric loss tangent of 0.003 to 0.014 at a frequency of 40 GHz by a perturbation method split cylinder resonator method, and the following formula (3): 3 < tanδ 40×WVTR < 10 (3) {wherein, tanδ 40 represents the dielectric loss tangent at a frequency of 40 GHz by the perturbation method split cylinder resonator method, and WVTR represents the moisture permeability of the polyimide cured film converted to a film thickness of 10 μm.}, a polyimide cured film that satisfies

[19] The photosensitive resin composition is the photosensitive resin composition according to any one of Items 1 to 15, which is used for a rewiring layer.

Advantages of the Invention

[0012] By using the photosensitive resin composition of the present disclosure, a cured resin film excellent in the resolution of a relief pattern, having low dielectric characteristics, low moisture permeability, and good chemical resistance can be manufactured. By using a polyimide precursor having a specific terminal crosslinking group and an aliphatic hydrocarbon group, the solubility in a developer of the pre-baked film is improved, and thus the resolution of the relief pattern is improved. In addition, the hydrophobicity and crosslink density in the cured film are improved, so that the moisture permeability is lowered, the chemical resistance is improved, and the dielectric loss tangent is lowered by increasing the excluded volume.

Brief Description of the Drawings

[0013]

Figure 1

Embodiments for Carrying Out the Invention

[0014] Hereinafter, embodiments of the present disclosure will be described in detail. Throughout this specification, in the general formula, structures represented by the same reference numerals are independently selected respectively as long as not otherwise specified when there are a plurality in the molecule, and they may be the same or different from each other. Also, structures represented by common reference numerals in different general formulas are also independently selected respectively as long as not otherwise specified, and they may be the same or different from each other.

[0015] <Photosensitive Resin Composition> The photosensitive resin composition of the present disclosure contains 100 parts by mass of at least one resin selected from (A) a polyimide and a polyimide precursor, (B) 0.5 to 10 parts by mass of a photopolymerization initiator, and (C) 50 to 500 parts by mass of a solvent. Further, the photosensitive resin composition of the present disclosure may further contain, if desired, in addition to the above components, (D) a silane coupling agent, (E) an ethylenically unsaturated group-containing compound, (F) a thermal crosslinking agent, (G) a filler, and other components.

[0016] [[(A) Polyimide and polyimide precursor]] (A) At least one resin selected from a polyimide and a polyimide precursor preferably contains a structure represented by the following general formula (14) from the viewpoints of resolution, moisture permeability, and low dielectric constant. [Chemical formula] {In the formula, R 15 is an organic group having 1 to 5 carbon atoms, and R 16 , R 17 and R 18 are each independently a single bond that may form a ring structure, an alkyl group having 1 to 10 carbon atoms, or an organic group containing an aromatic ring having 6 to 10 carbon atoms, m9 is an integer selected from 1 to 4, and m 10 , m 11 and m 12 are each independently an integer selected from 0 to 4, Z2 is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and * represents a connecting portion to the main chain of the above resin.}

[0017] In the above general formula (14), Z2 is preferably a structure selected from a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and the organic group having a heteroatom is preferably a structure selected from the following formulas. The organic group having a heteroatom is an organic group having at least one heteroatom selected from N, O, P, S, Cl, I, and Br. Examples of the organic group include unsaturated hydrocarbons and saturated hydrocarbons, and more preferably saturated hydrocarbons. The organic group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

[0018] By including the structure of the general formula (14) above, a cured film with good resolution of the relief pattern and low moisture permeability can be obtained. Although not bound by theory, it is considered that by introducing an organic group into the aromatic ring, the solubility of the polyimide precursor in the developer is improved, the contrast with the exposed area is easily ensured, and the resolution of the relief pattern is improved. Also, although not bound by theory, it is considered that by introducing an organic group into the aromatic ring, the hydrophobicity of the film increases and it becomes difficult for moisture to permeate.

[0019] Examples of the structure of the general formula (14) above include at least one structure selected from the group consisting of the following general formula (9).

Chemical formula

[0020] When the structure of the above formula (14) is derived from the tetracarboxylic dianhydride in adjusting the polyimide and the polyimide precursor, it preferably includes at least one structure selected from the group consisting of the following general formula (10).

Chemical formula

[0021] When the structure of the above formula (14) is derived from the diamine compound in adjusting the polyimide and the polyimide precursor, it preferably includes at least one structure selected from the group consisting of the following general formula (11).

Chemical formula

[0022] At least one resin selected from polyimide and polyimide precursors preferably also contains a structure represented by the following general formula (15) from the viewpoints of resolution, moisture permeability, and low dielectric constant. [Chemical formula] {In the formula, each Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom and may form a cyclic structure, a represents an integer of 0 to 4, each A independently represents an oxygen atom or a sulfur atom, and B represents a single bond or the following formula: [Chemical formula] One of them.}

[0023] In the photosensitive resin composition of the present disclosure, the imide group concentration U in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition is 12 wt% to 26 wt%. In the present specification, the "imide group concentration U" means the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing the structure derived from the tetracarboxylic dianhydride and the diamine compound in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C. The condition of heating and curing at 350°C is to clarify the standard of the aliphatic hydrocarbon group concentration T based on the state where the polyimide precursor is almost 100% imidized, and it is not intended that the photosensitive resin composition be heated and cured at 350°C in actual use.

[0024] If the imide group concentration U is 12.0 wt% or more, the resolution of the relief pattern tends to be good. The imide group concentration U is preferably 12.5 wt% or more, more preferably 13.5 wt% or more. On the other hand, when the imide group concentration U is 26 wt% or less, the dielectric constant of the obtained polyimide cured film tends to be good. The imide group concentration U is more preferably 23.0 wt% or less, still more preferably 21.0 wt% or less.

[0025] The imide group concentration U in the repeating unit of the polyimide cured film is determined using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used during the preparation of the polyimide precursor, according to the following formula (I): 70.02×2 / [Mw(A)+Mw(B)-36]×100 (I) {In formula (I), Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine.} When two or more types of tetracarboxylic dianhydrides and / or diamine compounds are used, for example, when adjusting using two types of tetracarboxylic dianhydrides and / or diamines, the following formula (II): 70.02×2 / [Mw(A1)×a1+Mw(A2)×a2+Mw(B1)×b1+Mw(B2)×b2-36]×100 (II) {In formula (II), Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride, Mw(A2) represents the molecular weight of the second tetracarboxylic dianhydride, a1 represents the content of the first tetracarboxylic dianhydride, a2 represents the content of the second tetracarboxylic dianhydride, Mw(B1) represents the molecular weight of the first diamine compound, Mw(B2) represents the molecular weight of the second diamine compound, b1 represents the content of the first diamine compound, and b2 represents the content of the second diamine compound. However, a1, a2, b1, and b2 satisfy a1 + a2 = 1 and b1 + b2 = 1, respectively.} The same applies when using three or more types of tetracarboxylic dianhydrides and / or diamines. When tetracarboxylic acid and / or tetracarboxylic acid dichloride are used as raw materials, the calculation is performed using the mass of the corresponding tetracarboxylic dianhydride.

[0026] The polyimide and / or polyimide precursor resin may have at least one terminal structure selected from the group consisting of the following general formulas (1) to (3).

Chemical formula

[0027] The structure of W is not particularly limited, but is preferably a divalent to trivalent organic group having a weight average molecular weight of less than 300, more preferably a divalent to trivalent organic group having 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms.

[0028] (A) The polyimide precursor may have a polymerizable group at the terminal of the main chain. The (A) polyimide precursor having a polymerizable group preferably has a structure represented by the following general formula.

Chemical formula

Chemical formula

[0029] It is preferable that f1 contains at least one group among an amide group, an imide bond, a urea group, and a urethane group. If f1 is an ester group, it is likely to be hydrolyzed and may not be crosslinked. These four groups (amide group, imide bond, urea group, and urethane group) are difficult to be hydrolyzed and thus have high chemical resistance.

[0030] The reactive substituent b1 that crosslinks by heat or light is preferably at least one selected from, for example, an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, an ethynyl group, an imino group, an isocyanato group, a cyanato group, a cycloalkyl group, an epoxy group, an oxetanyl group, a carbonate group, a hydroxyl group, a mercapto group, a methylol group, and an alkoxyalkyl group. From the viewpoint of film thickness uniformity, b1 is preferably at least one selected from an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, and an ethynyl group. Particularly, the methacrylic group is preferable.

[0031] The reactive substituent g1 that crosslinks with heat or light is, for example, at least one selected from an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, an ethynyl group, an imino group, an isocyanato group, a cyanato group, a cycloalkyl group, an epoxy group, an oxetanyl group, a carbonate group, a hydroxyl group, a mercapto group, a methylol group, and an alkoxyalkyl group. From the viewpoint of film thickness uniformity, g1 is preferably at least one selected from an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, and an ethynyl group. Particularly preferred for g1 is the methacrylic group.

[0032] Compounds having a reactive substituent that reacts with heat or light and having a site that also reacts with a carboxyl group, and specific examples of the main chain terminals of the polyimide precursor modified with the reactive substituent are shown below.

[0033] [Chemical formula]

[0034] The aliphatic hydrocarbon group concentration T of the polyimide cured film obtained by heating and curing the photosensitive resin composition is preferably 4 wt% to 35 wt%. In the specification of the present application, the "aliphatic hydrocarbon group concentration T" refers to the proportion of the total molecular weight of the aliphatic hydrocarbon groups in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 °C, relative to the molecular weight of the repeating unit composed of the tetracarboxylic dianhydride and the diamine compound. The basis of heating and curing at 350 °C is to make it easier to adjust the aliphatic hydrocarbon group concentration T by using the state where the polyimide precursor is almost 100% imidized as a reference, and it is not intended that the photosensitive resin composition be heated and cured at 350 °C in actual use. Here, the "aliphatic hydrocarbon group" is a hydrocarbon group having at least one structure selected from the group consisting of a saturated aliphatic chain, an unsaturated aliphatic chain, and an alicyclic structure that branches from the main chain of the polyimide precursor and does not contain heteroatoms, and may be either a straight chain or a branched chain. The alkylene skeleton portion constituting a part of the main chain and the quaternary carbon (carbon substituted twice and constituting a part of the main chain) constituting a part of the main chain are not included in the "aliphatic hydrocarbon group" in the calculation of the aliphatic hydrocarbon group concentration. The aliphatic hydrocarbon groups constituting the side chain portion branched from the main chain are included in the "aliphatic hydrocarbon group" in the calculation of the aliphatic hydrocarbon group concentration, whether saturated or unsaturated, and whether chain-like or alicyclic. Examples of the structure of the "aliphatic hydrocarbon group" include structures represented by the following general formula (A1), the following general formula (A2), and the following general formula (A3).

[0035] [Chemical formula]

[0036] In general formulas (A1) to (A3), L is a single bond or an a-valent organic group that may be either a straight-chain or branched-chain saturated hydrocarbon or a straight-chain or branched-chain unsaturated hydrocarbon group, b is an integer from 1 to 6, and R a1 is an organic group having 1 to 8 carbon atoms or a hydrogen atom that may have a ring structure. * is a connecting group to the main chain structure.

[0037] From the perspective of the dielectric loss tangent of the polyimide cured film, the aliphatic hydrocarbon group preferably has a monovalent aliphatic saturated hydrocarbon group having 1 to 3 carbon atoms, such as a methyl group. If the group concentration T is 4 wt% or more, the dielectric loss tangent of the polyimide cured film tends to be good. The aliphatic hydrocarbon group concentration T is preferably 5 wt% or more, more preferably 7 wt% or more, and still more preferably 8 wt% or more. When the aliphatic hydrocarbon group concentration T is 5 wt% or more, the moisture permeability tends to be good. On the other hand, when the aliphatic hydrocarbon group concentration T is 35 wt% or less, the resolution and moisture permeability of the obtained polyimide cured film tend to be good. The aliphatic hydrocarbon group concentration T is more preferably 28 wt% or less, more preferably 17 wt% or less, and still more preferably 12% or less.

[0038] The aliphatic hydrocarbon group concentration T is determined by using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in the preparation of the polyamide and / or polyimide precursor, according to the following formula (I): [Mw(P)+Mw(Q)] / [Mw(A)+Mw(B)-36]×100 (I) {In formula (I), Mw(P) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the tetracarboxylic dianhydride, Mw(Q) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the diamine compound, Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine compound.} It is represented by

[0039] When two or more types of tetracarboxylic dianhydrides and / or diamine compounds are used, for example, when two types of tetracarboxylic dianhydrides and two types of diamine compounds are used, the following formula (II): [Mw(P1)×a1+Mw(P2)×a2+Mw(Q1)×b1+Mw(Q2)×b2] / [Mw(A1)×a1+Mw(A2)×a2+Mw(B1)×b1+Mw(B2)×b2-36] ×100 (II) In formula (II), Mw(P1) represents the sum of the molecular weights of aliphatic hydrocarbon groups in the first tetracarboxylic dianhydride, Mw(P2) represents the sum of the molecular weights of aliphatic hydrocarbon groups in the second tetracarboxylic dianhydride, Mw(Q1) represents the sum of the molecular weights of aliphatic hydrocarbon groups in the first diamine compound, and Mw(Q2) represents the sum of the molecular weights of aliphatic hydrocarbon groups in the second diamine compound. Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride, Mw(A2) represents the molecular weight of the second tetracarboxylic dianhydride, a1 represents the content ratio of the first tetracarboxylic dianhydride, and a2 represents the content ratio of the second tetracarboxylic dianhydride. Mw(B1) represents the molecular weight of the first diamine compound, Mw(B2) represents the molecular weight of the second diamine compound, b1 represents the content ratio of the first diamine compound, and b2 represents the content ratio of the second diamine compound. Also, a1, a2, b1, and b2 each satisfy a1 + a2 = 1 and b1 + b2 = 1.} It is represented by. When three or more types of tetracarboxylic dianhydrides and / or diamine compounds are used, it is similarly determined. When tetracarboxylic acid and / or tetracarboxylic acid chloride is used as a raw material, it is calculated using the molecular weight of the corresponding tetracarboxylic dianhydride.

[0040] At least one of the tetracarboxylic dianhydride and the diamine compound preferably has an aliphatic hydrocarbon group. When the diamine compound has an aliphatic hydrocarbon group, it is preferable because the moisture permeability tends to be low. When both the diamine compound and the tetracarboxylic dianhydride have an aliphatic hydrocarbon group, it is preferable because the solubility in the developer is improved and the development rate tends to be improved.

[0041] (A) In the IR spectrum of the polyimide obtained by heating and curing the polyimide precursor at 230 ° C, 1450 cm -1 Above 1550 cm -1 The maximum peak intensity of the absorption peak in the following range is Ph1, the second peak intensity is Ph2, and the peak intensity near 1380 cm -1 When normalized with Ph1 as 1, the following formula (2): 0.34 ≦ Ph2 × Im1 ≦ 1.2 (2) It is preferable to satisfy the following condition

[0042] The measurement conditions of the IR spectrum are carried out by the method described in the examples below. Peaks are those where the peak intensities on the low-wavelength side and the high-wavelength side of the peak top are lower than the peak intensity of the peak top. When either the peak intensity on the low-wavelength side or the high-wavelength side is higher than the peak intensity of the peak top, it is not considered a peak.

[0043] For example, in the case of a polyimide having an IR spectrum shown in the graph of FIG. 1, Ph1 = 1 (1500 cm -1 ), Ph2 = 0.42 (1473 cm -1 ), Im1 = 0.68 (1373 cm -1 ). The signal found on the high-frequency side of Ph1 (1512 cm -1 ) is not considered a peak.

[0044] If there is only one peak in the range of 1450 cm -1 or higher and 1550 cm -1 or lower, Ph2 is set to 0. The peak intensity around 1380 cm -1 is the value of the largest peak within the range of ±10 cm -1 of each wavenumber as the peak intensity.

[0045] It is preferable that Ph2 × Im1 is 0.34 or more, more preferably 0.36 or more, still more preferably 0.40 or more, and 0.45 or more, and in this case, the resolution tends to be good. Although not bound by theory, it is considered that when Ph2 × Im1 is 0.34 or more, the solubility of the polyimide precursor is improved and the resolution is improved. On the other hand, it is preferable that Ph2 × Im1 is 1.2 or less, and when it is 1.1 or less, the dielectric tangent tends to be good. Although not bound by theory, it is considered that when Ph2 × Im1 is 1.2 or less, the molecular motion in the high-frequency region decreases.

[0046] In the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ° C, the following formula (1): -12.6 < U - T < 16.0 (1) {In the formula, U represents the imide group concentration of the polyimide, and T represents the aliphatic hydrocarbon group concentration of the polyimide.} It is preferable to satisfy. U - T is preferably -12.6 or more, more preferably -11.0 or more, and preferably -10 or more, and the resolution tends to be preferable. U - T is preferably 16.0 or less, more preferably 12.5 or less, preferably 12.0 or less, and preferably 11.0 or less, and tends to have excellent moisture permeability. The reference for heating and curing at 350 ° C is to make it easy to adjust the aliphatic hydrocarbon group concentration T by using the state in which the polyimide precursor is almost 100% imidized as a reference, and the photosensitive resin composition is not intended to be heated and cured at 350 ° C in actual use.

[0047] (A) Examples of the polyimide precursor include polyamide precursors having a structural unit represented by the following general formula (4).

Chemical formula

Chemical formula

[0048] From the viewpoints of resolution and low dielectric properties, the ratio of the photosensitive group per repeating unit in the (A) polyimide precursor resin represented by the general formula (4) is preferably 15 wt% to 35 wt%. From the viewpoint of dielectric properties, it is preferable that the photosensitive group is less, and from the viewpoint of resolution, it is preferable that the photosensitive group is more. In the present specification, the "ratio of the photosensitive group" means the ratio of the molecular weight of the photopolymerizable group-containing compound constituting the repeating unit based on the molecular weight of the entire repeating unit represented by the general formula (4). Examples of the photopolymerizable group include an unsaturated double bond.

[0049] The ratio of the photosensitive group per repeating unit of the polyimide precursor resin is determined using the molecular weights of the tetracarboxylic dianhydride and the diamine compound used during the preparation of the polyimide precursor, by the following formula (I): [Mw(R)] / [Mw(A)+Mw(B)+Mw(R)-36]×100 (I) {In the formula (I), Mw(R) represents the sum of the molecular weights of the compounds containing the photopolymerizable group (photopolymerizable group-containing compounds), Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine compound.} It is represented by. Note that when two or more types of tetracarboxylic dianhydrides and / or diamine compounds are used, calculations are performed according to the ratio of the raw materials, in the same manner as the definition of the aliphatic hydrocarbon group concentration T. Further, in the case of a copolymer of a photopolymerizable group-containing compound and a compound not containing a photopolymerizable group, the following formula (II): [Mw(R)×c1] / [Mw(A)+Mw(B)+Mw(R)×c1+Mw(S)×c2-36]×100 (II) {In formula (II), Mw(R) represents the sum of the molecular weights of the photopolymerizable group-containing compounds, Mw(S) represents the sum of the molecular weights of the compounds not containing a photopolymerizable group, Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine compound. c1 represents the content of the photopolymerizable group-containing compound, c2 represents the content of the compound not containing a photopolymerizable group, and c1 and c2 satisfy c1 + c2 = 1, respectively.} It is represented by. When tetracarboxylic acid and / or tetracarboxylic acid chloride is used as a raw material, it is calculated using the molecular weight of the corresponding tetracarboxylic dianhydride.

[0050] From the viewpoint of the photosensitive characteristics and mechanical characteristics of the photosensitive resin composition, n1 in the general formula (4) is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

[0051] In the general formula (4), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive characteristics, and more preferably an aromatic group or an alicyclic aliphatic group in which a -COOR1 group, a -COOR2 group, and a -CONH- group are in ortho positions to each other. As the tetravalent organic group represented by X1, specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (7): [Chemical formula] {In formula (7), R 11 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, m5 is an integer of 0 to 2, m6 is an integer of 0 to 3, and m7 is an integer of 0 to 4.} Examples of the group having the structure represented by are included, but are not limited thereto. Also, the structure of X1 may be one kind or a combination of two or more kinds. The X1 group having the structure represented by the above formula (7) is particularly preferable in terms of achieving both heat resistance and photosensitive characteristics.

[0052] In the above general formula (4), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties. For example, the following general formula (8): [Chemical formula] {In formula (8), R 11 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1 - C10 hydrocarbon group, and a C1 - C10 fluorinated hydrocarbon group, m5 is an integer from 0 to 2, m6 is an integer from 0 to 3, and m7 is an integer from 0 to 4.} Examples of the group having the structure represented by this formula include, but are not limited to, these. Also, the structure of Y1 may be one type or a combination of two or more types. The Y1 group having the structure represented by the above formula (8) is particularly preferable in terms of achieving both heat resistance and photosensitive properties.

[0053] In the polyimide precursor (A), it is preferable that at least one of X1, which is a skeletal component derived from a tetracarboxylic acid compound, or Y1, which is a skeletal component derived from a diamine compound, has a structure in which two or more benzene rings are bonded. The number of benzene rings may be 3 or more, 4 or more, 6 or less, 5 or less, or 4 or less, and more preferably 4. When the polyimide precursor (A) has such a structure, the resolution of the negative - type photosensitive resin composition is maintained, and in the resulting cured relief pattern, there is a tendency to have low dielectric properties.

[0054] In the above general formula (4), the divalent organic group represented by Y1 preferably has the structure of the above general formula (14). When the structure of the above general formula (14) is included in Y1 in the general formula (4), there is a tendency to have excellent resolution. Without being bound by theory, it is considered that the electron density of the aromatic ring increases and the CT transition is promoted, thereby suppressing the swelling of the film during development.

[0055] [Preparation method of polyimide precursor (A)] The ester - linked polyimide precursor having at least one terminal structure selected from the group consisting of the above general formulas (1) to (3) can be obtained by any of the following methods. For example, it can be obtained by first synthesizing an esterified tetracarboxylic dianhydride having a terminal structure, and then subjecting it to amide polycondensation with a diamine compound.

[0056] (Method for introducing terminal structure 1) To form the terminal structures of the above general formula (1) and the above general formula (2), after reacting a tetracarboxylic dianhydride having a desired tetravalent organic group X with a compound having an isocyanate group, alcohols having a photopolymerizable group (for example, an unsaturated double bond) are reacted to prepare a partially imidized or imide - derivative - formed (structure derived from the above general formula (2)) / esterified tetracarboxylic acid (hereinafter also referred to as acid / ester / imide form). In order to promote the reaction between the tetracarboxylic dianhydride and the compound having an isocyanate group, pyridine, triethylamine, dimethylaminopyridine, 1,4 - diazabicyclo[2.2.2]octane, etc. can be used. Optionally, saturated aliphatic alcohols may be used in combination with the above alcohols having a photopolymerizable group.

[0057] (Method for introducing terminal structure 2) To form the terminal structure of the above general formula (3), after reacting a tetracarboxylic dianhydride having a desired tetravalent organic group X with alcohols having a photopolymerizable group (for example, an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as acid / ester form), a compound having an isocyanate group is reacted to prepare a partially esterified / amidated tetracarboxylic acid (hereinafter also referred to as acid / ester / amide form). In order to promote the reaction between the tetracarboxylic dianhydride and the compound having an isocyanate group, pyridine, triethylamine, dimethylaminopyridine, 1,4 - diazabicyclo[2.2.2]octane, etc. can be used. Optionally, saturated aliphatic alcohols may be used in combination with the above alcohols having a photopolymerizable group.

[0058] (Preparation of acid / ester form) As the tetracarboxylic dianhydride having a tetravalent organic group X1 having 6 to 40 carbon atoms, which is preferably used for preparing an ester-bonded polyimide precursor, in addition to the tetracarboxylic dianhydride derived from the structures mentioned above, for example, pyromellitic dianhydride, diphenyl ether-3,3’,4,4’-tetracarboxylic dianhydride, benzophenone-3,3’,4,4’-tetracarboxylic dianhydride, biphenyl-3,3’,4,4’-tetracarboxylic dianhydride, diphenyl sulfone-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, 4,4‘-(4,4’-isopropylidenediphenoxy)diphthalic anhydride, 4,4‘-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, etc. can be mentioned, but are not limited thereto. Also, of course, these can be used alone, or two or more of them may be mixed and used.

[0059] Using these tetracarboxylic dianhydrides containing the tetravalent organic group X1 having 6 to 40 carbon atoms, the terminal structure is formed using the above introduction method 1 or introduction method 2. The order of the reaction differs depending on the introduction method.

[0060] Examples of the compound having a photopolymerizable group, which is preferably used for synthesizing an esterified tetracarboxylic acid having a reactive terminal represented by the above general formulas (1) to (3), include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and the like. Examples of the alcohols having a photopolymerizable group include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-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.

[0061] As the saturated aliphatic alcohols that can be optionally used together with the above alcohols having a photopolymerizable group, saturated aliphatic alcohols having 1 to 4 carbon atoms are preferred. Specific examples thereof include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, and the like.

[0062] The above-mentioned tetracarboxylic dianhydride and alcohols are preferably stirred and mixed at a temperature of 20 to 50°C for 4 to 10 hours in the presence of a basic catalyst such as pyridine, preferably in a suitable reaction solvent, whereby the esterification reaction of the acid anhydride proceeds to obtain a desired acid / ester form.

[0063] As the above-mentioned reaction solvent, those that can completely dissolve the raw material tetracarboxylic dianhydride and alcohols, as well as the product acid / ester form, are preferred. More preferably, it is a solvent that can also completely dissolve the polyimide precursor, which is an amide polycondensation product of the acid / ester form and diamine. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can be mentioned. Specific examples of these include Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Examples of esters include methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, etc. Examples of lactones include γ-butyrolactone, etc. Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, etc. Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, etc. Examples of hydrocarbons include hexane, heptane, benzene, toluene, xylene, etc. These may be used alone or in combination of two or more as needed.

[0064] (Preparation of Polyimide Precursor) To the above acid / ester compound (typically in a solution state dissolved in the above reaction solvent), a suitable dehydrating condensing agent is preferably added and mixed under ice-cooling to convert the acid / ester compound into a polyacid anhydride. Then, a diamine containing a divalent organic group Y1 having 6 to 40 carbon atoms, which is separately dissolved or dispersed in a solvent, is added dropwise thereto, and the two are subjected to amide polycondensation to obtain the target polyimide precursor. Diaminosiloxanes may be used in combination with the diamines having the divalent organic group Y1. Examples of the dehydrating condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and the like. As described above, a polyacid anhydride as an intermediate is obtained.

[0065] Examples of diamines having a divalent organic group Y1 with 6 to 40 carbon atoms, which are suitably used for the reaction with the polyanhydride obtained as described above, include, in addition to the diamines derived from the structures mentioned above, 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)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)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, bis{4-(4-aminophenoxy)phenyl}ketone, and those in which some of the hydrogen atoms on the benzene rings of these are substituted with an alkyl chain such as a methyl group or an ethyl group, for example, 2,2'-dimethyl-4,Examples thereof also include 4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, the diamines are not limited thereto. Of course, these can be used alone, or two or more of them can be used in combination.

[0066] In order to improve the adhesion between the photosensitive resin layer formed on the substrate by applying the photosensitive resin composition onto the substrate and various substrates, during the preparation of the (A) polyimide precursor, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized.

[0067] As a method for introducing a reactive substituent that reacts with heat or light at the end of the main chain, the following methods can be mentioned. First, during amide polycondensation, for example, by charging an excess of diamine, both ends of the main chain are made into amino groups. Then, a compound having a reactive substituent that reacts with heat or light and having a site that also reacts with the amino group is reacted with the amino group. At this time, examples of the site that reacts with the amino group include acid anhydrides, epoxies, isocyanates, etc. Additionally, the following methods can also be mentioned. First, during amide polycondensation, by charging an excess of partially esterified tetracarboxylic acid, both ends of the main chain are made into carboxyl groups. Then, a compound having a reactive substituent that reacts with heat or light and having a site that also reacts with the carboxyl group is reacted with the carboxyl group. At this time, examples of the site that reacts with the carboxyl group include amines, alcohols, etc. Furthermore, as another synthesis method, there is a method obtained by first synthesizing an esterified tetracarboxylic acid having a terminal structure and then subjecting it to amide polycondensation with diamines. For example, after reacting a tetracarboxylic dianhydride having a desired tetravalent organic group X1 with a compound having an isocyanate group, it is reacted with alcohols having a photopolymerizable group (for example, an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester form), or after reacting a tetracarboxylic dianhydride having a desired tetravalent organic group X1 with alcohols having a photopolymerizable group (for example, an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester form), it is reacted with a compound having an isocyanate group to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester form). Saturated aliphatic alcohols may be optionally used in combination with the above-mentioned alcohols having a photopolymerizable group.

[0068] Examples of the compound having a reactive substituent that reacts with heat or light and having a site that also reacts with an amino group, which is used for introducing a reactive substituent that reacts with heat or light at the end of the main chain, include maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, methacrylic anhydride, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 4-ethynyl phthalic anhydride, 4-vinyl phthalic anhydride, di-t-butyl carbonate, and the like. Examples of the compound having a reactive substituent that reacts with heat or light and having a site that also reacts with a carboxyl group include 4-aminostyrene, 4-ethynylaniline, and the like.

[0069] After completion of the amide polycondensation reaction, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off if necessary, and then a poor solvent suitable for the solution containing the polymer component, such as water, a lower aliphatic alcohol, a mixture thereof, etc., is added to precipitate the polymer component. Further, if necessary, operations such as redissolution and reprecipitation operations are repeated to purify the polymer, and then vacuum drying is performed to isolate the target polyimide precursor. In order to improve the degree of purification, the solution of this polymer may be passed through a column filled with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0070] (A) The weight average molecular weight of the polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000 when measured by polystyrene-equivalent weight average molecular weight using gel permeation chromatography (GPC) from the viewpoints of the heat resistance and mechanical properties of the film obtained after heat treatment. If the weight average molecular weight is 8,000 or more, it is preferable because the mechanical properties are good. On the other hand, if it is 150,000 or less, it is preferable because the dispersibility in the developer and the resolution performance of the relief pattern are good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0071] [(B) Photoinitiator] (B) The photoinitiator is a compound that can generate radicals by actinic rays and polymerize an ethylenically unsaturated group-containing compound or the like. Examples of initiators that generate radicals with actinic rays include compounds containing structures such as benzophenone, N-alkylaminoacetophenone, oxime ester, acridine, and phosphine oxide.Examples thereof include aromatic ketones such as benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetoxyoxime) (manufactured by BASF Japan Ltd., Irgacure Oxe02), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (manufactured by Joetsu Strong Electronic Materials Co., Ltd., PBG305), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetoxyoxime) (manufactured by Nikko Chemtech Co., Ltd., TR-PBG-326, product name); benzyl derivatives such as benzyldimethyl ketal; acridine derivatives such as 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, but are not limited thereto. The (C) polymerization initiator described above can be used alone or in combination of two or more. Among the above photopolymerization initiators, oxime ester compounds are more preferable particularly from the viewpoint of resolution. Among these, it is particularly preferable that the radical species is derived from a methyl group.

[0072] The blending amount of the photoinitiator is 0.5 parts by mass or more and 10 parts by mass or less, preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the polyimide precursor (A). The above blending amount is 0.5 parts by mass or more from the viewpoint of photosensitivity or patterning property, and on the other hand, it is preferably 10 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0073] [(C) Solvent] (C) The solvent is not limited as long as it can uniformly dissolve or suspend the (A) polyimide precursor and (B) photoinitiator. Examples of such solvents include γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, N,N-dimethylacetoacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and the like. These solvents may be used alone or in combination of two or more.

[0074] The above solvent can be used in the range of, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, based on 100 parts by mass of the polyimide precursor (A), according to the desired coating film thickness and viscosity of the photosensitive resin composition. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the above content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, and when it is 50% by mass or less, the solubility of the (A) polyimide precursor is improved.

[0075] [(D) Silane coupling agent] In order to improve the adhesion of the relief pattern, the photosensitive resin composition may optionally contain (D) a silane coupling agent. The (D) silane coupling agent preferably has a structure represented by the following general formula (12). [Chemical formula] {In the formula, R 12 is at least one selected from the group consisting of substituents containing an epoxy group, a phenylamino group, a urea group, an isocyanuric group, and a ureido group, and R 13 are each independently an alkyl group having 1 to 4 carbon atoms, R 14 is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, d is an integer of 1 to 3, and m8 is an integer of 1 to 6.}

[0076] In general formula (12), d is not limited as long as it is an integer of 1 to 3, but from the viewpoint of adhesion to the metal rewiring layer, etc., 2 or 3 is preferable, and 3 is more preferable. m8 is not limited as long as it is an integer of 1 to 6, but from the viewpoint of adhesion to the metal rewiring layer, 1 or more and 4 or less is preferable. From the viewpoint of developability, 2 or more and 5 or less is preferable.

[0077] R 12 is not limited as long as it is a substituent containing any structure from the group consisting of an epoxy group, a phenylamino group, a urea group, an isocyanuric group, and a ureido group. Among these, from the viewpoints of developability and adhesion to the metal rewiring layer, it is preferably at least one selected from the group consisting of a substituent containing a phenylamino group, a substituent containing a urea group, and a substituent containing a ureido group, and a substituent containing a phenylamino group is more preferable. R 13 is not limited as long as it is an alkyl group having 1 to 4 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. R 14 is not limited as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. As the alkyl group having 1 to 4 carbon atoms, the same alkyl groups as those of R 13 can be exemplified.

[0078] Examples of the silane coupling agent containing an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like. Examples of the silane coupling agent containing a phenylamino group include N-phenyl-3-aminopropyltrimethoxysilane. Examples of the silane coupling agent containing a ureido group include 3-ureidopropyltrialkoxysilane. Examples of the silane coupling agent containing an isocyanate group include 3-isocyanatopropyltriethoxysilane.

[0079] [(E) Radical polymerizable compound] In order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain an (E) radically polymerizable compound. Such compounds are preferably (meth)acrylic compounds that undergo a radical polymerization reaction with a photoinitiator, and are not particularly limited to the following, but include, for example, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and mono- or di-acrylates or methacrylates of ethylene glycol or polyethylene glycol, mono- or di-acrylates or methacrylates of propylene glycol or polypropylene glycol, mono-, di- or tri-acrylates or methacrylates of glycerol, cyclohexane diacrylate or dimethacrylate, diacrylate or dimethacrylate of 1,4-butanediol, diacrylate or dimethacrylate of 1,6-hexanediol, diacrylate or dimethacrylate of neopentyl glycol, mono- or di-acrylates or methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate or methacrylate, acrylamide, its derivatives, methacrylamide, its derivatives, trimethylolpropane triacrylate or methacrylate, di- or tri-acrylates or methacrylates of glycerol, di-, tri- or tetra-acrylates or methacrylates of pentaerythritol, and compounds such as ethylene oxide or propylene oxide adducts of these compounds. Also, these monomers may be used alone or as a mixture of two or more.

[0080] The blending amount of the compound having an ethylenically unsaturated double bond is 0.5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0081] [(F) Thermal crosslinking agent] In order to improve the chemical resistance of the cured film, the photosensitive resin composition may optionally contain an (F) thermal crosslinking agent.

[0082] (F) A heat crosslinking agent means a compound that undergoes an addition reaction or a condensation polymerization reaction by heat. These reactions occur between (A) the resin and (F) the heat crosslinking agent, between (F) heat crosslinking agents, and in combinations of (F) the heat crosslinking agent with other components described later. The reaction temperature is preferably 150°C or higher.

[0083] (F) The heat crosslinking agent preferably contains a nitrogen atom. This enhances the interaction with the polyimide resin, and higher chemical resistance can be expected. Examples of (F) the heat crosslinking agent include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds, etc.

[0084] Examples of alkoxymethyl compounds include, but are not limited to, the following compounds.

Chemical formula

Chemical formula

[0085] Examples of epoxy compounds include epoxy compounds containing bisphenol A type groups, hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.), and the like. Examples of oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4′-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3-ethyl-3-oxetanylmethyl)diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silsesquioxane] derivative, oxetanyl silicate, phenol novolac type oxetane, 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei Co., Ltd., trade name), OXT221 (manufactured by Toagosei Co., Ltd., trade name), and the like. Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylene bis(maleimide), 4-methyl-N,N'-1,3-phenylene bis(maleimide), N,N'-1,4-phenylene bis(maleimide), 3-methyl-N,N'-1,4-phenylene bis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.Examples of allyl compounds include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allylphenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, triallyl citrate, and the like. Examples of blocked isocyanate compounds include hexamethylene diisocyanate-based blocked isocyanates (for example, Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation; Takenate B-882N manufactured by Mitsui Chemicals, Inc.; 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), tolylene diisocyanate-based blocked isocyanates (for example, Takenate B-830 manufactured by Mitsui Chemicals, Inc.), 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (for example, Takenate B-815N manufactured by Mitsui Chemicals, Inc.; Bronate PMD-OA01 and PMD-MA01 manufactured by Daiwing Sangyo Co., Ltd.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (for example, Takenate B-846N manufactured by Mitsui Chemicals, Inc.; Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (for example, 7950, 7951, and 7990 manufactured by Baxenden). Among these, from the viewpoint of storage stability, blocked isocyanates and bismaleimide compounds are preferred. (F) The thermal crosslinking agent may be used alone or in combination of two or more kinds.

[0086] The content of the (F) thermal crosslinking agent in the resin composition is 0.2% by mass to 40% by mass based on the total solid mass of the resin composition. From the viewpoints of low dielectric properties and chemical resistance, it is more preferably 1% by mass to 20% by mass, and even more preferably 2% by mass to 10% by mass.

[0087] [(G) filler] In order to improve the chemical resistance of the cured film, the photosensitive resin composition may optionally contain a (G) filler. The filler is not limited as long as it is an inert substance added to improve strength and various properties.

[0088] The filler is preferably particulate from the viewpoint of suppressing an increase in viscosity when forming a resin composition. Examples of particulate forms include acicular, plate-like, spherical, etc. From the viewpoint of suppressing an increase in viscosity when forming a resin composition, the filler is preferably spherical.

[0089] Examples of acicular fillers include wollastonite, potassium titanate, zonalite, aluminum borate, acicular calcium carbonate, etc.

[0090] Examples of plate-like fillers include talc, mica, sericite, glass flake, montmorillonite, boron nitride, plate-like calcium carbonate, etc.

[0091] Examples of spherical fillers include calcium carbonate, silica, alumina, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, barium titanate, etc. Among these, from the viewpoints of electrical properties and storage stability when forming a resin composition, silica, alumina, titanium oxide, and barium titanate are preferred, and silica and alumina are more preferred.

[0092] As the size of the filler, in the case of spherical shape, the primary particle diameter is defined as the size, and in the case of plate-like or needle-like shape, the length of the long side is defined as the size. 5 nm to 1000 nm is preferable, and 10 nm to 1000 nm is more preferable. If it is 10 nm or more, it tends to be sufficiently uniform when made into a resin composition, and if it is 1000 nm or less, photosensitivity can be imparted. From the viewpoint of imparting photosensitivity, 800 nm or less is preferable, 600 nm or less is more preferable, and 300 nm or less is particularly preferable. From the viewpoints of adhesion and resin composition uniformity, 15 nm or more is preferable, 30 nm or more is more preferable, and 50 nm or more is particularly preferable.

[0093] The content of the (G) filler in the resin composition is 1 vol% to 20 vol% based on the mass of the resin composition. From the viewpoint of dielectric properties, it is preferably 5 vol% to 20 vol%, and from the viewpoint of resolution, it is more preferably 5 vol% to 10 vol%.

[0094] [Other components] The photosensitive resin composition may further contain components other than the above components (A) to (G). Examples of other components include resin components other than the (A) polyimide precursor; organic compounds containing metal elements, sensitizers, thermal polymerization inhibitors, azole compounds, and hindered phenol compounds.

[0095] The photosensitive resin composition may further contain a resin component other than the (A) polyimide precursor. Examples of resin components that can be contained in the photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, acrylic resin, etc. The blending amount of these resin components is preferably in the range of 0.01 part by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0096] The photosensitive resin composition may contain an organic compound containing a metal element. The organic compound containing a metal element preferably contains at least one metal element selected from the group consisting of titanium and zirconium in one molecule. The organic group preferably includes a hydrocarbon group and a hydrocarbon group containing a heteroatom. By containing the organic compound, the imidization rate of the polyimide precursor contained in the photosensitive resin composition increases, and the dielectric tangent of the cured film decreases. Examples of usable organic titanium or zirconium compounds include those in which an organic group is bonded to a titanium atom or a zirconium atom via a covalent bond or an ionic bond.

[0097] Specific examples of the organic titanium or zirconium compound are shown in the following I) to VII): I) As the chelate compound, a compound having two or more alkoxy groups is more preferable because good storage stability and a good pattern of the photosensitive resin composition can be obtained. Specific examples of the chelate compound include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), and compounds in which the titanium atom of these compounds is replaced with a zirconium atom, but are not limited thereto.

[0098] II) Examples of the tetraalkoxy compound include, but are not limited to, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetrastearate, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and compounds in which the titanium atoms of these compounds are replaced with zirconium atoms.

[0099] III) Examples of the titanocene or zirconocene compound include, but are not limited to, 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 compounds in which the titanium atoms of these compounds are replaced with zirconium atoms.

[0100] IV) Examples of the monoalkoxy compound include, but are not limited to, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and compounds in which the titanium atoms of these compounds are replaced with zirconium atoms.

[0101] V) Examples of the titanium oxide or zirconium oxide compound include, but are not limited to, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and compounds in which the titanium atoms of these compounds are replaced with zirconium atoms.

[0102] VI) Examples of the titanium tetraacetylacetonate or zirconium tetraacetylacetonate compound include, but are not limited to, titanium tetraacetylacetonate and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0103] VII) Examples of the titanate coupling agent include, but are not limited to, isopropyltridodecylbenzenesulfonyl titanate and the like.

[0104] Among the above I) to VII), it is preferable from the viewpoint of exhibiting better dielectric loss tangent that the organic titanium compound is at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. 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 are preferable.

[0105] When blending the organic titanium or zirconium compound, the blending amount is 0.01 part by mass to 5 parts by mass, preferably 0.1 part by mass to 3 parts by mass, based on 100 parts by mass of the (A) resin. If the blending amount is 0.01 part by mass or more, the imidization rate of the good resin composition and the dielectric loss tangent of the cured film are exhibited. On the other hand, if it is 10 parts by mass or less, it is preferable because of excellent storage stability.

[0106] By containing an organic compound containing the above metal element, the photosensitive resin composition can improve the imidization rate of the polyimide precursor contained in the resin composition and reduce the dielectric tangent of the cured film using the resin composition. Without being bound by theory, the reason for improving the imidization rate of the polyimide precursor is that the metal element contained in the organic compound containing the metal element coordinates to the carbonyl group derived from the ester group and / or carboxyl group of the polyimide precursor, thereby reducing the electron density of the carbon atom of the carbonyl group and promoting the ring closure reaction.

[0107] The photosensitive resin composition can 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, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 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-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, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combination of two or more (for example, 2 to 5 types). The blending amount of the sensitizer is preferably 0.1 part by mass to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0108] The photosensitive resin composition can optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition particularly during storage in the state of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, and the like. Further, these thermal polymerization inhibitors may be used singly or as a mixture of two or more. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0109] When using a substrate made of copper or a copper alloy, the photosensitive resin composition can optionally contain an azole compound in order to suppress substrate discoloration. 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, 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. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or as a mixture of two or more.

[0110] The compounding amount of the azole compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the (A) polyimide precursor. When the compounding amount of the azole compound based on 100 parts by mass of the (A) polyimide precursor is 0.1 part by mass or more, discoloration of the surface of copper or a copper alloy is suppressed when the photosensitive resin composition is formed on copper or a copper alloy. On the other hand, when it is 20 parts by mass or less, it is preferable because of excellent photosensitivity.

[0111] When using a substrate made of copper or a copper alloy, the photosensitive resin composition can contain a hindered phenol compound in order to suppress substrate discoloration. 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'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(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,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5 - Triazine - 2,4,6 - (1H,3H,5H) - trione, 1,3,5 - tris[4 - triethylmethyl - 3 - hydroxy - 2,6 - dimethylbenzyl] - 1,3,5 - triazine - 2,4,6 - (1H,3H,5H) - trione, 1,3,5 - tris(3 - hydroxy - 2,6 - dimethyl - 4 - phenylbenzyl) - 1,3,5 - triazine - 2,4,6 - (1H,3H,5H) - trione, 1,3,5 - tris(4 - t - butyl - 3 - 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, 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, 1,3,5 - tris(4 - t - butyl - 5 - ethyl - 3 - hydroxy - 2 - methylbenzyl) - 1,3,5 - triazine - 2,4,6 - (1H,3H,5H) - trione, etc. may be mentioned, but are not limited thereto. 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.,

[0112] The compounding amount of the hindered phenol compound is preferably 0.1 part by mass to 20 parts by mass, more preferably 0.5 part by mass to 10 parts by mass, based on 100 parts by mass of the polyimide precursor (A). When the compounding amount of the hindered phenol compound with respect to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, for example, when a photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented. On the other hand, when it is 20 parts by mass or less, it is preferable because of excellent photosensitivity.

[0113] <Polyimide cured film and method for producing the same> The present disclosure also provides a method for producing a polyimide cured film including a step of converting a photosensitive resin composition into polyimide. The method for producing a polyimide cured film of the present disclosure includes, for example, the following steps (1) to (5): (1) A step of applying the photosensitive resin composition of the present disclosure onto a substrate to form a photosensitive resin layer on the substrate; (2) A step of heating and drying the obtained photosensitive resin layer; (3) A step of exposing the photosensitive resin layer after heating and drying; (4) A step of developing the photosensitive resin layer after exposure; and (5) A step of heat-treating the photosensitive resin layer after development to form a polyimide cured film; including.

[0114] The photosensitive resin composition used in the method for producing a cured film preferably contains 100 parts by mass of a polyimide precursor, 0.5 to 10 parts by mass of a photosensitizer, and 100 to 300 parts by mass of a solvent, more preferably contains a photo radical polymerization initiator as the photosensitizer, and still more preferably the photosensitive resin composition is a negative type.

[0115] The specific steps in the method for producing a cured film can be carried out according to the steps (1) to (5) of the above-described method for producing a cured film. Hereinafter, typical embodiments of each step will be described.

[0116] (1) A step of applying the photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate In this process, the photosensitive resin composition of the present disclosure is applied onto a substrate, and if necessary, dried thereafter to form a photosensitive resin layer. As the coating method, methods conventionally used for coating photosensitive resin compositions, for example, methods of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc., methods of spray coating with a spray coater, etc. can be used.

[0117] (2) Step of heating and drying the obtained photosensitive resin layer If necessary, the photosensitive resin composition film can be heated and dried. As the drying method, methods such as air drying, heat drying by an oven or a hot plate, vacuum drying, etc. are used. Also, it is desirable to carry out the drying of the coating film under conditions such that imidization of the (A) polyimide precursor (polyamic acid ester) in the photosensitive resin composition does not occur. Specifically, when performing air drying or heat drying, drying can be carried out under the conditions of 20°C to 140°C for 1 minute to 1 hour. Thus, a photosensitive resin layer can be formed on the substrate.

[0118] (3) Step of exposing the photosensitive resin layer after heating and drying In this process, the photosensitive resin layer formed above is exposed. As the exposure apparatus, for example, exposure apparatuses such as a contact aligner, a mirror projection, a stepper, etc. are used. Exposure can be carried out through a photomask or reticle having a pattern, or directly. The light rays used for exposure are, for example, an ultraviolet light source, etc.

[0119] After exposure, for the purpose of improving photosensitivity, etc., if necessary, post-exposure bake (PEB) and / or pre-development bake may be performed in any combination of temperature and time. The range of the bake conditions is preferably a temperature of 40 to 120°C and a time of 10 seconds to 240 seconds, but is not limited to this range as long as it does not inhibit the various properties of the negative-type photosensitive resin composition of this embodiment.

[0120] (4) Step of developing the photosensitive resin layer after exposure In this process, the photosensitive resin layer after exposure is developed to form a relief pattern. When the photosensitive resin composition is of the negative type, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), an arbitrarily selected method can be used from conventionally known photoresist developing methods, for example, a spin spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, etc. Further, after development, for the purpose of adjusting the shape of the relief pattern, etc., a post-development bake at an arbitrary combination of temperature and time may be performed as necessary. As the developer used for development, for example, a good solvent for the negative type photosensitive resin composition, or a combination of the good solvent and a poor solvent is preferable. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water, etc. are preferable. When mixing and using the good solvent and the poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative type photosensitive resin composition. Also, two or more kinds of each solvent, for example, several kinds can be combined and used. In the step of developing the photosensitive resin layer after exposure, it is preferable to perform the above coating - developing step so that a photosensitive resin layer with a film thickness of 10 μm to 15 μm is obtained. The development time is preferably 30 seconds or less, more preferably 25 seconds or less, and even more preferably 20 seconds or less. Although not bound by theory, when the development time is 30 seconds or less, a contrast is obtained due to the difference in solubility with the exposed portion, and the resolution of the pattern is improved.

[0121] (5) A step of heat-treating the photosensitive resin layer after development to form a polyimide cured film In this process, the relief pattern obtained by the above-described development is heated to disperse the photosensitive component, and (A) the polyimide precursor is imidized to convert it into a cured relief pattern made of polyimide. As the method of heat curing, various methods such as those using a hot plate, those using an oven, and those using a temperature-programmable heating oven can be selected. The heating can be carried out, for example, under the conditions of 160°C to 400°C for 30 minutes to 5 hours. As the atmospheric gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may be used. In this way, a cured relief pattern (polyimide cured film) can be manufactured.

[0122] The method for manufacturing a polyimide cured film of the present disclosure is, for example, a method for manufacturing a cured film including coating the photosensitive resin composition of the present disclosure on a substrate, performing an exposure process, a development process, and then a heat treatment, and the cured film preferably has a dielectric loss tangent of 0.003 to 0.012 when measured at 40 GHz by the perturbation method split cylinder resonator method. The dielectric loss tangent can be measured by the perturbation method split cylinder resonator method shown in the examples described later.

[0123] The present disclosure also provides a polyimide cured film obtained from the photosensitive resin composition described above. The cured film preferably has a water vapor transmission rate of less than 800, more preferably less than 700. From the viewpoint of the dielectric loss tangent, the lower the water vapor transmission rate, the better the tendency for the frequency dependence of the dielectric loss tangent to be small. On the other hand, from the viewpoint of resolution, the lower the water vapor transmission rate, the worse the solubility of the unexposed portion during patterning, and the resolution deteriorates. Therefore, it is more preferably 500 or more and less than 800. By being less than 800, a highly reliable cured film can be obtained. Details of the method for measuring the water vapor transmission rate are described later. From the viewpoints of resolution, dielectric properties, and frequency dependence in the dielectric loss tangent, it is preferable that the product (tanδ 40 ×WVTR) is within a certain range. When using the value of the dielectric loss tangent at 40 GHz, the following formula (3): 3.0 < tanδ 40 ×WVTR < 10.0 (3) It is preferable to satisfy. tanδ 40 When tanδ × WVTR is in the range of 3.0 to 10.0, a polyimide cured product excellent in resolution and dielectric properties and having little frequency dependence can be obtained. The difference in dielectric tangent at 40 GHz and 10 GHz is preferably 0.0015 or less, and preferably 0.001 or less.

[0124] The base on which the cured relief pattern manufactured according to the present disclosure is formed is preferably formed on a substrate selected from the group consisting of resin, silicon (Si), copper (Cu), aluminum (Al), and combinations thereof, and particularly preferably on Cu. When forming a cured relief pattern on Cu, it may be formed on a Cu layer formed on a Si wafer. Another metal layer may be formed between the Si wafer and the Cu layer. The metal layer formed between the Si wafer and the Cu layer is preferably a Ti layer.

[0125] The aspect ratio of the cured relief pattern is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more. By increasing the aspect ratio, finer wiring can be formed. The minimum opening size of the via is preferably such that a via of 20 μm or less opens in a cured film formed to a thickness of 10 μm, more preferably a via of 15 μm or less opens, and even more preferably a via of 10 μm or less opens.

[0126] <Semiconductor device> The present disclosure can also provide a semiconductor device having a cured relief pattern obtained by the above-described method for manufacturing a cured relief pattern using the photosensitive resin composition of the present disclosure. Accordingly, a semiconductor device is provided that includes a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described method for manufacturing a cured relief pattern. Further, the present disclosure can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern as part of the process. The semiconductor device can be manufactured by forming the cured relief pattern formed by the above-described method for manufacturing a cured relief pattern as a surface protection film, an interlayer insulating film, a rewiring insulating film, a protection film for a flip chip device, or a protection film of a semiconductor device having a bump structure, and combining it with a known method for manufacturing a semiconductor device.

[0127] The polyimide contained in the cured relief pattern (polyimide cured film) formed from the above polyimide precursor composition has the following general formula (13):

Chemical formula

[0128] <Display device> The present disclosure can also provide a display device including a display element and a cured film provided on top of the display element, using the photosensitive resin composition of the present disclosure, wherein the cured film is the above-described cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element or may be laminated with another layer interposed therebetween. For example, examples of the cured film include a surface protection film, an insulating film, and a planarizing film for a TFT liquid crystal display element and a color filter element, protrusions for an MVA type liquid crystal display device, and partitions for an organic EL element cathode.

[0129] In addition to the application to the semiconductor device as described above, the photosensitive resin composition of the present disclosure is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad laminates, solder resist films, and liquid crystal alignment films.

Examples

[0130] The physical properties of the photosensitive resin compositions in the examples, comparative examples, and production examples of the present disclosure were measured and evaluated according to the following methods.

[0131] [Measurement and Evaluation Methods] (1) Weight-average molecular weight The weight-average molecular weight (Mw) of each photosensitive resin was measured by gel permeation chromatography (in terms of standard polystyrene). The columns used for the measurement were Shodex 805M / 806M in series manufactured by Showa Denko K.K., the standard monodisperse polystyrene was Shodex STANDARD SM-105 manufactured by Showa Denko K.K., the developing solvent was N-methyl-2-pyrrolidone, and the detector was Shodex RI-930 manufactured by Showa Denko K.K.

[0132] (2) Resolution and development time of cured relief pattern on Cu substrate On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625 ± 25 μm), 200 nm thick Ti and 400 nm thick Cu were sputtered in this order using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva Corporation). Subsequently, the photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and heated and dried on a hot plate at 110 °C for 3 minutes to form a photosensitive resin layer with a thickness of about 13.5 μm. On this photosensitive resin layer, using a mask with a test pattern, 200 mJ / cm was irradiated with a plasma GHI (manufactured by Ultratech Inc.) equipped with an i-line filter. 2Irradiated with the energy of . Next, this photosensitive resin layer was spray-developed using cyclopentanone as a developer with a coater developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.) and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The time of spray development at this time was defined as the development time. The wafer with the relief pattern formed on Cu was heat-treated at 230 °C for 2 hours in a nitrogen atmosphere using a temperature-rising program type curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured relief pattern made of a resin with a thickness of about 10 μm on Cu. The produced relief pattern was observed under an optical microscope to determine the size of the minimum opening pattern of the via. At this time, if the area of the opening of the obtained pattern was 1 / 2 or more of the corresponding pattern mask opening area, it was regarded as resolved, and based on the length of the mask opening side (the size of the opening pattern) corresponding to the one with the minimum area among the resolved openings, the resolution was determined according to the following evaluation criteria. (Evaluation Criteria) A: The size of the minimum opening pattern is less than 10 μm B: The size of the minimum opening pattern is 10 μm or more and less than 15 μm C: The size of the minimum opening pattern is 15 μm or more and less than 20 μm D: The size of the minimum opening pattern is 20 μm or more

[0133] (3) Measurement of dielectric properties (relative permittivity: Dk, dielectric loss tangent: Df) On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625 ± 25 μm), 100 nm thick aluminum (Al) was sputtered using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. The photosensitive resin composition prepared by the method described below was spin-coated on the above sputtered Al wafer substrate using a spin coater (D-spin60A type, manufactured by SOKUDO Co., Ltd.) and heat-dried at 110 °C for 180 seconds to form a photosensitive resin layer with a thickness of about 13.5 μm. Then, using an aligner (PLA-501F, manufactured by Canon), the exposure dose was 600 mJ / cm 2The entire surface was exposed to g-line radiation and then cured for 2 hours at 230°C in a nitrogen atmosphere using a vertical curing oven (Koyo Lindberg, model VF-2000B), producing a cured resin film approximately 10 μm thick on the Al wafer. This cured film was cut into 80 mm x 62 mm (for 10 GHz measurements) and 40 mm x 30 mm (for 40 GHz measurements) using a dicing saw (Disco, model DAD-2H / 6T). The film was then immersed in a 10% hydrochloric acid solution and peeled off from the silicon wafer to obtain film samples. After drying for 24 hours in an oven at 50°C, the relative permittivity (Dk) and dielectric loss tangent (Df) of the film samples at 10 GHz and 40 GHz were measured using the resonator perturbation method. The measurement method is detailed below. (Measurement method) Perturbation split cylinder resonator method (Device configuration) Network analyzer: PNA Network analyzer N5224B (Keysight) Split Cylinder Resonator: CR-710 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approximately 10 GHz) CR-740 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approximately 40 GHz)

[0134] (4) Moisture permeability test A 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 100 nm thick aluminum (Al) using a sputtering device (L-440S-FHL, Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. The photosensitive resin composition prepared by the method described below was spin-coated onto the sputtered Al wafer substrate using a spin coater (D-spin60A, SOKUDO Co., Ltd.), and the resulting substrate was dried by heating at 110°C for 180 seconds to form a photosensitive resin layer approximately 13.5 μm thick. An aligner (PLA-501F, Canon Inc.) was then used to apply an exposure dose of 600 mJ / cm. 2Exposed the entire surface with the ghi line, and using a vertical curing furnace (manufactured by Kouyou Lindberg, model name VF-2000B), performed a heat curing treatment at 230 °C for 2 hours in a nitrogen atmosphere to produce a cured film made of resin with a thickness of about 10 μm on the Al wafer. This cured film was cut into 80 mm in length and 62 mm in width using a dicing saw (manufactured by DISCO, model name DAD-2H / 6T), immersed in a 10% hydrochloric acid aqueous solution, peeled off from the silicon wafer, and used as a film sample. The measurement of water vapor permeability was carried out according to the cup method of JIS Z0208. The amount of calcium chloride used was 40 g, and the water vapor permeation conditions were carried out at a temperature of 65 °C / humidity of 90% RH. The test was conducted for 24 hours, then taken out from the thermo-hygrostat, left at room temperature for 30 minutes, and weighed. The water vapor transmission rate (WVTR) was calculated from the following formula. WVTR = {(weight after the test) - (weight before the test)} / (0.03 2 × π) (Formula X) {In Formula X, 0.03 indicates the radius (m) of the cup} Here, the WVTR is the value for the 10-μm cured film and is a value that depends on the film thickness. For example, when the film thickness is 20 μm, it becomes 1 / 2 of the WVTR value obtained at 10 μm. The lower the WVTR value, the lower the water vapor transmission rate of the film. Also, the more hydrophobic the film is and the higher the density of the film, the lower the WVTR tends to be.

[0135] (5) IR measurement For the IR measurement, the film obtained in (3) above was scanned 50 times in the range of 700 cm -1 to 4000 cm -1 and below using Nicolet 380 by the ATR method. A silicon prism was used for the sample contact part. The peak intensity of the largest absorption peak, the second largest peak intensity, and the peak intensity around 1380 cm -1 to 1550 cm -1 and below were defined as Ph1, Ph2, and Im1 respectively. By normalizing Ph1 to 1, Ph2 and Im1 were calculated. The peak intensity around 1380 cm -1 was used as Im1. -1 The peak intensity near 1380 cm -1±10 cm -1 was taken as the largest peak among them.

[0136] [Production of Diamine X-1] A 5 L four-necked flask was purged with Ar, charged with 172.02 g of 4,4'-butylindene bis(6-tert-butyl-m-cresol), 155.84 g of 4-chloronitrobenzene, and 1.5 L of DMF, and stirred. 186.42 g of K2CO3 was added thereto, and the mixture was heated at 150 °C for 5 hours. The disappearance of the raw materials and intermediates was confirmed by TLC. After cooling to room temperature, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure at 80 °C. The concentrated residue was poured into 1.6 L of ion-exchanged water, and 2.5 L of ethyl acetate was further added thereto, followed by liquid-liquid extraction and purification three times. The organic layer was recovered, dried over MgSO4. After drying, it was filtered to remove impurities, and 800 mL of toluene was added thereto to dissolve the obtained solution, which was then added to 4.0 L of methanol and stirred for 30 minutes. After stirring, it was filtered to recover the filtrate, which was dried at 80 °C for 12 hours. The dried reaction product was charged into a 5 L four-necked flask purged with Ar, and further charged with 19.04 g of 5% Pd / C (EA) and 1.9 L of THF, and stirred. The flask was heated to 40 °C, and H2 bubbling (10 mL / min) was carried out to perform a reduction reaction for 24 hours. The reaction solution was filtered through Celite, and the fraction of the target product was recovered by silica gel chromatography and concentrated under reduced pressure to obtain diamine X-1.

[0137] [Production of (A) Polyimide Precursor] Synthesis of polyimide precursor (polymer A-1): 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 79.1 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the heat generation by the reaction ended, it was allowed to cool to room temperature and further allowed to stand for 16 hours.

[0138] Next, under ice cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension prepared by suspending 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0139] The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst TM 15" manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was added dropwise to 28 liters of water to precipitate the polymer. The obtained precipitate was collected by filtration and then vacuum dried to obtain powdery polymer A-1. When the weight average molecular weight (Mw) of this polymer A-1 was measured, it was 21,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-1 was 19.6 wt%, and the aliphatic hydrocarbon group concentration T was 8.4 wt%. Note that the "imide group concentration U" and "aliphatic hydrocarbon group concentration T" were calculated by converting to the polyimide of the polyimide cured film obtained by heating and curing at 350 °C (the same applies hereinafter).

[0140] Synthesis of polyimide precursor (polymer A-2): In the synthesis of the above polymer A-1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) dianhydride was used instead of 155.1 g of ODPA, and 92.88 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, the reaction was carried out in the same manner as the method described for the synthesis of polymer A-1 to obtain polymer A-2. When the weight average molecular weight (Mw) of this polymer A-2 was measured, it was 23,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-2 was 20.1 wt%, and the aliphatic hydrocarbon group concentration T was 8.6 wt%.

[0141] Synthesis of polyimide precursor (polymer A-3): In the synthesis of the above polymer A-1, except that 146.3 g of 1,4-bis(4-aminophenoxy)-2,3,5-trimethylbenzene was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, the reaction was carried out in the same manner as the method described for the synthesis of polymer A-1 to obtain polymer A-3. When the weight average molecular weight (Mw) of this polymer A-3 was measured, it was 20,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-3 was 23.0 wt%, and the aliphatic hydrocarbon group concentration T was 7.4 wt%.

[0142] Synthesis of polyimide precursor (polymer A-4): In the synthesis of the above polymer A-1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of ODPA, the reaction was carried out in the same manner as the method described for the synthesis of polymer A-1 to obtain polymer A-4. When the weight average molecular weight (Mw) of this polymer A-4 was measured, it was 21,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-4 was 20.1 wt%, and the aliphatic hydrocarbon group concentration T was 8.6 wt%.

[0143] Synthesis of polyimide precursor (Polymer A-5): In the synthesis of the above Polymer A-1, a reaction was carried out in the same manner as the method described in the synthesis of Polymer A-1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) dianhydride was used instead of 155.1 g of ODPA, to obtain Polymer A-5. When the weight-average molecular weight (Mw) of this Polymer A-5 was measured, it was 24,000. The imide group concentration U per repeating unit of the polyimide obtained from Polymer A-5 was 15.2 wt%, and the aliphatic hydrocarbon group concentration T was 9.8 wt%.

[0144] Synthesis of polyimide precursor (Polymer A-6): In the synthesis of the above Polymer A-1, a reaction was carried out in the same manner as the method described in the synthesis of Polymer A-1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) dianhydride was used instead of 155.1 g of ODPA, and 176.98 g of 1,4-bis(4-aminophenoxy)-2,5-di-t-butylbenzene was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, to obtain Polymer A-6. When the weight-average molecular weight (Mw) of this Polymer A-6 was measured, it was 22,000. The imide group concentration U per repeating unit of the polyimide obtained from Polymer A-6 was 15.8 wt%, and the aliphatic hydrocarbon group concentration T was 16.2 wt%.

[0145] Synthesis of polyimide precursor (Polymer A-7): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) dianhydride was used instead of 155.1 g of ODPA, and 247.1 g of diamine X-1 was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, to obtain polymer A-7. When the weight average molecular weight (Mw) of this polymer A-7 was measured, it was 20,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-7 was 13.3 wt%, and the aliphatic hydrocarbon group concentration T was 20.7 wt%.

[0146] Synthesis of polyimide precursor (polymer A-8): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, except that 109.06 g of pyromellitic dianhydride was used instead of 150.1 g of ODPA, and 247.1 g of diamine X-1 was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, to obtain polymer A-8. When the weight average molecular weight (Mw) of this polymer A-8 was measured, it was 14,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-8 was 18.7 wt%, and the aliphatic hydrocarbon group concentration T was 25.1 wt%.

[0147] Synthesis of polyimide precursor (polymer A-9): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described for the synthesis of polymer A-1, except that 95.93 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane and 89.8 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane were used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, to obtain polymer A-9. When the weight-average molecular weight (Mw) of this polymer A-9 was measured, it was 21,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-9 was 20.0 wt%, and the aliphatic hydrocarbon group concentration T was 6.5 wt%.

[0148] Synthesis of polyimide precursor (polymer A-10): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described for the synthesis of polymer A-1, except that 247.1 g of diamine X-1 was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, to obtain polymer A-10. When the weight-average molecular weight (Mw) of this polymer A-10 was measured, it was 16,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-10 was 16.7 wt%, and the aliphatic hydrocarbon group concentration T was 22.3 wt%.

[0149] Synthesis of polyimide precursor (polymer A-11): As the acid component, 93.7 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was placed in a 1-liter separable flask, 175 g of γ-butyrolactone was added, and while stirring at room temperature, a γ-butyrolactone solution prepared separately by dissolving 4.7 g of 2-isocyanatoethyl methacrylate and 28.9 g of pyridine in 20 g of γ-butyrolactone was added over 5 minutes, and the mixture was heated at 50°C for 1 hour. Then, 48.7 g of 2-hydroxyethyl methacrylate (HEMA) was added, and the mixture was further heated at 50°C for 4 hours. After the heat generation due to the reaction ended, it was allowed to cool to room temperature. It was allowed to stand for another 16 hours to obtain a reaction mixture.

[0150] Next, under ice-cooling, a solution prepared by dissolving 69.5 g of dicyclohexylcarbodiimide (DCC) in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution prepared by dissolving 34.0 g of m-TB as a diamine component in 110 g of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2.5 hours, 15 g of ethyl alcohol was added and stirred for 30 minutes, and then 150 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0151] The obtained reaction solution was added to 2700 g of ethyl alcohol to form a precipitate consisting of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst TM 15" manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer. The obtained precipitate was collected by filtration and then vacuum dried to obtain powdery polymer A-11. When the weight average molecular weight (Mw) of this polymer A-11 was measured, it was 22,000, the imide group concentration U per repeating unit was 20.1 wt%, and the aliphatic hydrocarbon group concentration T was 8.6 wt%.

[0152] (A) Synthesis of polyimide precursor (polymer A-12): As the acid component, 93.7 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was placed in a 1-liter separable flask, 48.7 g of 2-hydroxyethyl methacrylate (HEMA) and 175 g of γ-butyrolactone were added, and 28.5 g of pyridine was added while stirring at room temperature. The mixture was heated at 50 °C for 4 hours. After the exothermic reaction ended, it was allowed to cool to room temperature. It was further allowed to stand for 16 hours to obtain a reaction mixture.

[0153] Next, 4.7 g of 2-isocyanatoethyl methacrylate and 0.4 g of pyridine were dissolved in 20 g of γ-butyrolactone, and the γ-butyrolactone solution was added over 5 minutes while stirring, heated at 50 °C for 7 hours, and after the exothermic reaction ended, allowed to cool to room temperature. It was further left standing for 16 hours to obtain a reaction mixture.

[0154] Next, under ice cooling, a solution prepared by dissolving 69.5 g of dicyclohexylcarbodiimide (DCC) in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, as a diamine component, a solution prepared by dissolving 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) in 110 g of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2.5 hours, 15 g of ethyl alcohol was added and stirred for 30 minutes, and then 150 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0155] The obtained reaction solution was added to 2700 g of ethyl alcohol to form a precipitate composed of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst TM 15" manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain powdery polymer A-12. When the weight average molecular weight (Mw) of this polymer A-12 was measured, it was 15,000, the imide group concentration U per repeating unit was 20.1 wt%, and the aliphatic hydrocarbon group concentration T was 8.6 wt%.

[0156] Synthesis of polyimide precursor (polymer A-13): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described for the synthesis of polymer A-1, except that 147.1 g of BPDA was used instead of 155.1 g of ODPA and 85.8 g of diaminodiphenyl ether was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, to obtain polymer A-13. When the weight average molecular weight (Mw) of this polymer A-13 was measured, it was 22,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-13 was 30.5 wt%, and the aliphatic hydrocarbon group concentration T was 0 wt%.

[0157] Synthesis of polyimide precursor (polymer A-14): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described for the synthesis of polymer A-1, except that 92.88 g of m-TB was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, to obtain polymer A-14. When the weight average molecular weight (Mw) of this polymer A-14 was measured, it was 19,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-14 was 28.8 wt%, and the aliphatic hydrocarbon group concentration T was 6.2 wt%.

[0158] Synthesis of polyimide precursor (polymer A-15): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described for the synthesis of polymer A-1, except that 179.59 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, to obtain polymer A-15. When the weight average molecular weight (Mw) of this polymer A-15 was measured, it was 22,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-15 was 20.5 wt%, and the aliphatic hydrocarbon group concentration T was 4.4 wt%.

[0159] Synthesis of polyimide precursor (polymer A-16): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described for the synthesis of polymer A-1, except that 309.29 g of 2,2’,3,3’,5,5’-hexamethyl[1,1’-biphenyl]-4,4’-diyl bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate) was used instead of 155.1 g of ODPA, and 179.59 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, to obtain polymer A-16. When the weight average molecular weight (Mw) of this polymer A-16 was measured, it was 29,000. The imide group concentration U per repeating unit of the polyimide obtained from polymer A-16 was 14.1 wt%, and the aliphatic hydrocarbon group concentration T was 12.1 wt%.

[0160] [Manufacture of photosensitive resin composition] The following compounds were used in the examples and comparative examples. Photoinitiator B-1: TR-PBG-304 (manufactured by Changzhou Qiangli Electronics Co., Ltd.) Photoinitiator B-2: TR-PBG-305 (manufactured by Changzhou Qiangli Electronics Co., Ltd.) Photoinitiator B-3: TR-PBG-3057 (manufactured by Changzhou Qiangli Electronics Co., Ltd.) C-1: γ-butyrolactone (GBL) C-2: Dimethyl sulfoxide (DMSO) D-1: 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) D-2: N-Phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) D-3: (3-Triethoxysilylpropyl)-tert-butylcarbamate D-4: Ureidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) E-1: 1,9-Nonanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) E-2: 1,6-Hexanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) E-3: Diacrylate of polyoxypropylene bisphenol A (manufactured by Kyoeisha Chemical Co., Ltd.) F-1: BMI-5100 (manufactured by Daiwa Kasei Kogyo Co., Ltd.) F-2: SBB70P (manufactured by Asahi Kasei) G-1: K180SP-CY1 (manufactured by Admatechs Co., Ltd.)

[0161] <Example 1> As shown in Table 1, a negative photosensitive resin composition was prepared using polyimide precursor A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of A-1 as a polyimide precursor, (B) 5 g of B-1 as a photoinitiator, and (C) dissolved in 180 g of GBL and 20 g of DMSO as solvents. The viscosity of the obtained solution was adjusted to about 40 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the aforementioned method. The results are shown in Table 2 below.

[0162] <Examples 2 to 26, Comparative Examples 1 to 3> Negative photosensitive resin compositions similar to those in Example 1 were prepared and evaluated in the same manner as in Example 1, except that they were prepared at the compounding ratios shown in Tables 1, 3, and 5 below. The results are shown in Tables 2, 4, and 6 below.

[0163]

Table 1

[0164]

Table 2

[0165]

Table 3

[0166]

Table 4

[0167]

Table 5

[0168]

Table 6

[0169] As shown in Tables 1 to 6, the dielectric tangent (Df) at 40 GHz of the photosensitive resin compositions of Examples 1 to 27 showed lower values of 0.0059 to 0.012 as compared with Comparative Examples 1 to 3. Further, in the photosensitive resin compositions of Examples 1 to 27, the product of the moisture permeability and the dielectric tangent was 3.91 to 9.41, which was a lower value as compared with the comparative examples. Comparative Examples 1 and 2 had long development times, and Comparative Example 1 had a resolution of "D".

Industrial Applicability

[0170] By using the photosensitive resin composition according to the present invention, it is possible to obtain a cured film having high resolution in a thick film and showing a low dielectric tangent. Therefore, the photosensitive resin composition according to the present invention can be suitably used in the field of photosensitive materials useful for the production of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) at least one resin selected from 100 parts by mass of polyimide and polyimide precursor; (B) 0.5 to 10 parts by mass of a photosensitizer; (C) 100 to 300 parts by mass of a solvent; A photosensitive resin composition comprising: based on the polyimide or the polyimide obtained by 100% imidization of the polyimide precursor, the imide group concentration U, which is the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit derived from the tetracarboxylic dianhydride and diamine, is 12 wt% to 26 wt%; The resin contains at least one structure selected from the group consisting of the following formulas (9) to (11); 【Chemical 1】 [Chemical 2] 【Chemical Formula 3】 In the formulas (9) to (11), * represents a connecting portion with the main chain of the resin; The imide group concentration U is calculated using the molecular weight of the tetracarboxylic dianhydride monomer and the molecular weight of the diamine compound monomer that constitute the repeating unit of the polyimide or the polyimide precursor resin, according to the following formula (I): 70.02×2 / [Mw(A)+Mw(B)-36]×100 (I) {In formula (I), Mw(A) represents the molecular weight of the tetracarboxylic dianhydride monomer, and Mw(B) represents the molecular weight of the diamine compound monomer.}, provided that when there are structures derived from n types (n≧2) of the tetracarboxylic dianhydride and / or the diamine compound, the following formula (II): 70.02 × 2 / [Mw(A1) × a １ + ··· + Mw(An) × a ｎ + Mw(B1) × b １ + ··· + Mw(Bn) × b ｎ − 36] × 100 (II) In formula (II), Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride in monomer form, Mw(An) represents the molecular weight of the n-th tetracarboxylic dianhydride in monomer form, a １ represents the content of the first tetracarboxylic dianhydride, a ｎ represents the content of the n-th tetracarboxylic dianhydride, Mw(B1) represents the molecular weight of the first diamine compound in monomer form, Mw(Bn) represents the molecular weight of the n-th diamine compound in monomer form, b １ represents the content of the first diamine compound, and b ｎ represents the content of the n-th diamine compound. However, a １・・・ a ｎ , b １ ...b ｎ each satisfy a １ +...+a ｎ = 1, b １ +...+b ｎ = 1.} It is calculated by Based on the polyimide or the polyimide obtained by 100% imidization of the polyimide precursor, the aliphatic hydrocarbon group concentration T, which is the ratio of the total molecular weight of the aliphatic hydrocarbon groups to the molecular weight of the repeating unit derived from the tetracarboxylic dianhydride and diamine compound, is 4 wt% to 35 wt%. The aliphatic hydrocarbon group is a straight-chain or branched-chain hydrocarbon group having at least one structure selected from the group consisting of a saturated aliphatic chain, an unsaturated aliphatic chain, and an alicyclic structure, branched from the main chain and containing no heteroatoms. The aliphatic hydrocarbon group concentration T is calculated using the molecular weight of the tetracarboxylic dianhydride monomer and the molecular weight of the diamine compound monomer that constitute the repeating unit of the polyimide or the polyimide precursor resin, according to the following formula (I): [Mw(P)+Mw(Q)] / [Mw(A)+Mw(B)-36]×100 (I) {In formula (I), Mw(P) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the tetracarboxylic dianhydride, Mw(Q) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the diamine compound, Mw(A) represents the molecular weight of the tetracarboxylic dianhydride in the monomer form, and Mw(B) represents the molecular weight of the diamine compound in the monomer form.}, provided that when there are structures derived from n types (n ≧ 2) of the tetracarboxylic dianhydride and / or the diamine compound, the following formula (II): [Mw(P1) × a1 + ··· + Mw(Pn) × an + Mw(Q1) × b1 + ··· + Mw(Qn) × bn] / [Mw(A1) × a1 + ··· + Mw(An) × an + Mw(B1) × b1 + ··· + Mw(Bn) × bn - 36] × 100 (II) {In formula (II), Mw(P1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first tetracarboxylic dianhydride, Mw(Pn) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the nth tetracarboxylic dianhydride, Mw(Q1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first diamine compound, and Mw(Qn) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the nth diamine compound. Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride in the monomer form, Mw(An) represents the molecular weight of the nth tetracarboxylic dianhydride in the monomer form, a1 represents the content ratio of the first tetracarboxylic dianhydride, and an represents the content ratio of the nth tetracarboxylic dianhydride. Mw(B1) represents the molecular weight of the first diamine compound in the monomer form, Mw(Bn) represents the molecular weight of the nth diamine compound in the monomer form, b1 represents the content ratio of the first diamine compound, and bn represents the content ratio of the nth diamine compound. Also, a1 ··· an, b1 ··· bn each satisfy a1 + ··· + an = 1, b1 + ··· + bn = 1.}, calculated by The photosensitive resin composition is a photosensitive resin composition used for a rewiring layer application.

2. The photosensitive resin composition according to claim 1, wherein the resin contains at least one structure selected from the group consisting of the formula (9).

3. The photosensitive resin composition according to claim 1 or 2, wherein the resin is a polyimide precursor.

4. The photosensitive resin composition according to claim 3, wherein the polyimide precursor contains a structure represented by the following general formula (4). 【Chemical Formula 4】 {In the formula, 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 of 2 to 150, R ４ and R ５ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R ４ and R ５ is a group represented by the following general formula (5).}{{END}} [Chemical Formula 5] {In the formula, R ６ , R ７ and R ８ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ２ is an integer of 2 to 10.}

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the resin is a reaction product of a tetracarboxylic dianhydride and a diamine.

6. The photosensitive resin composition according to claim 5, wherein at least one of the tetracarboxylic dianhydrides constituting the resin and at least one of the diamines have an aliphatic hydrocarbon group.

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (D) a silane coupling agent.

8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising (E) a radically polymerizable compound.

9. The photosensitive resin composition according to claim 8, wherein the radically polymerizable compound (E) has an alkyl group.

10. The photosensitive resin composition according to any one of claims 1 to 9, further comprising (F) a thermal crosslinking agent.

11. The photosensitive resin composition according to any one of claims 1 to 10, further comprising (G) a filler.

12. The following steps: A step of applying the photosensitive resin composition according to any one of claims 1 to 11 onto a substrate to form a photosensitive resin layer on the substrate; A step of heating and drying the obtained photosensitive resin layer; A step of exposing the photosensitive resin layer after heating and drying; A step of developing the photosensitive resin layer after exposure; A step of heat-treating the photosensitive resin layer after development to form a polyimide cured film; A method for producing a polyimide cured film, comprising:

13. The method for producing a polyimide cured film according to claim 12, wherein the coating to development steps are performed such that a photosensitive resin layer having a film thickness of 10 μm to 15 μm is obtained in the development step, and the development time during development is 30 seconds or less.

14. A polyimide cured film which is a cured product of the photosensitive resin composition according to any one of claims 1 to 11, having a dielectric loss tangent of 0.003 to 0.014 at a frequency of 40 GHz by a perturbation mode split cylinder resonator method, and the following formula (3): 3 < tan δ ４０ × WVTR < 10 (3) {where tanδ ４０ represents the dielectric tangent at a frequency of 40 GHz by the perturbation method split cylinder resonator method, and WVTR represents the water vapor transmission rate of the polyimide cured film converted to a film thickness of 10 μm.} A polyimide cured film that satisfies this condition.

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