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

Abstract

To provide, e.g., a photosensitive resin composition which has low dielectric properties and low moisture permeability, and is capable of forming a high-resolution cured relief pattern.SOLUTION: The photosensitive resin composition contains 100 parts by mass of one or more resins selected from a polyimide and a polyimide precursor, 0.5-10 pts.mass of a photosensitizer, and 100-300 pts.mass of a solvent. The imide group concentration in a polyimide cured film obtained by heating the photosensitive resin composition at 350°C and curing the same is 12-26 wt.%, and the resin contains a structure represented by general formula (14).SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which combine excellent heat resistance and electrical and mechanical properties, have been used as insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these resins, those provided in the form of photosensitive resin compositions can easily form heat-resistant relief pattern films by coating, exposing, developing, and curing the composition to a ring closure treatment (imidization, benzoxazole formation) or thermal crosslinking. Such photosensitive resin compositions have the advantage of enabling significant process shortening compared to conventional non-photosensitive materials, and are therefore used in the fabrication of semiconductor devices.

[0003] Semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards using various methods depending on the purpose. Conventional elements have generally been fabricated using wire bonding, which connects the external terminals (pads) of the element to the lead frame with thin wires. However, as elements have become faster and their operating frequencies have reached GHz, differences in the wiring length of each terminal during mounting have come to affect the operation of the element. As a result, when mounting elements for high-end applications, it has become necessary to accurately control the length of the mounting wiring, and wire bonding has become difficult to meet this requirement.

[0004] To address this issue, flip-chip packaging has been proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the redistribution layer, and the chip is then flipped over and directly mounted on a printed circuit board. Because flip-chip packaging allows for precise control of wiring distance, it has been adopted for high-end applications that handle high-speed signals, and for mobile phones and other devices due to its small packaging size, resulting in rapidly expanding demand. More recently, a semiconductor chip packaging technology called fan-out wafer-level packaging (FOWLP) has been proposed, in which individual chips are manufactured by dicing a pre-processed wafer, the individual chips are reassembled on a support, encapsulated with molding resin, and a redistribution layer is formed after the support is peeled off (see, for example, Patent Document 1). In fan-out wafer-level packaging, the redistribution layer is formed with a thin film thickness, which allows for a thinner package, as well as higher-speed transmission and lower costs.

[0005] In recent years, the dramatic increase in the volume of information and communication has necessitated a shift to faster communication speeds than conventional standards, necessitating a transition to fifth-generation (5G) communications using frequencies above 3 GHz, or communications in ultra-high frequency bands from the quasi-millimeter wave band (20 GHz to 30 GHz) to the millimeter wave band (30 GHz or higher), where wider frequency bandwidths are more readily available. This has led to demands for high-frequency compatibility not only for printed circuit boards but also for the semiconductor chips on which the boards are mounted. To address this issue, antenna-in-package (AiP) devices have been developed that integrate antennas with front-end modules (FEMs) that transmit and receive radio waves (see, for example, Patent Document 2 below) to reduce transmission loss. AiPs use short wiring lengths, making it possible to suppress transmission loss, which increases in proportion to the wiring length.

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

[0007] The interlayer material for protecting the rewiring layer is required to have not only low dielectric properties but also high adhesion between the rewiring metal layer and the resin layer from the viewpoint of reliability, and in recent years, there has been a demand for a lower temperature for heat curing the rewiring layer. Patent Document 4, for example, discloses such a photosensitive resin composition. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-167191 [Patent Document 2] US Patent Application Publication No. 2016 / 0104940 [Patent Document 3] International Publication No. 2019 / 044874 [Patent Document 4] Japanese Patent Application Laid-Open No. 2018-200470 Summary of the Invention [Problem to be solved by the invention]

[0009] In recent years, the diversification of packaging technologies has led to a proliferation of support types and the multi-layering of rewiring layers, significantly increasing the impact of the dielectric constant and dielectric dissipation factor (tanδ) of insulating materials used in wiring formation. High dielectric constants and dielectric dissipation factors increase transmission loss due to increased dielectric loss. While polyimide resins offer excellent insulation performance and thermomechanical properties, their high dielectric constant and dielectric dissipation factor are problematic due to the polar functional groups derived from imide groups, the addition of polar functional groups for photosensitization, and additives. Furthermore, the frequency dependence of the dielectric dissipation factor can be problematic, and low moisture permeability of insulating layers is considered desirable.

[0010] An object of the present disclosure is to provide a photosensitive resin composition that has low dielectric properties and low moisture permeability and is capable of forming a cured relief pattern with high resolution, as well as a method for producing a cured polyimide film using the same, and the cured polyimide film. [Means for solving the problem]

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

[19] . [1] (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors; (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: a polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C, wherein the polyimide in the polyimide cured film has an imide group concentration U, which is the ratio of the molecular weight of imide groups to the molecular weight of a repeating unit containing a structure derived from a tetracarboxylic dianhydride and a diamine, of 12 wt% to 26 wt%; The photosensitive resin composition, wherein the resin comprises a structure represented by the following general formula (14): [ka] {where, 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 which 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; 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 hetero atom, or an organic group having 1 to 13 carbon atoms, and * represents a connecting portion to the main chain of the resin.} [2] Item 2. The photosensitive resin composition according to Item 1, wherein the polyimide in the cured polyimide film obtained by heating and curing the photosensitive resin composition at 350°C has an aliphatic hydrocarbon group concentration T, which is the ratio of the total molecular weight of aliphatic hydrocarbon groups to the molecular weight of repeating units containing a structure derived from a tetracarboxylic dianhydride and a diamine compound, of 4 wt% to 35 wt%. [3] 3. The photosensitive resin composition according to item 1 or 2, wherein the structure represented by general formula (14) is derived from a diamine. [4] 4. The photosensitive resin composition according to any one of items 1 to 3, wherein the resin is a polyimide precursor. [5] 5. The photosensitive resin composition according to item 4, wherein the polyimide precursor comprises a structure represented by the following general formula (4): [ka] {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, provided that at least one of R4 and R5 is a group represented by the following general formula (5).} [ka] {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) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors; (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 resin contains a polyimide precursor, the polyimide precursor is a compound represented by the following general formula (4): [ka] {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, provided that at least one of R4 and R5 is a group represented by the following general formula (5).} [ka] {wherein R6, R7, and R8 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m2 represents an integer of 2 to 10.} The resin is represented by the following general formula (15): [ka] In the formula, each Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom and which 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 group represented by the following formula: [ka] It is one of the following. The resin is represented by the following general formula (14): [ka] 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 which 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; 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 hetero atom, or an organic group having 1 to 13 carbon atoms, and * represents a connecting portion to the main chain of the resin. [7] (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors; (B) 0.5 to 10 parts by mass of a photosensitizer; (C) 100 to 300 parts by mass of a solvent; In the polyimide of the cured polyimide film obtained by heating and curing the photosensitive resin composition at 350°C, the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing a structure derived from a tetracarboxylic dianhydride and a diamine is defined as the imide group concentration U, and the ratio of the total molecular weight of the aliphatic hydrocarbon group to the molecular weight of the repeating unit containing a structure derived from a tetracarboxylic dianhydride and a diamine is defined as the aliphatic hydrocarbon group concentration T, where U is 12 wt% to 26 wt%, and -12.6 <U-T<16.0 (1) {A photosensitive resin composition satisfying the above conditions. [8] (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors; (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: (A) IR spectrum of polyimide obtained by heating and curing polyimide precursor at 230 °C, 1450 cm -1 More than 1550cm -1 The largest absorption peak intensity in the following range is Ph1, the second largest is Ph2, and 1380cm -1 When the peak intensity around Im1 is normalized to Ph1 as 1, the following equation (2) is obtained: 0.34≦Ph2×Im1≦1.2 (2) A photosensitive resin composition that satisfies the above requirements. [9] 9. The photosensitive resin composition according to any one of items 1 to 8, wherein the resin is a reaction product of a tetracarboxylic dianhydride and a diamine.

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

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

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

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

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

[16] The following steps: A step of applying the photosensitive resin composition according to any one of items 1 to 15 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 developed photosensitive resin layer to form a cured polyimide film; A method for producing a cured polyimide film, comprising:

[17] Item 17. The method for producing a polyimide cured film according to Item 16, wherein the coating to developing steps are carried out so as to obtain a photosensitive resin layer having a film thickness of 10 μm to 15 μm in the developing step, and the developing time is 30 seconds or less.

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

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

[0012] By using the photosensitive resin composition of the present disclosure, it is possible to produce a cured resin film that has excellent relief pattern resolution, low dielectric properties, low moisture permeability, and good chemical resistance. By using a polyimide precursor having a specific terminal crosslinking group and an aliphatic hydrocarbon group, the solubility of the prebaked film in a developer is improved, thereby improving the relief pattern resolution. Furthermore, by improving the hydrophobicity and crosslink density of the cured film, the moisture permeability is reduced, improving chemical resistance, and the dielectric loss tangent is reduced due to the increased excluded volume. [Brief explanation of the drawings]

[0013] [Figure 1] This is an example of the IR spectrum of a polyimide obtained by heat-curing a polyimide precursor at 230°C. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments of the present disclosure will be described in detail. Throughout this specification, when a structure represented by the same symbol in a general formula is present in a molecule, it is independently selected and may be the same or different from each other unless otherwise specified. Furthermore, structures represented by a common symbol in different general formulas are also independently selected and may be the same or different from each other unless otherwise specified.

[0015] <Photosensitive resin composition> The photosensitive resin composition of the present disclosure contains (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors having a specific structure, (B) 0.5 to 10 parts by mass of a photopolymerization initiator, and (C) 50 to 500 parts by mass of a solvent. The photosensitive resin composition of the present disclosure may further contain, 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, or other components, as desired.

[0016] [(A) Polyimide and polyimide precursor] From the viewpoints of resolution, moisture permeability, and low dielectric loss tangent, it is preferable that (A) at least one resin selected from polyimides and polyimide precursors contains a structure represented by the following general formula (14). [ka] {where, 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 which 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; 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 hetero atom, or an organic group having 1 to 13 carbon atoms, and * represents a connecting portion to the main chain of the resin.}

[0017] In the above general formula (14), Z2 is preferably a single bond, an organic group having a heteroatom, or a structure selected from organic groups 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 saturated hydrocarbons are more preferred. The organic group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

[0018] By including the structure of the above general formula (14), a cured film with good relief pattern resolution and low moisture permeability can be obtained. Without being bound by theory, it is believed that introducing an organic group into the aromatic ring improves the solubility of the polyimide precursor in a developer, making it easier to ensure contrast with the exposed area and improving the resolution of the relief pattern. Also, without being bound by theory, it is believed that introducing an organic group into the aromatic ring increases the hydrophobicity of the film and makes it less permeable to moisture.

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

[0020] When the structure of the above formula (14) is derived from a tetracarboxylic dianhydride when preparing a polyimide or a polyimide precursor, it preferably contains at least one structure selected from the group consisting of the following general formula (10): [ka]

[0021] When the structure of the above formula (14) is derived from a diamine compound when preparing a polyimide or a polyimide precursor, it preferably contains at least one structure selected from the group consisting of the following general formula (11): [ka] The structure of the general formula (14) is not limited to the structures (9) to (11) above, and the above structures may be one type or a combination of two or more types.

[0022] From the viewpoints of resolution, moisture permeability, and low dielectric loss tangent, it is also preferable that the at least one resin selected from (A) polyimides and polyimide precursors contains a structure represented by the following general formula (15). [ka] In the formula, each Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom and which 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 a group represented by the following formula: [ka] It is one of the types.

[0023] The photosensitive resin composition of the present disclosure has an imide group concentration U of 12 wt% to 26 wt% in the polyimide of a cured polyimide film obtained by heating and curing the photosensitive resin composition. In this specification, "imide group concentration U" refers to the ratio of the molecular weight of imide groups to the molecular weight of repeating units containing structures derived from tetracarboxylic dianhydride and diamine compounds in the polyimide of the cured polyimide film obtained by heating and curing the photosensitive resin composition at 350°C. The reason for the condition of heating and curing at 350°C is to clarify the standard for the aliphatic hydrocarbon group concentration T by using a state in which the polyimide precursor is nearly 100% imidized as the standard, but it is not intended that the photosensitive resin composition will 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, and more preferably 13.5 wt% or more. On the other hand, if the imide group concentration U is 26 wt% or less, the dielectric loss tangent of the resulting polyimide cured film tends to be good. The imide group concentration U is more preferably 23.0 wt% or less, and even more preferably 21.0 wt% or less.

[0025] The imide group concentration U in the repeating unit of the polyimide cured film is calculated using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in preparing the polyimide precursor by 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 preparing using two types of tetracarboxylic dianhydrides and / or diamines, the molecular weight of the diamine compound is calculated by 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. Note that a1, a2, b1, and b2 satisfy the relationships a1 + a2 = 1 and b1 + b2 = 1, respectively. The same calculation can be performed when three or more types of tetracarboxylic dianhydrides and / or diamines are used. When tetracarboxylic acid and / or tetracarboxylic 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). [ka] {In the formula, W is a divalent or trivalent organic group, R1 to R3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, m1 is an integer of 1 or 2, m2 is an integer of 2 to 10, and * means bonding to the main chain of the resin.} When the polyimide and / or polyimide precursor has such an end structure, a negative-type photosensitive resin composition having low dielectric properties, low moisture permeability, and good chemical resistance and high resolution can be obtained.

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

[0028] The polyimide precursor (A) may have a polymerizable group at the end of the main chain. The polyimide precursor (A) having a polymerizable group preferably has a structure represented by the following general formula: [ka] In formula (E1), a1 contains at least one bond selected from the group consisting of an amide bond, an imide bond, a urea bond, and a urethane bond; b1 is a reactive substituent that crosslinks with heat or light; e1 is a monovalent organic group having 1 to 30 carbon atoms; and R 19 , R 22 are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and R 20 , R 21 are each independently a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, or a part of an aromatic ring or an aliphatic ring. 20 and R 21 and cannot both be hydrogen atoms. [ka] (In the formula, f1 contains at least one bond selected from the group consisting of an amide bond, an imide bond, a urea bond, a urethane bond, and an ester bond, g1 is a reactive substituent that crosslinks with heat or light, and R 23 ~R 27are each independently a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, or together form an aromatic ring or an aliphatic ring, provided that R 24 , R 25 , R 26 and do not simultaneously become hydrogen atoms.) When the polyimide precursor has such terminal polymerizable groups, a negative-type photosensitive resin composition having low dielectric properties, low moisture permeability, and good chemical resistance and high resolution can be obtained.

[0029] It is preferable that f1 contains at least one group selected from the group consisting of an amide group, an imide bond, a urea group, and a urethane group. If f1 is an ester group, it is prone to hydrolysis and may not be crosslinked. These four groups (amide group, imide bond, urea group, and urethane group) are resistant to hydrolysis and therefore have high chemical resistance.

[0030] The reactive substituent b1 that crosslinks with 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. A methacrylic group is particularly preferred.

[0031] The reactive substituent g1 that crosslinks when exposed to 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. g1 is particularly preferably a methacrylic group.

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

[0033] [ka]

[0034] The aliphatic hydrocarbon group concentration (T) of the cured polyimide film obtained by heating and curing the photosensitive resin composition is preferably 4 wt% to 35 wt%. In this specification, the term "aliphatic hydrocarbon group concentration (T)" refers to the ratio of the total molecular weight of the aliphatic hydrocarbon groups to the molecular weight of the repeating units consisting of tetracarboxylic dianhydride and diamine compound in the polyimide of the cured polyimide film obtained by heating and curing the photosensitive resin composition at 350°C. The reason for using 350°C as the standard temperature for heating and curing is to facilitate adjustment of the aliphatic hydrocarbon group concentration (T) by using a state in which the polyimide precursor is nearly 100% imidized as the standard temperature. However, it is not intended that the photosensitive resin composition be heated and cured at 350°C in actual use. Here, the term "aliphatic hydrocarbon group" refers to a hydrocarbon group branched from the main chain of the polyimide precursor, containing no heteroatoms, and having at least one structure selected from the group consisting of a saturated aliphatic chain, an unsaturated aliphatic chain, and an alicyclic structure, and may be either linear or branched. The alkylene skeleton portion constituting part of the main chain and the quaternary carbon (carbon that is disubstituted and also constitutes part of the main chain) constituting part of the main chain are not included in the "aliphatic hydrocarbon group" when calculating the aliphatic hydrocarbon group concentration. The aliphatic hydrocarbon group constituting the side chain portion branching from the main chain, whether saturated or unsaturated, linear or alicyclic, is included in the "aliphatic hydrocarbon group" when calculating the aliphatic hydrocarbon group concentration. Structural examples of the "aliphatic hydrocarbon group" include structures represented by the following general formula (A1), (A2), and (A3).

[0035] [ka]

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

[0037] From the viewpoint of the dielectric loss tangent of the cured polyimide film, the aliphatic hydrocarbon group preferably has a monovalent aliphatic saturated hydrocarbon group having 1 to 3 carbon atoms, such as a methyl group. When the group concentration T is 4 wt% or more, the dielectric loss tangent of the cured polyimide film tends to be good. The aliphatic hydrocarbon group concentration T is preferably 5 wt% or more, more preferably 7 wt% or more, and even 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 cured polyimide 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 even more preferably 12% or less.

[0038] The aliphatic hydrocarbon group concentration T is calculated using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in preparing 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.

[0039] When two or more kinds of tetracarboxylic dianhydrides and / or diamine compounds are used, for example, when two kinds of tetracarboxylic dianhydrides and two kinds 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 the aliphatic hydrocarbon groups in the first tetracarboxylic dianhydride, Mw(P2) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the second tetracarboxylic dianhydride, Mw(Q1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first diamine compound, and Mw(Q2) represents the sum of the molecular weights of the 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. Furthermore, a1, a2, b1, and b2 satisfy a1+a2=1 and b1+b2=1, respectively. The molecular weight can be calculated in the same way when three or more types of tetracarboxylic dianhydrides and / or diamine compounds are used. When tetracarboxylic acids and / or tetracarboxylic acid chlorides are used as raw materials, the molecular weight of the corresponding tetracarboxylic dianhydrides is used for the calculation.

[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, the moisture permeability tends to be low, which is preferable. When both the diamine compound and the tetracarboxylic dianhydride have an aliphatic hydrocarbon group, the solubility in the developer is improved, which tends to increase the development rate, which is preferable.

[0041] (A) IR spectrum of polyimide obtained by heating and curing polyimide precursor at 230 °C, 1450 cm -1 More than 1550cm -1 The largest absorption peak intensity in the following range is Ph1, the second largest is Ph2, and 1380cm -1 When the peak intensity around Im1 is normalized to Ph1 as 1, the following equation (2) is obtained: 0.34≦Ph2×Im1≦1.2 (2) It is preferable that the following is satisfied.

[0042] The IR spectrum is measured under the conditions described in the Examples below. A peak is defined as a peak whose peak intensity on the lower and higher wavelength sides of the peak top is lower than the peak intensity of the peak top, and is not defined as a peak if either the lower or higher wavelength side of the peak intensity is higher than the peak intensity of the peak top.

[0043] For example, in the case of polyimide having an IR spectrum shown in the graph of Figure 1, Ph1 = 1 (1500 cm -1 ), Ph2=0.42(1473cm -1 ), Im1=0.68(1373cm -1 ) on the high frequency side of Ph1 (1512 cm -1 ) are not considered as peaks.

[0044] 1450cm -1 More than 1550cm -1 If there is only one peak in the range below, Ph2 is set to 0. 1380 cm -1 The peak intensities in the vicinity are ±10 cm for each wave number. -1 The value of the largest peak within this range is taken as the peak intensity.

[0045] Ph2×Im1 is preferably 0.34 or more, more preferably 0.36 or more, and even more preferably 0.40 or more. When it is 0.45 or more, the resolution tends to be good. Without being bound by theory, it is thought that when Ph2×Im1 is 0.34 or more, the solubility of the polyimide precursor improves and the resolution improves. On the other hand, Ph2×Im1 is preferably 1.2 or less, and when it is 1.1 or less, the dielectric tangent tends to be good. Without being bound by theory, it is thought that when Ph2×Im1 is 1.2 or less, molecular motion in the high frequency range decreases.

[0046] The photosensitive resin composition is heated and cured at 350°C to form a cured polyimide film, and the cured polyimide film is formed by curing the photosensitive resin composition at 350°C. The polyimide is represented by the following formula (1): -12.6 <U-T<16.0 (1) {wherein U represents the imide group concentration of the polyimide, and T represents the aliphatic hydrocarbon group concentration of the polyimide.} is preferably satisfied. UT is preferably -12.6 or higher, more preferably -11.0 or higher, and when it is -10 or higher, the resolution tends to be favorable. UT is preferably 16.0 or lower, more preferably 12.5 or lower, and preferably 12.0 or lower, and when it is 11.0 or lower, the moisture permeability tends to be excellent. The reason for using 350°C as the standard for heating and curing is that by using a state in which the polyimide precursor is almost 100% imidized as the standard, it is possible to easily adjust the aliphatic hydrocarbon group concentration T, but it is not intended that the photosensitive resin composition will be heated and cured at 350°C in actual use.

[0047] The (A) polyimide precursor may be a polyamide precursor having a structural unit represented by the following general formula (4). [ka] {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, provided that at least one of R4 and R5 is a group represented by the following general formula (5).} [ka] {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.} R4 and R5 in general formula (4) are also referred to as the side chain or side chain structure of the polyimide precursor. In general formula (5), R6 is preferably a hydrogen atom or a methyl group, and R7 and R8 are preferably hydrogen atoms from the viewpoint of photosensitivity. Furthermore, m2 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitivity.

[0048] From the viewpoints of resolution and low dielectric properties, the proportion of photosensitive groups per repeating unit in the polyimide precursor resin (A) represented by the above general formula (4) is preferably 15 wt% to 35 wt%. From the viewpoint of dielectric properties, the fewer the photosensitive groups, the better, and from the viewpoint of resolution, the more the photosensitive groups. In this specification, "proportion of photosensitive groups" refers to the proportion 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 above general formula (4). Examples of photopolymerizable groups include unsaturated double bonds.

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

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

[0051] In the above general formula (4), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group or an alicyclic aliphatic group in which the -COOR1 group, the -COOR2 group, and the -CONH- group are located at the ortho positions relative to each other. Specific examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, such as those represented by the following general formula (7): [ka] {In formula (7), 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 of 0 to 2, m6 is an integer of 0 to 3, and m7 is an integer of 0 to 4. Examples of groups having a structure represented by the formula (7) include, but are not limited to, groups having a structure represented by the formula (7). X1 may be of one type or a combination of two or more types. X1 groups having a structure represented by the formula (7) are particularly preferred in that they achieve both heat resistance and photosensitivity.

[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 order to achieve both heat resistance and photosensitive properties, and is, for example, a group represented by the following general formula (8): [ka] {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 of 0 to 2, m6 is an integer of 0 to 3, and m7 is an integer of 0 to 4. Examples of groups having a structure represented by the formula (8) include, but are not limited to, groups having a structure represented by the formula (8). Furthermore, the structure of Y1 may be one type or a combination of two or more types. A Y1 group having a structure represented by the formula (8) is particularly preferred in that it achieves both heat resistance and photosensitivity.

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

[0054] In the general formula (4), the divalent organic group represented by Y1 preferably has the structure of the general formula (14). When the structure of the general formula (14) is included in Y1 in the general formula (4), the resolution tends to be excellent. Without being bound by theory, it is believed that the electron density of the aromatic ring increases, promoting CT transitions, thereby suppressing film expansion during development.

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

[0056] (Method 1 for introducing terminal structures) To form the terminal structures of the general formulas (1) and (2), a tetracarboxylic acid dianhydride having the desired tetravalent organic group X is reacted with a compound having an isocyanate group, followed by reaction with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially imidized or imide-derivatized (structure derived from the general formula (2)) / esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester / imide). To promote the reaction between the tetracarboxylic acid dianhydride and the compound having an isocyanate group, pyridine, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, etc. may be used. Saturated aliphatic alcohols may also be used in combination with the alcohol having a photopolymerizable group.

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

[0058] (Preparation of Acid / Ester Forms) Examples of tetracarboxylic acid dianhydrides having a tetravalent organic group X1 having 6 to 40 carbon atoms, which are preferably used for preparing an ester bond type polyimide precursor, include, in addition to the tetracarboxylic acid dianhydrides derived from the structures listed above, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3, Examples of suitable dianhydrides include, but are not limited to, 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, and 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride. These may be used alone or in combination of two or more.

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

[0060] Compounds having a photopolymerizable group that are suitably used to synthesize the esterified tetracarboxylic acids having reactive terminals 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, etc. Furthermore, examples of alcohols having a photopolymerizable group include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclo ... Examples include hexyloxypropyl 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, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0061] The saturated aliphatic alcohols that can be optionally used together with the alcohols having a photopolymerizable group are preferably saturated aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

[0062] The tetracarboxylic dianhydride and the alcohol are mixed and stirred preferably in the presence of a basic catalyst such as pyridine, preferably in an appropriate reaction solvent, at a temperature of 20 to 50°C for 4 to 10 hours, whereby the esterification reaction of the acid anhydride proceeds, and the desired acid / ester can be obtained.

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

[0064] (Preparation of Polyimide Precursor) The acid / ester compound (typically in solution in the reaction solvent) is mixed with an appropriate dehydration condensation agent, preferably under ice cooling, to convert the acid / ester compound into a polyacid anhydride. Next, a diamine containing a divalent organic group Y1 having 6 to 40 carbon atoms, dissolved or dispersed in a separate solvent, is added dropwise to the acid / ester compound, and the two compounds are subjected to amide polycondensation to obtain the desired polyimide precursor. Diaminosiloxanes may be used in combination with the diamine containing the divalent organic group Y1. Examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. In this manner, the intermediate polyacid anhydride is obtained.

[0065] Diamines having a divalent organic group Y1 having 6 to 40 carbon atoms that can be suitably used in the reaction with the polyacid anhydride obtained as described above include, in addition to the diamines derived from the structures listed 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 compounds in which some of the hydrogen atoms on the benzene ring are substituted with alkyl chains such as methyl groups or ethyl groups, for example, 2,2'-dimethyl-4,Examples of the diamines include 4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, the diamines are not limited to these. They can be used alone or in combination of two or more.

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

[0067] Examples of methods for introducing reactive substituents that react with heat or light into the terminals of the main chain include the following: First, during amide polycondensation, for example, an excess of diamine is added to convert both terminals of the main chain into amino groups. Then, a compound having a reactive substituent that reacts with heat or light and has a site that also reacts with the amino group is reacted with the amino group. Examples of the site that reacts with the amino group include acid anhydrides, epoxies, and isocyanates. Other examples include the following: First, during amide polycondensation, a partially esterified tetracarboxylic acid is added in excess to convert both terminals of the main chain into carboxyl groups. Then, a compound having a reactive substituent that reacts with heat or light and has a site that also reacts with the carboxyl group is reacted with the carboxyl group. Examples of the site that reacts with the carboxyl group include amines and alcohols. Another synthesis method includes first synthesizing an esterified tetracarboxylic acid that forms a terminal structure, and then performing amide polycondensation with diamines. For example, a method of reacting a tetracarboxylic acid dianhydride having the desired tetravalent organic group X1 with a compound having an isocyanate group, followed by reaction with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester form), or a method of reacting a tetracarboxylic acid dianhydride having the desired tetravalent organic group X1 with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester form), followed by reaction with a compound having an isocyanate group to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester form), etc. Saturated aliphatic alcohols may be used in combination with the alcohols having the photopolymerizable group.

[0068] Examples of compounds that have a reactive substituent that reacts with heat or light and that also have a site that reacts with an amino group, and that are used to introduce the reactive substituent into 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-ethynylphthalic anhydride, 4-vinylphthalic anhydride, di-t-butyl dicarbonate, etc. Examples of compounds that have a reactive substituent that reacts with heat or light and that also have a site that reacts with a carboxyl group include 4-aminostyrene, 4-ethynylaniline, etc.

[0069] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off if necessary, and then a suitable poor solvent (e.g., water, aliphatic lower alcohol, or a mixture thereof) is added to the solution containing the polymer component to precipitate the polymer component. The polymer is further purified by repeated redissolution and reprecipitation procedures, if necessary, and then vacuum-dried to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0070] From the viewpoint of the heat resistance and mechanical properties of the film obtained after heat treatment, the weight-average molecular weight of the (A) polyimide precursor, as measured by gel permeation chromatography (GPC) in terms of polystyrene equivalent, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000. A weight-average molecular weight of 8,000 or more is preferred because it provides good mechanical properties, while a weight-average molecular weight of 150,000 or less is preferred because it provides good dispersibility in the developer and good resolution performance of the relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0071] [(B) Photopolymerization initiator] (B) Photopolymerization initiator is a compound that generates radicals when exposed to actinic rays and can polymerize an ethylenically unsaturated group-containing compound, etc. Examples of initiators that generate radicals when exposed to actinic rays include compounds containing structures such as benzophenone, N-alkylaminoacetophenone, oxime ester, acridine, and phosphine oxide.Examples include 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 aromatic ketones such as benzoin sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (manufactured by BASF Japan Ltd., Irgacure Examples of the oxime ester compounds include oxime ester compounds such as 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (manufactured by Joshu Kyowa Electronic Materials Co., Ltd., PBG305), and 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(o-acetyloxime) (manufactured by Nikko Chemtech Co., Ltd., product name TR-PBG-326); benzyl derivatives such as benzyl dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; and phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. The polymerization initiator (C) described above can be used alone or in combination of two or more. Among the above photopolymerization initiators, oxime ester compounds are more preferred, particularly from the viewpoint of resolution. Among these, those in which the radical species is derived from a methyl group are particularly preferred.

[0072] The amount of the photopolymerization initiator is 0.5 to 10 parts by mass, and preferably 1 to 8 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor. The amount is 0.5 parts by mass or more from the viewpoint of photosensitivity or patterning ability, and 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] The solvent (C) is not limited as long as it can uniformly dissolve or suspend the polyimide precursor (A) and the photopolymerization initiator (B). 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, and N,N-dimethylacetamide. These solvents may be used alone or in combination.

[0074] The solvent can be used in an amount of, for example, 30 to 1,500 parts by mass, preferably 100 to 1,000 parts by mass, per 100 parts by mass of the (A) polyimide precursor, depending on the desired coating 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 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] To improve the adhesion of the relief pattern, the photosensitive resin composition may optionally contain (D) a silane coupling agent, which preferably has a structure represented by the following general formula (12): [ka] {where, R 12 is at least one selected from the group consisting of a substituent 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, and 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 redistribution layer, it is preferably 2 or 3, and more preferably 3. m8 is not limited as long as it is an integer of 1 to 6, but from the viewpoint of adhesion to the metal redistribution layer, it is preferably 1 or more and 4 or less. From the viewpoint of developability, it is preferably 2 or more and 5 or less.

[0077] R 12 is not limited as long as it is a substituent containing any one of the structures of the group consisting of an epoxy group, a phenylamino group, a urea group, an isocyanuric group, and a ureido group. Among these, from the viewpoint of developability and adhesion of the metal redistribution layer, it is preferable that R is 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. 13 is not limited as long as it is an alkyl group having 1 to 4 carbon atoms. Examples of R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. 14 is not limited as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include R 13 The alkyl groups are the same as those shown above.

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

[0079] [(E) Radical polymerizable compound] In order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain (E) a radically polymerizable compound. Such a compound is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, and examples thereof include, but are not limited to, mono- or diacrylates or methacrylates of ethylene glycol or polyethylene glycol, including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates or methacrylates of propylene glycol or polypropylene glycol, mono-, di-, or triacrylates or methacrylates of glycerol, cyclohexane diacrylate or dimethacrylate, diacrylate or dimethacrylate of 1,4-butanediol, and 1,6 Examples of suitable monomers include diacrylate or dimethacrylate of 1-hexanediol, diacrylate or dimethacrylate of neopentyl glycol, mono- or diacrylate or methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate or methacrylate, acrylamide or a derivative thereof, methacrylamide or a derivative thereof, trimethylolpropane triacrylate or methacrylate, di- or triacrylate or methacrylate of glycerol, di-, tri-, or tetraacrylate or methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds. These monomers may be used alone or in a mixture of two or more.

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

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

[0082] The (F) thermal crosslinking agent refers to a compound that undergoes an addition reaction or a condensation polymerization reaction due to heat. These reactions occur between the (A) resin and the (F) thermal crosslinking agent, between the (F) thermal crosslinking agents, and between the (F) thermal crosslinking agent and other components described below, and the reaction temperature is preferably 150°C or higher.

[0083] The (F) thermal crosslinking agent preferably contains a nitrogen atom, which enhances interaction with the polyimide resin and is expected to provide higher chemical resistance. Examples of the (F) thermal crosslinking agent include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds.

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

[0085] Examples of epoxy compounds include epoxy compounds containing bisphenol A groups and hydrogenated bisphenol A diglycidyl ethers (e.g., Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.). 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, and bis(3-ethyl-3-oxetanylmethyl) Examples of suitable oxetane derivatives include diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicate, phenol novolac-type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei, trade name), and OXT221 (manufactured by Toagosei, trade name). 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-phenylenebis(maleimide), 4-methyl-N,N'-1,3-furan

[0033] Examples of suitable phenylene bis(maleimide) include 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, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allyl phenyl 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, and triallyl citrate. Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., 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., and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc.), and 4-methyl-4-isocyanate. Examples of the blocked isocyanate include 4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Inc., and Coronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N manufactured by Mitsui Chemicals, Inc., and Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (e.g., 7950, 7951, and 7990 manufactured by Baxenden). Among these, blocked isocyanates and bismaleimide compounds are preferred from the viewpoint of storage stability. (F) Thermal crosslinking agents may be used alone or in combination of two or more.

[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 mass of the solid content of the resin composition, and 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 filler (G). 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 the resin composition is prepared. Examples of particulate shapes include needle-like, plate-like, and spherical shapes, but from the viewpoint of suppressing an increase in viscosity when the resin composition is prepared, the filler is preferably spherical.

[0089] Examples of the needle-like filler include wollastonite, potassium titanate, xonotlite, aluminum borate, and needle-like calcium carbonate.

[0090] Examples of the plate-like filler include talc, mica, sericite, glass flakes, montmorillonite, boron nitride, and plate-like calcium carbonate.

[0091] Examples of the spherical filler 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 formed into a resin composition, silica, alumina, titanium oxide, and barium titanate are preferred, and silica and alumina are more preferred.

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

[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, and 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 ingredients] The photosensitive resin composition may further contain components other than the above components (A) to (G), such as 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, phenolic resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass per 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 contains a hydrocarbon group or a hydrocarbon group containing a heteroatom. By containing an organic compound, the imidization rate of the polyimide precursor contained in the photosensitive resin composition increases, and the dielectric loss tangent of the cured film decreases. Usable organic titanium or zirconium compounds include, for example, those in which an organic group is bonded to a titanium or zirconium atom via a covalent bond or an ionic bond.

[0097] Specific examples of the organic titanium or zirconium compounds are shown below in I) to VII): I) As the chelate compound, a compound having two or more alkoxy groups is more preferred because it improves the storage stability of the photosensitive resin composition and enables the formation of good patterns. 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(ethylacetoacetate), and compounds in which the titanium atom of these compounds is substituted with a zirconium atom, but are not limited thereto.

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

[0099] III) Examples of titanocene or zirconocene compounds include pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 Examples of the titanium-containing compound include, but are not limited to, bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and compounds in which the titanium atom in these compounds is replaced with a zirconium atom.

[0100] IV) Examples of monoalkoxy compounds include, but are not limited to, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, and compounds in which the titanium atom of these compounds is substituted with a zirconium atom.

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

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

[0103] VII) Examples of titanate coupling agents include, but are not limited to, isopropyl tridodecylbenzenesulfonyl titanate.

[0104] Among the above I) to VII), it is preferable that the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting a better dielectric tangent. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0105] When an organic titanium or zirconium compound is blended, the blending amount is 0.01 to 5 parts by mass, and preferably 0.1 to 3 parts by mass, per 100 parts by mass of the (A) resin. If the blending amount is 0.01 part by mass or more, a good imidization rate of the resin composition and a good dielectric loss tangent of the cured film are exhibited, while if the blending amount is 10 parts by mass or less, excellent storage stability is achieved, which is preferable.

[0106] By including an organic compound containing the metal element in the photosensitive resin composition, the imidization rate of the polyimide precursor contained in the resin composition can be improved, and the dielectric loss tangent of a cured film using the resin composition can be reduced. Without being bound by theory, it is believed that 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-closing reaction.

[0107] The photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylideneindano. p-Dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combination of two or more (for example, two to five kinds). The amount of the sensitizer to be added is preferably 0.1 to 25 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0108] The photosensitive resin composition may optionally contain a thermal polymerization inhibitor to improve the viscosity and photosensitivity stability of the photosensitive resin composition, particularly during storage in a solvent-containing solution. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. These thermal polymerization inhibitors may be used alone or in combination. The amount of the thermal polymerization inhibitor to be added is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0109] When a substrate made of copper or a copper alloy is used, the photosensitive resin composition may optionally contain an azole compound to suppress discoloration of the substrate. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and the like. Examples of benzotriazole include 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0110] The amount of the azole compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity. If the amount of the azole compound is 0.1 part by mass or more relative to 100 parts by mass of the (A) polyimide precursor, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or a copper alloy, while if the amount is 20 parts by mass or less, excellent photosensitivity is achieved, which is preferable.

[0111] When a substrate made of copper or a copper alloy is used, the photosensitive resin composition may contain a hindered phenol compound to suppress discoloration of the substrate. 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), and 4,4'-butylidene-bis(3-methyl-6 -t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl -6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 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 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 Examples of the hydroxybenzoates include, but are not limited to, 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0112] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity. If the amount of the hindered phenol compound is 0.1 part by mass or more relative to 100 parts by mass of the (A) polyimide precursor, for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while if the amount is 20 parts by mass or less, excellent photosensitivity is achieved, which is preferable.

[0113] <Cured polyimide film and method for producing the same> The present disclosure also provides a method for producing a cured polyimide film, which includes a step of converting a photosensitive resin composition into a polyimide. The method for producing a cured polyimide film of the present disclosure includes, for example, the following steps (1) to (5): (1) 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) developing the exposed photosensitive resin layer; and (5) a step of heat-treating the developed photosensitive resin layer to form a cured polyimide film; Includes.

[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 photoradical polymerization initiator as the photosensitizer, and further preferably the photosensitive resin composition is negative-working.

[0115] Specific steps in the method for producing a cured film can be carried out in accordance with steps (1) to (5) of the method for producing a cured film described above. A typical embodiment of each step will be described below.

[0116] (1) A step of applying a photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate. In this step, the photosensitive resin composition of the present disclosure is applied to a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0117] (2) A step of heating and drying the obtained photosensitive resin layer If necessary, the photosensitive resin composition film can be heated and dried. Drying methods include air drying, heat drying using an oven or a hot plate, vacuum drying, and the like. It is desirable to dry the coating film under conditions that do not cause imidization of the (A) polyimide precursor (polyamic acid ester) in the photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be carried out under conditions of 20°C to 140°C for 1 minute to 1 hour. In this way, a photosensitive resin layer can be formed on the substrate.

[0118] (3) A step of exposing the photosensitive resin layer after heating and drying In this step, the photosensitive resin layer formed above is exposed to light. Examples of the exposure device that can be used include a contact aligner, a mirror projection device, and a stepper. The exposure can be performed directly or through a photomask or reticle having a pattern. The light used for exposure is, for example, an ultraviolet light source.

[0119] After the exposure, post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as needed for the purpose of improving photosensitivity, etc. The baking conditions are preferably a temperature of 40 to 120°C and a time of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the negative-type photosensitive resin composition of this embodiment.

[0120] (4) A step of developing the exposed photosensitive resin layer In this step, the exposed photosensitive resin layer is developed to form a relief pattern. When the photosensitive resin composition is a negative type, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The development method for developing the exposed (irradiated) photosensitive resin layer can be selected from conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment. Furthermore, after development, post-development baking may be performed at any temperature and time combination, as needed, for the purpose of adjusting the shape of the relief pattern. The developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of such a good solvent and a poor solvent. Examples of suitable good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the good solvent to the poor solvent depending on the solubility of the polymer in the negative photosensitive resin composition. Two or more types of each solvent, for example, several types, can also be used in combination. In the step of developing the photosensitive resin layer after exposure, it is preferable to perform the above coating to development steps so as to obtain a photosensitive resin layer with a film thickness of 10 μm to 15 μm. The development time is preferably 30 seconds or less, more preferably 25 seconds or less, and even more preferably 20 seconds or less. Without being bound by theory, a development time of 30 seconds or less creates a difference in solubility with the exposed area, resulting in contrast and improved pattern resolution.

[0121] (5) A process of heat-treating the developed photosensitive resin layer to form a cured polyimide film. In this step, the relief pattern obtained by the development is heated to dissolve the photosensitive component and imidize the (A) polyimide precursor, converting it into a cured relief pattern made of polyimide. Various methods can be selected for heat curing, including those using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be carried out, for example, at 160°C to 400°C for 30 minutes to 5 hours. The atmospheric gas used for heat curing may be air, or an inert gas such as nitrogen or argon. In this manner, a cured relief pattern (cured polyimide film) can be produced.

[0122] A method for producing a cured polyimide film according to the present disclosure includes, for example, applying the photosensitive resin composition according to the present disclosure onto a substrate, exposing the substrate to light, developing the substrate, and then heating the substrate. The cured film preferably has a dielectric loss tangent of 0.003 to 0.012 when measured at 40 GHz by a perturbation split cylinder resonator method. The dielectric loss tangent can be measured by the perturbation split cylinder resonator method described in the Examples below.

[0123] The present disclosure also provides a polyimide cured film obtained from the photosensitive resin composition described above. The cured film preferably has a moisture permeability of less than 800, more preferably less than 700. From the viewpoint of dielectric loss tangent, a lower moisture permeability is preferable because the frequency dependence of the dielectric loss tangent tends to be less. However, from the viewpoint of resolution, a lower moisture permeability leads to poorer solubility of unexposed areas during patterning, resulting in poorer resolution, so a moisture permeability of 500 or more and less than 800 is more preferable. A moisture permeability of less than 800 results in a highly reliable cured film. See below for details on the method for measuring moisture permeability. From the viewpoint of resolution, dielectric properties, and frequency dependence of the dielectric loss tangent, the product of the dielectric loss tangent and the moisture permeability (tanδ 40 × WVTR) is preferably within a certain range, and when the dielectric loss tangent value at 40 GHz is used, the following formula (3): 3.0 <tanδ 40 ×WVTR<10.0 (3) It is preferable to satisfy tan δ 40 When ×WVTR is in the range of 3.0 to 10.0, a polyimide cured product having excellent resolution and dielectric properties and little frequency dependency can be obtained. The difference in dielectric loss tangent between 40 GHz and 10 GHz is preferably 0.0015 or less, and more preferably 0.001 or less.

[0124] The base on which the cured relief pattern produced 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. A higher aspect ratio enables the formation of finer wiring. The minimum opening size of vias is, for example, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less, in a cured film formed to a thickness of 10 μm.

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

[0127] The polyimide contained in the cured relief pattern (cured polyimide film) formed from the polyimide precursor composition is represented by the following general formula (13): [ka] It is preferable that the compound has a structure represented by the following formula: {In general formula (13), X1 and Y1 are the same as X1 and Y1 in general formula (4), and n2 is an integer of 2 to 150.}

[0128] <Display device> The present disclosure also provides a display device using the photosensitive resin composition of the present disclosure, the display device including a display element and a cured film provided on the display element, the cured film having the above-described cured relief pattern. The cured relief pattern may be laminated directly on the display element or may be laminated via another layer. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA-type liquid crystal display devices, and partition walls for cathodes of organic EL elements.

[0129] In addition to being applicable to the semiconductor devices described above, the photosensitive resin composition of the present disclosure is also useful for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. [Example]

[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 (standard polystyrene equivalent). The columns used were Shodex 805M / 806M (trademark) series manufactured by Showa Denko K.K. The standard monodisperse polystyrene was Shodex STANDARD SM-105 (manufactured by Showa Denko K.K.), N-methyl-2-pyrrolidone, and a Shodex RI-930 (trademark) detector manufactured by Showa Denko K.K.

[0132] (2) Resolution and development time of cured relief patterns on Cu substrates A 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti layer and a 400 nm thick Cu layer, in that order, using a sputtering system (L-440S-FHL, Canon Anelva Corporation). A photosensitive resin composition prepared by the method described below was then spin-coated onto the wafer using a coater developer (D-Spin60A, SOKUDO Co., Ltd.) and dried by heating on a hot plate at 110°C for 3 minutes, forming a photosensitive resin layer approximately 13.5 μm thick. A test pattern mask was used to apply 200 mJ / cm of light to this photosensitive resin layer using a Prisma GHI (Ultratech Co., Ltd.) equipped with an i-line filter. 2The photosensitive resin layer was then spray-developed using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) with cyclopentanone as the developer and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on the Cu. The spray development time was defined as the development time. The wafer with the relief pattern formed on the Cu was then heat-treated in a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) at 230°C for 2 hours under a nitrogen atmosphere to obtain a cured relief pattern of approximately 10 μm thick resin on the Cu. The relief pattern was observed under an optical microscope to determine the minimum via opening size. If the area of ​​the opening in the resulting pattern was at least half the area of ​​the corresponding pattern mask opening, it was considered resolved. The resolution was evaluated based on the length of the mask opening side (opening pattern size) corresponding to the smallest area among the resolved openings, using the following evaluation criteria: (Evaluation criteria) A: The minimum opening pattern size is less than 10 μm B: The minimum opening pattern size is 10 μm or more and less than 15 μm C: The minimum opening pattern size is 15 μm or more and less than 20 μm D: The minimum opening pattern size is 20 μm or more

[0133] (3) Measurement of dielectric properties (relative permittivity: Dk, dielectric loss tangent: Df) 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. 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. 2The entire surface was exposed to ghi rays and then heat-cured for 2 hours at 230°C under a nitrogen atmosphere using a vertical curing oven (Koyo Lindberg, model VF-2000B) to produce a cured resin film approximately 10 μm thick on the Al wafer. This cured film was cut into 80 mm long and 62 mm wide pieces using a dicing saw (Disco, model DAD-2H / 6T), immersed in a 10% hydrochloric acid solution, and peeled off from the silicon wafer to produce a film sample. Moisture permeability was measured according to the cup method of JIS Z0208. The amount of calcium chloride used was 40 g, and the moisture permeability conditions were 65°C and 90% RH. The test was run for 24 hours, after which the sample was removed from the thermo-hygrostat, left at room temperature for 30 minutes, and then weighed. Water permeability (WVTR) was calculated using the following formula: WVTR = {(weight after test) - (weight before test)} / (0.03 2 ×π) (Formula X) {In the formula X, 0.03 represents the radius of the cup (m)} The WVTR here is a value for a 10 μm cured film and is a value that depends on the film thickness. For example, a 20 μm film thickness will be half the WVTR value obtained at 10 μm. The lower the WVTR value, the lower the film's water vapor transmission rate. Furthermore, the more hydrophobic the film is and the higher the film's density, the lower the WVTR tends to be.

[0135] (5) IR measurement IR measurement was performed on the film obtained in (3) above using Nicolet 380 by the ATR method at 700 cm -1 More than 4000cm -1 The following range was measured with 50 scans. A silicon prism was used for the sample contact area. 1450 cm -1 More than 1550cm -1 The largest absorption peak intensity in the following range is Ph1, the second largest is Ph2, and 1380cm -1 The peak intensity around 1380 cm was taken as Im1, and Ph1 was normalized to 1 to calculate Ph2 and Im1. -1 The peak intensity around 1380 cm -1±10cm -1 The largest peak was

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

[0137] [(A) Preparation of 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 generated by the reaction had ceased, the mixture was allowed to cool to room temperature and then left to stand for a further 16 hours.

[0138] Next, under ice cooling, a solution of 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 of 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, followed by stirring for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

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

[0140] Synthesis of polyimide precursor (polymer A-2): Polymer A-2 was obtained by the same procedure as in the synthesis of Polymer A-1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid 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 weight-average molecular weight (Mw) of this polymer A-2 was measured and found to be 23,000. The polyimide obtained from Polymer A-2 had an imide group concentration (U) per repeating unit of 20.1 wt% and an aliphatic hydrocarbon group concentration (T) of 8.6 wt%.

[0141] Synthesis of polyimide precursor (polymer A-3): Polymer A-3 was obtained by the same reaction procedure as in the synthesis of 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 weight average molecular weight (Mw) of this polymer A-3 was measured and found to be 20,000. The polyimide obtained from Polymer A-3 had an imide group concentration (U) per repeating unit of 23.0 wt% and an aliphatic hydrocarbon group concentration (T) of 7.4 wt%.

[0142] Synthesis of polyimide precursor (polymer A-4): Polymer A-4 was obtained by the same reaction method as in the synthesis of 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 weight average molecular weight (Mw) of this polymer A-4 was measured and found to be 21,000. The polyimide obtained from Polymer A-4 had an imide group concentration U per repeating unit of 20.1 wt% and an aliphatic hydrocarbon group concentration T of 8.6 wt%.

[0143] Synthesis of polyimide precursor (polymer A-5): Polymer A-5 was obtained by the same reaction method as in the synthesis of Polymer A-1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride was used instead of 155.1 g of ODPA. The weight average molecular weight (Mw) of this polymer A-5 was measured and found to be 24,000. The polyimide obtained from Polymer A-5 had an imide group concentration U per repeating unit of 15.2 wt% and an aliphatic hydrocarbon group concentration T of 9.8 wt%.

[0144] Synthesis of polyimide precursor (polymer A-6): Polymer A-6 was obtained by the same procedure as in the synthesis of Polymer A-1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid 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. The weight-average molecular weight (Mw) of this polymer A-6 was measured and found to be 22,000. The polyimide obtained from Polymer A-6 had an imide group concentration (U) per repeating unit of 15.8 wt% and an aliphatic hydrocarbon group concentration (T) of 16.2 wt%.

[0145] Synthesis of polyimide precursor (polymer A-7): Polymer A-7 was obtained by the same procedure as in the synthesis of Polymer A-1, except that 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid 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. The weight-average molecular weight (Mw) of this polymer A-7 was measured and found to be 20,000. The polyimide obtained from Polymer A-7 had an imide group concentration (U) per repeating unit of 13.3 wt% and an aliphatic hydrocarbon group concentration (T) of 20.7 wt%.

[0146] Synthesis of polyimide precursor (polymer A-8): Polymer A-8 was obtained by the same reaction procedure as 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. The weight-average molecular weight (Mw) of this polymer A-8 was measured and found to be 14,000. The polyimide obtained from Polymer A-8 had an imide group concentration (U) per repeating unit of 18.7 wt% and an aliphatic hydrocarbon group concentration (T) of 25.1 wt%.

[0147] Synthesis of polyimide precursor (polymer A-9): Polymer A-9 was obtained by the same reaction procedure as in 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. The weight-average molecular weight (Mw) of this polymer A-9 was measured to be 21,000. The polyimide obtained from Polymer A-9 had an imide group concentration (U) per repeating unit of 20.0 wt% and an aliphatic hydrocarbon group concentration (T) of 6.5 wt%.

[0148] Synthesis of polyimide precursor (polymer A-10): Polymer A-10 was obtained by the same reaction method as in 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. The weight-average molecular weight (Mw) of this polymer A-10 was measured and found to be 16,000. The polyimide obtained from Polymer A-10 had an imide group concentration U per repeating unit of 16.7 wt% and an aliphatic hydrocarbon group concentration T of 22.3 wt%.

[0149] Synthesis of polyimide precursor (polymer A-11): 93.7 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (as the acid component) was placed in a 1-liter separable flask, 175 g of γ-butyrolactone was added, and while stirring at room temperature, a separately prepared γ-butyrolactone solution prepared 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 heated at 50°C for 1 hour, then 48.7 g of 2-hydroxyethyl methacrylate (HEMA) was added and heated at 50°C for a further 4 hours. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature. The mixture was then left to stand for a further 16 hours to obtain a reaction mixture.

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

[0151] The resulting reaction solution was added to 2700 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was then washed with an anion exchange resin ("Amberlyst" manufactured by Organo Corporation). TM 15") to obtain a polymer solution. The obtained polymer solution was added dropwise to 8,000 g of water to precipitate the polymer, and the resulting precipitate was collected by filtration and dried in vacuum to obtain powdered polymer A-11. The weight-average molecular weight (Mw) of this polymer A-11 was measured to be 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): 93.7 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (as the acid component) 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, and after the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature. After leaving it to stand for a further 16 hours, a reaction mixture was obtained.

[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 with stirring. The mixture was heated at 50°C for 7 hours, and after the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature. After standing for a further 16 hours, a reaction mixture was obtained.

[0154] Next, under ice cooling, a solution of 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 of 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) dissolved in 110 g of γ-butyrolactone was added as the diamine component over 60 minutes with stirring. After stirring at room temperature for another 2.5 hours, 15 g of ethyl alcohol was added, and the mixture was stirred for 30 minutes, after which 150 g of γ-butyrolactone was added. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0155] The resulting reaction solution was added to 2700 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was then washed with an anion exchange resin ("Amberlyst" manufactured by Organo Corporation). TM The polymer solution was purified using a solvent such as PEG-15 to obtain a polymer solution. The resulting polymer solution was added dropwise to 8,000 g of water to precipitate the polymer, and the resulting precipitate was collected by filtration and dried in vacuo to obtain powdered polymer A-12. The weight-average molecular weight (Mw) of this polymer A-12 was measured to be 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): Polymer A-13 was obtained by the same reaction procedure as in 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. The weight-average molecular weight (Mw) of this polymer A-13 was measured and found to be 22,000. The polyimide obtained from Polymer A-13 had an imide group concentration (U) per repeating unit of 30.5 wt% and an aliphatic hydrocarbon group concentration (T) of 0 wt%.

[0157] Synthesis of polyimide precursor (polymer A-14): Polymer A-14 was obtained by the same reaction method as in 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. The weight-average molecular weight (Mw) of this polymer A-14 was measured and found to be 19,000. The polyimide obtained from Polymer A-14 had an imide group concentration (U) per repeating unit of 28.8 wt% and an aliphatic hydrocarbon group concentration (T) of 6.2 wt%.

[0158] Synthesis of polyimide precursor (polymer A-15): Polymer A-15 was obtained by carrying out the reaction in the same manner as in 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. The weight-average molecular weight (Mw) of this polymer A-15 was measured and found to be 22,000. The polyimide obtained from Polymer A-15 had an imide group concentration (U) per repeating unit of 20.5 wt% and an aliphatic hydrocarbon group concentration (T) of 4.4 wt%.

[0159] Synthesis of polyimide precursor (polymer A-16): Polymer A-16 was obtained by carrying out the reaction in the same manner as in 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. The weight average molecular weight (Mw) of this polymer A-16 was measured and found to be 29,000. The polyimide obtained from polymer A-16 had an imide group concentration U per repeating unit of 14.1 wt % and an aliphatic hydrocarbon group concentration T of 12.1 wt %.

[0160] [Production of Photosensitive Resin Composition] The following compounds were used in the examples and comparative examples. Photoinitiator B-1: TR-PBG-304 (manufactured by Changzhou Strong Electronics Co., Ltd.) Photoinitiator B-2: TR-PBG-305 (manufactured by Changzhou Strong Electronics Co., Ltd.) Photoinitiator B-3: TR-PBG-3057 (manufactured by Changzhou Strong Electronics Co., Ltd.) C-1: γ-butyrolactone (GBL) C-2: Dimethyl sulfoxide (DMSO) D-1: 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) D-2: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) D-3: (3-triethoxysilylpropyl)-tert-butylcarbamate D-4: Ureidopropyltriethoxysilane (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: Polyoxypropylene-modified bisphenol A diacrylate (Kyoeisha Chemical Co., Ltd.) F-1: BMI-5100 (manufactured by Daiwa Chemical Industry Co., Ltd.) F-2: SBB70P (Asahi Kasei) G-1: K180SP-CY1 (Admatechs)

[0161] Example 1 As shown in Table 1, negative-type photosensitive resin compositions were prepared using polyimide precursor A-1 by the following method, and the prepared compositions were evaluated. (A) 100 g of A-1 as polyimide precursor, (B) 5 g of B-1 as photopolymerization initiator, and (C) 180 g of GBL and 20 g of DMSO as solvents were dissolved. The viscosity of the resulting solution was adjusted to approximately 40 poise by further adding a small amount of GBL, yielding a negative-type 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 and Comparative Examples 1 to 3> Negative photosensitive resin compositions similar to those in Example 1 were prepared, except that they were prepared at the blending ratios shown in Tables 1, 3, and 5 below, and were evaluated in the same manner as in Example 1. 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 loss tangents (Df) at 40 GHz of the photosensitive resin compositions of Examples 1 to 27 were 0.0059 to 0.012, which were lower than those of Comparative Examples 1 to 3. Furthermore, the photosensitive resin compositions of Examples 1 to 27 had a product of moisture permeability and dielectric loss tangent of 3.91 to 9.41, which were lower than those of the comparative examples. Comparative Examples 1 and 2 required long development times, and Comparative Example 1 had a resolution of "D". [Industrial Applicability]

[0170] The photosensitive resin composition of the present invention can be used to obtain a cured film having high resolution and a low dielectric loss tangent even in a thick film. Therefore, the photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors; (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: a polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C, wherein the polyimide in the cured film has an imide group concentration U, which is the ratio of the molecular weight of imide groups to the molecular weight of a repeating unit containing a structure derived from a tetracarboxylic dianhydride and a diamine, of 12 wt % to 26 wt %; The photosensitive resin composition, wherein the resin comprises a structure represented by the following general formula (14): 【Chemical 1】 {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 or an alkyl group having 1 to 10 carbon atoms, which may form a ring structure, or an organic group containing an aromatic ring having 6 to 10 carbon atoms; m ９ 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, and Z ２ represents a single bond, an organic group having a hetero atom, or an organic group having 1 to 13 carbon atoms, and * represents the connecting portion with the main chain of the resin.

2. 2. The photosensitive resin composition according to claim 1, wherein the polyimide in the cured polyimide film obtained by heating and curing the photosensitive resin composition at 350°C has an aliphatic hydrocarbon group concentration, which is the ratio of the total molecular weight of aliphatic hydrocarbon groups to the molecular weight of repeating units containing a structure derived from a tetracarboxylic dianhydride and a diamine compound, of 4 wt % to 35 wt %.

3. 3. The photosensitive resin composition according to claim 1, wherein the structure represented by general formula (14) is derived from a diamine.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the resin is a polyimide precursor.

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

6. (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors; (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 case where the resin contains a polyimide precursor, the polyimide precursor is a compound represented by the following general formula (4): 【Chemistry 4】 {In the formula, X １ is a tetravalent organic group having 6 to 40 carbon atoms, and Y １ is a divalent organic group having 6 to 40 carbon atoms, and n １ is an integer from 2 to 150, and R ４ and R ５ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. ４ and R ５ At least one of these is a group represented by the following general formula (5): 【Chemistry 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 from 2 to 10. The resin is represented by the following general formula (15): 【Chemistry 6】 In the formula, each Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom and which 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 group represented by the following formula: 【Chemistry 7】 The compound is one of the compounds represented by the formula: The resin is represented by the following general formula (14): 【Chemistry 8】 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 or an alkyl group having 1 to 10 carbon atoms, which may form a ring structure, or an organic group containing an aromatic ring having 6 to 10 carbon atoms; m ９ 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, and Z ２ is a single bond, an organic group having a hetero atom, or an organic group having 1 to 13 carbon atoms, and * represents a connecting portion to the main chain of the resin.

7. (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors; (B) 0.5 to 10 parts by mass of a photosensitizer; (C) 100 to 300 parts by mass of a solvent; In a polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C, the polyimide has a molecular weight of an imide group relative to a molecular weight of a repeating unit containing a structure derived from a tetracarboxylic dianhydride and a diamine, and the polyimide has an aliphatic hydrocarbon group concentration T, where U is the ratio of the molecular weight of an imide group to the molecular weight of a repeating unit containing a structure derived from a tetracarboxylic dianhydride and a diamine, and T is the ratio of the total molecular weight of an aliphatic hydrocarbon group to the molecular weight of a repeating unit containing a structure derived from a tetracarboxylic dianhydride and a diamine, and X is 12 wt% to 26 wt%, and the following formula (1): -12.6<UT<16.0 (1) A photosensitive resin composition that satisfies the above requirements.

8. (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors; (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: (A) The IR spectrum of the polyimide obtained by heating and curing the polyimide precursor at 230°C shows a peak at 1450 cm －１ More than 1550cm －１ The largest peak intensity of the absorption peaks in the following range is Ph １ , the second peak intensity is Ph ２ , 1380 cm －１ The peak intensity around Im １ and Ph １ When normalized to 1, the following equation (2): 0.34≦Ph ２ ×Im １ ≦1.2 (2) A photosensitive resin composition that satisfies the above requirements.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the resin is a reaction product of a tetracarboxylic dianhydride and a diamine.

10. The photosensitive resin composition according to claim 9 , wherein the at least one tetracarboxylic dianhydride and the at least one diamine constituting the resin have an aliphatic hydrocarbon group.

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

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

13. The photosensitive resin composition according to claim 12, wherein the radical polymerizable compound (E) has an alkyl group.

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

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

16. The following steps: A step of applying the photosensitive resin composition according to any one of claims 1 to 15 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 cured polyimide film; A method for producing a cured polyimide film, comprising:

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

18. A cured polyimide film having a dielectric loss tangent of 0.003 to 0.014 at a frequency of 40 GHz as measured by a perturbation split cylinder resonator method, and satisfying the following formula (3): 3<tanδ ４０ ×WVTR<10 (3) {In the formula, tanδ ４０ represents the dielectric loss tangent at a frequency of 40 GHz as determined by a perturbation split cylinder resonator method, and WVTR represents the moisture permeability of the cured polyimide film converted into a film thickness of 10 μm.

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

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