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

Abstract

To provide, e.g., a photosensitive resin composition that has low dielectric characteristics, low water vapor permeability, and good chemical resistance, and can form a cured relief pattern at high resolution.SOLUTION: The photosensitive resin composition includes 100 pts.mass of a polyimide precursor resin, 0.5-10 pts.mass of a photopolymerization initiator, and 50-500 pts.mass of a solvent. The polyimide precursor resin includes a terminal structure selected from the general formulas (1)-(3). The total of the aliphatic hydrocarbon group concentrations of the polyimide precursor resin is 4-35 wt.%.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

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

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

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

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

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

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

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

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

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

Means for Solving the Problems

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

[16] . [1] (A) 100 parts by mass of a polyimide precursor resin; (B) 0.5 to 10 parts by mass of a photoinitiator; (C) 50 to 500 parts by mass of a solvent; A photosensitive resin composition comprising: The above (A) polyimide precursor resin contains at least one terminal structure selected from the group consisting of the following general formulas (1) to (3), [Chemical Formula] {In the formula, W is a divalent to trivalent organic group, and R 1 ~R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, m 1 is a group represented by an integer of 1 to 2, m 2 is a group represented by an integer of 2 to 10, and * means bonding to the main chain of the resin.} In the polyimide of the polyimide cured film obtained by heating and curing the above photosensitive resin composition at 350 °C, the aliphatic hydrocarbon group concentration T, which is the ratio of the total molecular weight of the aliphatic hydrocarbon groups to the molecular weight of the repeating unit containing the structures derived from the tetracarboxylic dianhydride and the diamine compound, is 4 wt% to 35 wt%. A photosensitive resin composition. [2] (A) 100 parts by mass of a polyimide precursor resin; (B) 0.5 to 10 parts by mass of a photosensitizer; (C) 100 to 300 parts by mass of a solvent; A photosensitive resin composition comprising: In the polyimide of the polyimide cured film obtained by heating and curing the above photosensitive resin composition at 350 ° C, with respect to the molecular weight of the repeating unit containing the structure derived from the tetracarboxylic dianhydride and the diamine compound, the aliphatic hydrocarbon group concentration T which is the ratio occupied by the total molecular weight of the aliphatic hydrocarbon groups, and the photosensitive group concentration S which is the ratio occupied by the total molecular weight of the photosensitive groups with respect to the molecular weight of the repeating unit in the above (A) polyimide precursor resin, are represented by the following formula (1): -77 ≦ 4T - 3S ≦ 44 (1) and satisfy The above (A) polyimide precursor resin is a photosensitive resin composition having, at the resin terminal, another reactive unsaturated bond that polymerizes by heat or light, which is different from the reactive unsaturated bond side chain contained in its repeating unit. [3] The photosensitive resin composition according to any one of items 1 or 2, wherein the above (A) polyimide precursor resin is represented by the following general formula (4). [Chemical formula] {In the formula, X 1 is a tetravalent organic group having 6 to 40 carbon atoms, Y 1 is a divalent organic group having 6 to 40 carbon atoms, n 1 is an integer of 2 to 150, R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, among R 4 and R 5 , at least one is a group represented by the following general formula (5).} [Chemical formula] {In the formula, R 6 , R 7 and R 8 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m 2 is an integer of 2 to 10.} [4] The photosensitive resin composition according to any one of Items 1 to 3, wherein the photosensitive group concentration S, which is the ratio of the total molecular weight of the photosensitive groups to the molecular weight of the repeating unit in the (A) polyimide precursor resin represented by the general formula (4), is 15 wt% to 35 wt%. [5] The photosensitive resin composition according to any one of Items 1 to 4, wherein the (A) polyimide precursor resin contains a structure represented by the following general formula (6). [Chemical formula] {In the formula, R 9 , R 10 are each independently an organic group having 1 to 10 carbon atoms, m 3 , m 4 is an integer selected from 1 to 4, Z is selected from the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a hetero atom, and * means bonding to the main chain of the resin.} [6] The photosensitive resin composition according to any one of Items 1 to 5, further comprising (D) a silane coupling agent. [7] The photosensitive resin composition according to any one of Items 1 to 6, further comprising (E) a radically polymerizable compound. [8] The photosensitive resin composition according to any one of Items 1 to 7, further comprising (F) a thermal crosslinking agent. [9] The photosensitive resin composition according to any one of Items 1 to 8, further comprising (G) a filler.

[10] The (A) polyimide precursor resin contains a terminal structure derived from a tetracarboxylic dianhydride at the terminal of the main chain, 1 The photosensitive resin composition according to any one of Items 1 to 9, wherein when the peak area of the amide group derived from the main chain structure is 1.0 in 1H-NMR, the terminal blocking value indicating the terminal blocking rate is 0.02 or more.

[11] (A) 100 parts by mass of a polyimide precursor resin; (B) 0.5 to 10 parts by mass of a photoinitiator; (C) 50 to 500 parts by mass of a solvent and; A photosensitive resin composition comprising: The above (A) polyimide precursor resin contains a terminal structure derived from a tetracarboxylic dianhydride at the end of the main chain, 1 A photosensitive resin composition in which, when the peak area of the amide group derived from the main chain structure is set to 1.0 by 1H-NMR, the terminal capping value indicating the terminal capping rate is 0.02 or more.

[12] (A) 100 parts by mass of a polyimide precursor resin and; (B) 0.5 to 10 parts by mass of a photoinitiator and; (C) 50 to 500 parts by mass of a solvent and; A photosensitive resin composition comprising: The above (A) polyimide precursor resin contains a terminal structure derived from a diamine at the end of the main chain, 1 A photosensitive resin composition in which, when the peak area of the amide group derived from the main chain structure is set to 1.0 by 1H-NMR, the terminal capping value indicating the terminal capping rate is 0.06 or more.

[13] A method for producing a polyimide cured film, the method comprising the following steps: Applying the photosensitive resin composition according to any one of Items 1 to 12 onto a substrate to form a photosensitive resin layer on the substrate; Heating and drying the obtained photosensitive resin layer; Exposing the photosensitive resin layer after heating and drying; Developing the photosensitive resin layer after exposure; Heat-treating the photosensitive resin layer after development to form a polyimide cured film; A method for producing a polyimide cured film, comprising:

[14] A method for producing a cured film, comprising applying the resin composition according to any one of Items 1 to 12 onto a substrate, performing an exposure treatment, a development treatment, and then a heat treatment, wherein the cured film is an insulating film used for rewiring applications, and the cured film has a dielectric loss tangent measured by the perturbed mode split cylinder resonator method at 40 GHz of 3.0×10-3 ~1.3×10 -2 A method for producing a polyimide cured film, which is in the range of

[15] A polyimide cured film, wherein the dielectric loss tangent at a frequency of 40 GHz by the perturbation mode split cylinder resonator method is 3.0×10 -3 ~1.3×10 -2 and satisfies the following formula (2): 3.0 < tanδ 40 ×WVTR < 10.0 (2) {In the formula, tanδ 40 represents the dielectric loss tangent at a frequency of 40 GHz by the perturbation mode split cylinder resonator method, and WVTR represents the water vapor transmission rate of the polyimide cured film with a thickness of 10 μm.}, a polyimide cured film that satisfies the above conditions.

[16] The dielectric loss tangent at a frequency of 40 GHz by the perturbation mode split cylinder resonator method is 3.0×10 -3 ~1.3×10 -2 and satisfies the following formula (3): 4.0 < tanδ 40 ×WVTR × DR < 29.0 (3) {In the formula, tanδ 40 represents the dielectric loss tangent at a frequency of 40 GHz by the perturbation mode split cylinder resonator method, WVTR represents the water vapor transmission rate of the polyimide cured film converted to a thickness of 10 μm, and DR represents the dissolution rate in the chemical resistance test.}, the polyimide cured film according to item 15, which satisfies the above conditions.

[17] A method for producing a photosensitive resin composition, wherein the photosensitive resin composition comprises (A) 100 parts by mass of a polyimide precursor resin; (B) 0.5 to 10 parts by mass of a photoinitiator; (C) 50 to 500 parts by mass of a solvent; and the method includes a step of synthesizing the above (A) polyimide precursor resin and a step of mixing the above (A) polyimide precursor resin, the above (B) photoinitiator, and (C) solvent to obtain a photosensitive resin composition, the above synthesis step includes the following steps: (i) Reacting a tetracarboxylic dianhydride with a first compound having a reactive substituent that reacts with heat or light to produce a first compound-introduced moiety and a carboxyl group, and then reacting with a second compound having a reactive substituent that reacts with heat or light different from that of the first compound, or reacting a tetracarboxylic dianhydride with a second compound having a reactive substituent that reacts with heat or light to produce a second compound-introduced moiety and a carboxyl group, and then reacting with a first compound having a reactive substituent that reacts with heat or light different from that of the second compound, thereby obtaining an acid component monomer having a second compound-introduced moiety, and / or (ii) Reacting a diamine compound with a second compound having a reactive substituent that reacts with heat or light to obtain a diamine monomer having a second compound-introduced moiety, Obtaining an acid component monomer and / or a diamine monomer having the second compound-introduced moiety by (i) and / or (ii) above, a monomer adjustment step, Condensing the acid component monomer and / or the diamine monomer having the second compound-introduced moiety, a tetracarboxylic dianhydride, and a diamine compound to synthesize a polyimide precursor, a polymerization step, comprising, The above (A) polyimide precursor resin has a reactive substituent derived from the second compound at the main chain terminals, A method for producing a photosensitive resin composition.

[18] A method for producing a polyimide precursor resin, the method comprising the following steps: (i) React a tetracarboxylic dianhydride with a first compound having a reactive substituent that reacts with heat or light to produce a first compound-introduced moiety and a carboxyl group, and then react with a second compound having a reactive substituent that reacts with heat or light different from that of the first compound, or react a tetracarboxylic dianhydride with a second compound having a reactive substituent that reacts with heat or light to produce a second compound-introduced moiety and a carboxyl group, and then react with a first compound having a reactive substituent that reacts with heat or light different from that of the second compound, thereby obtaining an acid component monomer having a second compound-introduced moiety, and / or (ii) React a diamine compound with a second compound having a reactive substituent that reacts with heat or light to obtain a diamine monomer having a second compound-introduced moiety, A monomer adjustment step of obtaining an acid component monomer and / or a diamine monomer having the second compound-introduced moiety by (i) and / or (ii) above, A polymerization step of subjecting the acid component monomer and / or diamine monomer having the second compound-introduced moiety, a tetracarboxylic dianhydride, and a diamine compound to a condensation reaction to synthesize a polyimide precursor, comprising The polyimide precursor resin has a reactive substituent derived from the second compound at the main chain terminal, A method for producing a polyimide precursor resin.

Advantages of the Invention

[0012] By using the photosensitive resin composition of the present disclosure, a cured resin film excellent in the resolution of a relief pattern, having low dielectric properties, low moisture permeability, and good chemical resistance can be produced. By using a polyimide precursor having a specific terminal crosslinking group and an aliphatic hydrocarbon group, the solubility in a developer in a pre-baked film is improved, thereby improving the resolution of the relief pattern. In addition, the hydrophobicity and crosslink density in the cured film are improved, resulting in a lower moisture permeability and improved chemical resistance. Moreover, the dielectric tangent decreases due to an increase in the excluded volume.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0014] Hereinafter, embodiments of the present disclosure will be described in detail. Throughout this specification, structures represented by the same reference numerals in the general formulae are independently selected respectively if there are a plurality in the molecule, and may be the same or different from each other unless otherwise specified. Also, structures represented by common reference numerals in different general formulae are also independently selected respectively unless otherwise specified, and may be the same or different from each other.

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

[0016] [(A) Polyimide Precursor]

[0017] (Condition 1) The polyimide precursor resin preferably satisfies both of the following two conditions (1-i) and (1-ii). (1-i) The polyimide precursor resin contains at least one terminal structure selected from the group consisting of the following general formulae (1) to (3). [Chemical Formula] {In the formula, W is a divalent or trivalent organic group, and R 1 ~R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, m 1 is an integer of 1 to 2, m 2 is an integer of 2 to 10, and * means bonding to the main chain of the polyimide precursor resin.} (1-ii) In the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 °C, the aliphatic hydrocarbon group concentration T, which is the ratio of the total molecular weight of the aliphatic hydrocarbon groups to the molecular weight of the repeating unit containing the structures derived from the tetracarboxylic dianhydride and the diamine compound, is 4 wt% to 35 wt%. By satisfying these conditions (1-i) and (1-ii) for the polyimide precursor, a negative photosensitive resin composition having low dielectric properties, low moisture permeability, and good chemical resistance and high resolution can be obtained.

[0018] (Method for introducing terminal structure 1) To form the terminal structures of the above general formula (1) and the above general formula (2), after reacting a tetracarboxylic dianhydride having a desired tetravalent organic group X with a compound having an isocyanate group, alcohols having a photopolymerizable group (for example, an unsaturated double bond) are reacted to prepare a partially imidized or imide-derivatized (structure derived from the above general formula (2)) / esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester / imide form). In order to accelerate the reaction between the tetracarboxylic dianhydride and the compound having an isocyanate group, pyridine, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, etc. can be used. Saturated aliphatic alcohols may be optionally used in combination with the above alcohols having a photopolymerizable group.

[0019] (Method for introducing terminal structure 2) To form the terminal structure of the general formula (3), a tetracarboxylic dianhydride having a desired tetravalent organic group X is reacted with alcohols 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). After that, 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). In order to promote the reaction between the tetracarboxylic dianhydride and the compound having an isocyanate group, pyridine, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, etc. can be used. Optionally, saturated aliphatic alcohols may be used in combination with the alcohols having the photopolymerizable group.

[0020] The structure of W is not particularly limited, but is preferably a divalent to trivalent organic group having a weight average molecular weight of less than 300, more preferably a divalent to trivalent organic group having 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.

[0021] In the reactive terminal structure derived from the tetracarboxylic dianhydride, the polymerization conditions are in an acid excess, and the polymerization system of the resin does not become basic. Therefore, the deactivation of the polymerization active terminal is suppressed, and it is difficult to form a terminal that is a factor in the deterioration of the dielectric tangent. Thus, it is preferable from the viewpoint of the dielectric tangent. Further, when the linking structure of the reactive terminal structure is an imide bond or an amide bond represented by the general formulas (1) to (3), the heat resistance and hydrolysis resistance are better than those of an ester bond or the like, and the polymerizable functional group does not detach from the terminal structure of the resin during the heat treatment process or the reliability test performed under high temperature and high humidity conditions. Therefore, it is preferable from the viewpoint of chemical resistance. Furthermore, since the terminal polymerizable functional group has a (meth)acrylate group, the reactivity during curing is high, which is more preferable from the viewpoint of chemical resistance.

[0022] "Aliphatic hydrocarbon group concentration T" refers to the ratio that the total molecular weight of aliphatic hydrocarbon groups occupies with respect to the molecular weight of repeating units containing structures derived from tetracarboxylic dianhydrides and diamine compounds in the polyimide of a polyimide cured film obtained by heating and curing a photosensitive resin composition at 350 °C. The condition of heating and curing at 350 °C is to clarify the standard of the aliphatic hydrocarbon group concentration T based on the state where the polyimide precursor is almost 100% imidized, and it is not intended that the photosensitive resin composition be heated and cured at 350 °C in actual use. Here, the "aliphatic hydrocarbon group" is a hydrocarbon group having at least one structure selected from the group consisting of a saturated aliphatic chain, an unsaturated aliphatic chain, and an alicyclic structure, which does not contain heteroatoms branched from the main chain of the polyimide precursor, and may be either linear or branched. The part of the alkylene skeleton constituting a part of the main chain and the quaternary carbon (a carbon substituted twice and constituting a part of the main chain) constituting a part of the main chain are not included in the "aliphatic hydrocarbon group" in the calculation of the aliphatic hydrocarbon group concentration. The aliphatic hydrocarbon group constituting the branched side chain part from the main chain is included in the "aliphatic hydrocarbon group" in the calculation of the aliphatic hydrocarbon group concentration, whether it is saturated or unsaturated, linear or alicyclic. Examples of the structure of the "aliphatic hydrocarbon group" include structures represented by the following general formula (A1), the following general formula (A2), and the following general formula (A3).

Chemical formula

[0023] In general formulas (A1) to (A3), L is either a single bond or an a-valent organic group that may be a linear or branched saturated hydrocarbon or a linear or branched unsaturated hydrocarbon group, b is an integer from 1 to 6, and R a1 is an organic group having 1 to 8 carbon atoms or a hydrogen atom that may have a ring structure. * is a connecting group to the main chain structure.

[0024] From the perspective of the dielectric loss tangent of the polyimide cured film, the aliphatic hydrocarbon group is preferably represented by the above general formula (4) or the above general formula (6). From the perspective of chemical resistance, it is more preferably a group having 1 to 3 carbon atoms, and for example, it preferably has a methyl group. When the concentration T of the aliphatic hydrocarbon group is 4 wt% or more, the dielectric loss tangent of the polyimide cured film tends to be good. The concentration T of the aliphatic hydrocarbon group is preferably 5 wt% or more, more preferably 7 wt% or more, and still more preferably 8 wt% or more. When the concentration T of the aliphatic hydrocarbon group is 5 wt% or more, the moisture permeability tends to be good. On the other hand, when the concentration T of the aliphatic hydrocarbon group is 35 wt% or less, the resolution and moisture permeability of the obtained polyimide cured film tend to be good. The concentration T of the aliphatic hydrocarbon group is more preferably 28 wt% or less, and still more preferably 17 wt% or less.

[0025] The concentration T of the aliphatic hydrocarbon group is calculated using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in the preparation of the 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.}

[0026] When two or more types of tetracarboxylic dianhydrides and / or diamine compounds are used, for example, when two types of tetracarboxylic dianhydrides and two types of diamine compounds are used, the following formula (II): [Mw(P1)×a 1 +Mw(P2)×a 2 +Mw(Q1)×b 1 +Mw(Q2)×b 2 / [Mw(A1)×a 1 +Mw(A2)×a 2 +Mw(B1)×b 1 +Mw(B2)×b 2 -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, and a 1 represents the content ratio of the first tetracarboxylic dianhydride, and a 2 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, and b 1 represents the content ratio of the first diamine compound, and b 2 represents the content ratio of the second diamine compound. Also, a 1 and a 2 and b 1 and b 2 respectively satisfy a 1 + a 2 = 1 and b 1 + b 2 = 1. It is represented by {}. When three or more types of tetracarboxylic dianhydrides and / or diamine compounds are used, it is similarly required. When tetracarboxylic acid and / or tetracarboxylic acid chloride are used as raw materials, the molecular weight of the corresponding tetracarboxylic dianhydride is used for calculation.

[0027] (Condition 2) It is also preferable that the polyimide precursor resin satisfies both of the following at least two conditions (2-i) and (2-ii). In the polyimide of a polyimide cured film obtained by heating and curing a (2-i) photosensitive resin composition at 350 °C, with respect to the molecular weight of the repeating unit containing the structures derived from the tetracarboxylic dianhydride and the diamine compound, the aliphatic hydrocarbon group concentration T, which is the ratio occupied by the total molecular weight of the aliphatic hydrocarbon groups, and the photosensitive group concentration S, which is the ratio occupied by the total molecular weight of the photosensitive groups with respect to the molecular weight of the repeating unit in the (A) polyimide precursor resin, satisfy the following general formula (1): -77 ≦ 4T - 3S ≦ 44 (1) (2-ii) The (A) polyimide precursor resin has, at the resin terminal, another reactive unsaturated bond structure that polymerizes by heat or light, which is different from the reactive unsaturated bond side chain contained in the repeating unit.

[0028] The aliphatic hydrocarbon group concentration T described in condition (2-i) has the same definition as the aliphatic hydrocarbon group concentration described in the above condition (1-ii). By the polyimide precursor satisfying these conditions (2-i) and (2-ii), a negative-type photosensitive resin composition having low dielectric properties, low moisture permeability, and good chemical resistance and high resolution can be obtained.

[0029] The photosensitive group concentration S is calculated using the molecular weights of the tetracarboxylic dianhydride and the diamine compound used during the preparation of the polyimide precursor, according to 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 the 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.} In addition, when two or more types of tetracarboxylic dianhydrides and / or diamine compounds are used, calculations are performed according to the ratio of the raw materials, in the same manner as the definition of the above aliphatic hydrocarbon group concentration T. Also, in the case of a copolymer of a photopolymerizable group-containing compound and a compound not containing a photopolymerizable group, the following formula (II): [Mw(R) × c 1 / [Mw(A) + Mw(B) + Mw(R) × c 1+Mw(S)×c 2 -36]×100 (II) {In formula (II), Mw(R) represents the sum of the molecular weights of the photopolymerizable group-containing compounds, Mw(S) represents the sum of the molecular weights of the compounds not containing a photopolymerizable group, Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine compound. c 1 represents the content of the photopolymerizable group-containing compound, c 2 represents the content of the compound not containing a photopolymerizable group, and also, c 1 c 2 each represents c 1 +c 2 = 1 is satisfied.}. When tetracarboxylic acid and / or tetracarboxylic acid chloride is used as a raw material, it is calculated using the molecular weight of the corresponding tetracarboxylic dianhydride.

[0030] (A) The polyimide precursor resin is different from the reactive unsaturated bond side chains contained in the repeating unit and is preferably at least one selected from, for example, an unsaturated bond structure that polymerizes with heat or light, such as a (meth)acrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, and an ethynyl group. From the viewpoint of low dielectric characteristics, the unsaturated bond structure is preferably at least one selected from a (meth)acrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, and a styryl group, and from the viewpoint of chemical resistance, a (meth)acrylic group is more preferable. These unsaturated bond structures may be bonded to either the structure derived from the tetracarboxylic dianhydride or the diamine compound used in the preparation of the polyimide precursor.

[0031] As the structure derived from the tetracarboxylic dianhydride, for example, an unsaturated bond structure is introduced via an imide group, an amide group, or an ester group. Further, as the structure derived from the diamine compound, for example, an unsaturated bond structure is introduced via a urea group or an amide group. Among these bonds, an imide group and a urea group are preferable from the viewpoint of low dielectric characteristics.

[0032] (A) Examples of the polyimide precursor include polyamide precursors having a structural unit represented by the following general formula (4). [Chemical formula] {In the formula, X 1 is a tetravalent organic group having 6 to 40 carbon atoms, Y 1 is a divalent organic group having 6 to 40 carbon atoms, n 1 is an integer of 2 to 150, and R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R 4 and R 5 is a group represented by the following general formula (5).} [Chemical formula] {In the formula, R 6 , R 7 and R 8 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m 2 is an integer of 2 to 10.} Incidentally, R 4 and R 5 in the general formula (4) are also referred to as the side chain or side chain structure of the polyimide precursor. R 6 in the above general formula (5) is preferably a hydrogen atom or a methyl group, and R 7 and R 8 are preferably hydrogen atoms from the viewpoint of photosensitive characteristics. Also, m 2 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitive characteristics.

[0033] From the viewpoints of resolution and low dielectric constant characteristics, the ratio of the photosensitive groups per repeating unit in the polyimide precursor resin is preferably 15 wt% to 35 wt%. From the viewpoint of dielectric constant characteristics, it is preferable that the number of photosensitive groups is small, and from the viewpoint of resolution, it is preferable that the number of photosensitive groups is large. In the present specification, the "ratio of photosensitive groups" has the same definition as the photosensitive group concentration S described in condition (2-i), and means the ratio of the molecular weight of the photopolymerizable group-containing compound constituting the repeating unit based on the molecular weight of the repeating unit. Examples of the photopolymerizable group include an unsaturated double bond.

[0034] n in the above general formula (4) 1 is preferably an integer of 3 to 100, more preferably an integer of 5 to 70, from the viewpoints of the photosensitive characteristics and mechanical characteristics of the photosensitive resin composition.

[0035] In the above general formula (4), X 1 The tetravalent organic group represented by is preferably an organic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive characteristics, and more preferably a -COOR 1 group and a -COOR 2 group and a -CONH- group are aromatic groups or alicyclic aliphatic groups in ortho positions to each other. As the tetravalent organic group represented by X 1 , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (7):

Chemical formula

[0036] In the general formula (7) above, Y 1 The divalent organic group represented by is preferably an aromatic group having 6 to 40 carbon atoms in that it achieves both heat resistance and photosensitive properties. For example, the following general formula (8):

Chemical formula

[0037] X of the (A) polyimide precursor resin described in the general formula (4) above 1 and / or Y 1 preferably contains the structure represented by the following general formula (6) from the viewpoints of resolution, moisture permeability, and low dielectric constant properties.

Chemical formula

[0038] By including the structure of the above general formula (6), the resolution of the relief pattern is good, and a cured film with low moisture permeability can be obtained. By introducing an alkyl chain into the aromatic ring, the solubility of the polyimide precursor in the developer is improved, the contrast with the exposed area is easily ensured, and the resolution of the relief pattern is improved. Further, by introducing an organic group into the aromatic ring, the hydrophobicity of the film is increased and it becomes difficult for moisture to permeate.

[0039] The structure of the above general formula (6) is not limited, but as an example, it preferably includes at least one structure selected from the group consisting of the following general formula (9).

Chemical formula

[0040] In the above general formula (4), X 1 The structure represented by is preferably included in at least one structure selected from the group consisting of the following general formula (10).

Chemical formula

[0041] In the above general formula (4), Y 1 The structure represented by is preferably included in at least one structure selected from the group consisting of the following general formula (11).

Chemical formula

[0042] (A) In the polyimide precursor, X 1 , which is a skeletal component derived from a tetracarboxylic acid compound, or Y 1It is preferable that at least one of them has a structure in which two or more benzene rings are bonded. The number of benzene rings may be 3 or more, 4 or more, 6 or less, 5 or less, or 4 or less, and more preferably 4. When the (A) polyimide precursor has such a structure, the resolution of the negative photosensitive resin composition is maintained, and the cured relief pattern obtained tends to have low dielectric characteristics.

[0043] [Preparation method of (A) polyimide precursor] (Formation of reactive terminal structure) As a method for forming a terminal structure having a reactive substituent at the main chain terminal of the polyimide precursor resin, the following steps: (i) React a first compound having a reactive substituent that reacts with heat or light with a tetracarboxylic dianhydride to generate a first compound introduction part and a carboxyl group, and then react with a second compound having a reactive substituent that reacts with heat or light different from the first compound, or react a second compound having a reactive substituent that reacts with heat or light with a tetracarboxylic dianhydride to generate a second compound introduction part and a carboxyl group, and then react with a first compound having a reactive substituent that reacts with heat or light different from the second compound, thereby obtaining an acid component monomer having a second compound introduction part, and / or (ii) React a second compound having a reactive substituent that reacts with heat or light with a diamine compound to obtain a diamine monomer having a second compound introduction part, By (i) and / or (ii) above, a monomer adjustment step of obtaining an acid component monomer and / or a diamine monomer having the second compound introduction part, A polymerization step of synthesizing a polyimide precursor by subjecting an acid component monomer and / or a diamine monomer having the above second compound introduction portion, a tetracarboxylic dianhydride, and a diamine compound to a condensation reaction is preferred. As described above, by using a synthesis method (hereinafter also referred to as "pre-sealing") in which a second compound is introduced into a tetracarboxylic dianhydride and / or a diamine compound before polymerizing the polyimide precursor, (A) the polyimide precursor resin can have a reactive substituent derived from the second compound at the main chain terminal. Examples of the first compound include alcohols having a photopolymerizable group, and examples of the second compound include isocyanate compounds having a photopolymerizable group.

[0044] (Preparation of acid / ester form) A tetravalent organic group X having 6 to 40 carbon atoms, which is preferably used for preparing an ester bond type polyimide precursor 1 Examples of the tetracarboxylic dianhydride having the group X include, in addition to the tetracarboxylic dianhydrides derived from the structures listed above, for example, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, 4,4'-(4,4'-isopropylidenediphenoxy)dianhydride phthalic acid, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, etc. can be mentioned, but are not limited thereto. Also, these can of course be used alone, or two or more of them can be mixed and used.

[0045] These tetravalent organic groups X having 6 to 40 carbon atoms 1Using a tetracarboxylic dianhydride containing the same, the terminal structure is formed by using the above introduction method 1 or introduction method 2. The order of the reaction varies depending on the introduction method.

[0046] Synthesis of an esterified tetracarboxylic acid having a reactive terminal represented by the above general formulas (1) to (3), and a compound having a photopolymerizable group (corresponding to the above "second compound") preferably used for introducing an unsaturated bond structure via a urea bond or an amide bond derived from a diamine compound includes 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, allylamine, methacrylic acid chloride, 5-norbornene-2-methylamine, 4-vinyl aniline, and the like. Further, examples of the alcohols having a photopolymerizable group (corresponding to the above "first compound") include 2-hydroxyethyl methacrylate (HEMA), 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.

[0047] As saturated aliphatic alcohols that can be optionally used together with the alcohols having the above photopolymerizable groups, saturated aliphatic alcohols having 1 to 4 carbon atoms are preferred. Specific examples thereof include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.

[0048] The above tetracarboxylic dianhydride and alcohols are preferably stirred and mixed at a temperature of 20 to 50 ° C for 4 to 10 hours in the presence of a basic catalyst such as pyridine, preferably in a suitable reaction solvent, whereby the esterification reaction of the acid anhydride proceeds and a desired acid / ester form can be obtained.

[0049] As the above reaction solvent, those that can completely dissolve the raw material tetracarboxylic dianhydride and alcohols, as well as the acid / ester form as the product, are preferred. More preferably, it is a solvent that can also completely dissolve the polyimide precursor, which is an amide polycondensation product of the acid / ester form and diamine. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can be mentioned. Specific examples thereof include As ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like can be mentioned. As esters, for example, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate and the like can be mentioned. As lactones, for example, γ-butyrolactone and the like can be mentioned. As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like can be mentioned. As halogenated hydrocarbons, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene and the like can be mentioned. As hydrocarbons, for example, hexane, heptane, benzene, toluene, xylene and the like can be mentioned. These may be used alone or in combination of two or more as necessary.

[0050] (Preparation of Polyimide Precursor) To the above acid / ester compound (typically in a solution state dissolved in the above reaction solvent), preferably under ice-cooling, a suitable dehydrating condensing agent is added and mixed to convert the acid / ester compound into a polyacid anhydride. Then, diamines containing a divalent organic group Y having 6 to 40 carbon atoms 1 dissolved or dispersed separately in a solvent are added dropwise, and the two are subjected to amide polycondensation to obtain the target polyimide precursor. The diamines having the above divalent organic group Y 1 may be used in combination with diaminosiloxanes. Examples of the above dehydrating condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and the like. In the above manner, a polyacid anhydride as an intermediate is obtained.

[0051] The divalent organic group Y having 6 to 40 carbon atoms, which is preferably used for the reaction with the polyacid anhydride obtained as described above 1Examples of diamines having it include, in addition to 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 those in which some of the hydrogen atoms on these benzene rings are substituted with an alkyl chain such as a methyl group or an ethyl group, for example, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichlorodiphenyl-4,4'-diamine, and their mixtures, etc. may also be mentioned. However, diamines are not limited to these. Of course, these can be used alone, and two or more of them may be mixed and used.,

[0052] In order to improve the adhesion between the photosensitive resin layer formed on the substrate by applying the photosensitive resin composition on the substrate and various substrates, during the preparation of the (A) polyimide precursor, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized.

[0053] After the amide polycondensation reaction is completed, the water-absorbing by-products of the dehydrating condensing agent coexisting in the reaction solution are filtered off if necessary, and then a poor solvent suitable for the solution containing the polymer component, such as water, lower aliphatic alcohol, a mixture thereof, etc., is added to precipitate the polymer component. Further, if necessary, operations such as redissolution and reprecipitation operations are repeated to purify the polymer, and then vacuum drying is performed to isolate the target polyimide precursor. In order to improve the degree of purification, the solution of this polymer may be passed through a column filled with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0054] (A) The weight-average molecular weight of the polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000 when measured by polystyrene-equivalent weight-average molecular weight using gel permeation chromatography (GPC) from the viewpoints of the heat resistance and mechanical properties of the film obtained after heat treatment. If the weight-average molecular weight is 8,000 or more, it is preferable because the mechanical properties are good. On the other hand, if it is 150,000 or less, it is preferable because the dispersibility in the developer and the resolution performance of the relief pattern are good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0055] [(B) Photoinitiator] (B) The photoinitiator is a compound that can generate radicals by actinic rays and polymerize compounds containing ethylenically unsaturated groups and the like. Examples of initiators that generate radicals by actinic rays include compounds containing structures such as benzophenone, N-alkylaminoacetophenone, oxime ester, acridine, and phosphine oxide.Examples thereof include aromatic ketones such as benzophenone, N,N,N’,N’-tetramethyl-4,4’-diaminobenzophenone (Michler's ketone), N,N,N’,N’-tetraethyl-4,4’-diaminobenzophenone, 4-methoxy-4’-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, acrylated benzophenone, 4-benzoyl-4’-methyldiphenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetoxyoxime) (manufactured by BASF Japan Ltd., Irgacure Oxe02), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (manufactured by Joushou Strong Electronic Materials Co., Ltd., PBG305), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetoxyoxime) (manufactured by Nikko Chemtech Co., Ltd., TR-PBG-326, product name); benzyl derivatives such as benzyldimethylketal; acridine derivatives such as 9-phenylacridine, 1,7-bis(9,9’-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, but are not limited thereto. The (C) polymerization initiator described above can be used alone or in combination of two or more. Among the above photoinitiators, oxime ester compounds are more preferable particularly from the viewpoint of resolution. Among these, it is particularly preferable that the radical species is derived from a methyl group.

[0056] The compounding amount of the photoinitiator is 0.5 parts by mass or more and 10 parts by mass or less, preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. The above compounding amount is 0.5 parts by mass or more from the viewpoint of photosensitivity or patterning property, and on the other hand, it is preferably 10 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0057] [(C) Solvent] (C) The solvent is not limited as long as it can uniformly dissolve or suspend the (A) polyimide precursor and the (B) photoinitiator. Examples of such solvents include γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, N,N-dimethylacetoacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, etc. These solvents may be used alone or in combination of two or more.

[0058] The above solvent can be used in the range of, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, based on 100 parts by mass of the (A) polyimide precursor, according to the desired coating film thickness and viscosity of the photosensitive resin composition. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the above content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition becomes good, and when it is 50% by mass or less, the solubility of the (A) polyimide precursor becomes good.

[0059] [(D) Silane coupling agent] In order to improve the adhesion of the relief pattern, the photosensitive resin composition may optionally contain a (D) silane coupling agent. The (D) silane coupling agent preferably has a structure represented by the following general formula (12). [Chemical formula] {In the formula, R 12 is at least one selected from the group consisting of substituents containing an epoxy group, a phenylamino group, a urea group, an isocyanuric group, and a ureido group, and R 13 are each independently an alkyl group having 1 to 4 carbon atoms, R 14 is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, d is an integer of 1 to 3, and m 8 is an integer of 1 to 6.}

[0060] In the general formula (12), d is not limited as long as it is an integer of 1 to 3, but from the viewpoint of adhesion to the metal rewiring layer, etc., 2 or 3 is preferable, and 3 is more preferable. m 8 is not limited as long as it is an integer of 1 to 6, but from the viewpoint of adhesion to the metal rewiring layer, 1 or more and 4 or less is preferable. From the viewpoint of developability, 2 or more and 5 or less is preferable.

[0061] R 12 is not limited as long as it is a substituent containing any structure 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 viewpoints of developability and adhesion to the metal rewiring layer, it is preferably at least one selected from the group consisting of a substituent containing a phenylamino group, a substituent containing a urea group, and a substituent containing a ureido group, and a substituent containing a phenylamino group is more preferable. R 13 is not limited as long as it is an alkyl group having 1 to 4 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, etc. R 14 is not limited as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. As the alkyl group having 1 to 4 carbon atoms, the same alkyl groups as R 13 can be exemplified.

[0062] Examples of the silane coupling agent containing an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like. Examples of the silane coupling agent containing a phenylamino group include N-phenyl-3-aminopropyltrimethoxysilane. Examples of the silane coupling agent containing a ureido group include 3-ureidopropyltrialkoxysilane. Examples of the silane coupling agent containing an isocyanate group include 3-isocyanatopropyltriethoxysilane.

[0063] [(E) Radical polymerizable compound] In order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain an (E) radically polymerizable compound. Such compounds are preferably (meth)acrylic compounds that undergo a radical polymerization reaction with a photoinitiator, and particularly include, but are not limited to, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and other mono- or di-acrylates or methacrylates of ethylene glycol or polyethylene glycol, mono- or di-acrylates or methacrylates of propylene glycol or polypropylene glycol, mono-, di- or tri-acrylates or methacrylates of glycerol, cyclohexane diacrylate or dimethacrylate, 1,4-butanediol diacrylate or dimethacrylate, 1,6-hexanediol diacrylate or dimethacrylate, neopentyl glycol diacrylate or dimethacrylate, mono- or di-acrylates or methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate or methacrylate, acrylamide, its derivatives, methacrylamide, its derivatives, trimethylolpropane triacrylate or methacrylate, di- or tri-acrylates or methacrylates of glycerol, di-, tri- or tetra-acrylates or methacrylates of pentaerythritol, and compounds such as ethylene oxide or propylene oxide adducts of these compounds. These monomers may be used alone or as a mixture of two or more.

[0064] The blending amount of the compound having an ethylenically unsaturated double bond is 0.5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0065] [(F) Thermal crosslinking agent] In order to improve the chemical resistance of the cured film, the photosensitive resin composition may optionally contain an (F) thermal crosslinking agent.

[0066] (F) A thermosetting agent means a compound that undergoes an addition reaction or a condensation polymerization reaction by heat. These reactions occur in combinations of (A) resin and (F) thermosetting agent, (F) thermosetting agents with each other, and (F) thermosetting agent and other components described later. As the reaction temperature, 150°C or higher is preferable.

[0067] (F) It is preferable that the thermosetting agent contains a nitrogen atom. Thereby, the interaction with the polyimide resin is enhanced, and higher chemical resistance can be expected. Examples of the (F) thermosetting agent include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds.

[0068] Examples of the alkoxymethyl compound include, but are not limited to, the following compounds.

Chemical formula

Chemical formula

[0069] Examples of epoxy compounds include epoxy compounds containing bisphenol A type groups, hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.), and the like. Examples of oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4′-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3-ethyl-3-oxetanylmethyl)diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silsesquioxane] derivative, oxetanyl silicate, phenol novolac type oxetane, 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei Co., Ltd., trade name), OXT221 (manufactured by Toagosei Co., Ltd., trade name), and the like. Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylene bis(maleimide), 4-methyl-N,N'-1,3-phenylene bis(maleimide), N,N'-1,4-phenylene bis(maleimide), 3-methyl-N,N'-1,4-phenylene bis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.Examples of allyl compounds include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allylphenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, triallyl citrate, and the like. Examples of blocked isocyanate compounds include hexamethylene diisocyanate-based blocked isocyanates (for example, Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation; Takenate B-882N manufactured by Mitsui Chemicals, Inc.; 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), tolylene diisocyanate-based blocked isocyanates (for example, Takenate B-830 manufactured by Mitsui Chemicals, Inc.), 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (for example, Takenate B-815N manufactured by Mitsui Chemicals, Inc.; Bronate PMD-OA01 and PMD-MA01 manufactured by Daiwing Sangyo Co., Ltd.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (for example, Takenate B-846N manufactured by Mitsui Chemicals, Inc.; Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), isophorone diisocyanate-based blocked isocyanates (for example, 7950, 7951, and 7990 manufactured by Baxenden). Among these, from the viewpoint of storage stability, blocked isocyanates and bismaleimide compounds are preferred. (F) The thermal crosslinking agent may be used alone or in combination of two or more kinds.

[0070] The content of the (F) thermal crosslinking agent in the resin composition is 0.2% by mass to 40% by mass based on the total solid mass of the resin composition. From the viewpoints of low dielectric properties and chemical resistance, it is more preferably 1% by mass to 20% by mass, and even more preferably 2% by mass to 10% by mass.

[0071] [(G) filler] In order to improve the chemical resistance of the cured film, the photosensitive resin composition can optionally contain a (G) filler. The filler is not limited as long as it is an inert substance added to improve strength and various properties.

[0072] The filler is preferably particulate from the viewpoint of suppressing the increase in viscosity when forming the resin composition. Examples of particulate forms include acicular, plate-like, spherical, etc. From the viewpoint of suppressing the increase in viscosity when forming the resin composition, the filler is preferably spherical.

[0073] Examples of acicular fillers include wollastonite, potassium titanate, zonnolite, aluminum borate, acicular calcium carbonate, etc.

[0074] Examples of plate-like fillers include talc, mica, sericite, glass flake, montmorillonite, boron nitride, plate-like calcium carbonate, etc.

[0075] Examples of spherical fillers include calcium carbonate, silica, alumina, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, barium titanate, etc. Among these, from the viewpoints of electrical properties and storage stability when forming the resin composition, silica, alumina, titanium oxide, and barium titanate are preferred, and silica and alumina are more preferred.

[0076] As the size of the filler, in the case of spherical shape, the primary particle diameter is defined as the size, and in the case of plate-like or needle-like shape, the length of the long side is defined as the size. 5 nm to 1000 nm is preferable, and 10 nm to 1000 nm is more preferable. If it is 10 nm or more, it tends to be sufficiently uniform when made into a resin composition, and if it is 1000 nm or less, photosensitivity can be imparted. From the viewpoint of imparting photosensitivity, 800 nm or less is preferable, 600 nm or less is more preferable, and 300 nm or less is particularly preferable. From the viewpoints of adhesion and resin composition uniformity, 15 nm or more is preferable, 30 nm or more is more preferable, and 50 nm or more is particularly preferable.

[0077] The content of the (G) filler in the resin composition is 1 vol% to 20 vol% based on the mass of the resin composition. From the viewpoint of dielectric properties, it is preferably 5 vol% to 20 vol%, and from the viewpoint of resolution, it is more preferably 5 vol% to 10 vol%.

[0078] [Other Components] The photosensitive resin composition may further contain components other than the above components (A) to (G). Examples of other components include resin components other than the (A) polyimide precursor; organic compounds containing metal elements, sensitizers, thermal polymerization inhibitors, azole compounds, and hindered phenol compounds.

[0079] The photosensitive resin composition may further contain a resin component other than the (A) polyimide precursor. Examples of the resin components that can be contained in the photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, acrylic resin, etc. The blending amount of these resin components is preferably in the range of 0.01 part by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0080] 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. As the organic group, it preferably includes a hydrocarbon group and a hydrocarbon group containing a heteroatom. By containing the organic compound, the imidization rate of the polyimide precursor contained in the photosensitive resin composition increases, and the dielectric tangent of the cured film decreases. Examples of usable organic titanium or zirconium compounds include those in which an organic group is bonded to a titanium atom or a zirconium atom via a covalent bond or an ionic bond.

[0081] Specific examples of the organic titanium or zirconium compound are shown in the following I) to VII): I) As the chelate compound, a compound having two or more alkoxy groups is more preferable because the storage stability of the photosensitive resin composition and a good pattern can be obtained. Specific examples of the chelate compound include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), and compounds in which the titanium atom of these compounds is replaced with a zirconium atom, but are not limited thereto.

[0082] II) Examples of the tetraalkoxy compound include, but are not limited to, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetrastearate, titanium tetrakis[bisd{2,2-(allyloxymethyl)butoxide}], and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0083] III) Examples of the titanocene or zirconocene compound include, but are not limited to, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0084] IV) Examples of the monoalkoxy compound include, but are not limited to, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0085] V) Examples of the titanium oxide or zirconium oxide compound include, but are not limited to, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0086] VI) Examples of the titanium tetraacetylacetonate or zirconium tetraacetylacetonate compound include, but are not limited to, titanium tetraacetylacetonate and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0087] VII) Examples of the titanate coupling agent include, but are not limited to, isopropyltridodecylbenzenesulfonyl titanate.

[0088] Among the above I) to VII), it is preferable that the organotitanium compound is at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound from the viewpoint of exhibiting 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 are preferable.

[0089] When the organotitanium or zirconium compound is blended, the blending amount is 0.01 part by mass to 5 parts by mass, preferably 0.1 part by mass to 3 parts by mass, based on 100 parts by mass of the (A) resin. If the blending amount is 0.01 part by mass or more, the imidization rate of the good resin composition and the dielectric tangent of the cured film are exhibited. On the other hand, if it is 10 parts by mass or less, it is preferable because of excellent storage stability.

[0090] The photosensitive resin composition can improve the imidization rate of the polyimide precursor contained in the resin composition and reduce the dielectric loss tangent of the cured film using the resin composition by containing an organic compound containing the above metal element. Although not bound by theory, as a reason for improving the imidization rate of the polyimide precursor, it is considered 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.

[0091] The photosensitive resin composition can optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combination of two or more (for example, 2 to 5 types). The blending amount of the sensitizer is preferably 0.1 part by mass to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0092] The photosensitive resin composition can optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, particularly during storage in the state of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, and the like. Further, these thermal polymerization inhibitors may be used singly or as a mixture of two or more. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0093] When using a substrate made of copper or a copper alloy, the photosensitive resin composition can optionally contain an azole compound in order to suppress substrate discoloration. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or as a mixture of two or more.

[0094] The compounding amount of the azole compound is preferably 0.1 part by mass to 20 parts by mass, more preferably 0.5 part by mass to 5 parts by mass, based on 100 parts by mass of the (A) polyimide precursor. When the compounding amount of the azole compound based on 100 parts by mass of the (A) polyimide precursor is 0.1 part by mass or more, discoloration of the surface of copper or a copper alloy is suppressed when the photosensitive resin composition is formed on copper or a copper alloy. On the other hand, when it is 20 parts by mass or less, it is preferable because of excellent photosensitivity.

[0095] When using a substrate made of copper or a copper alloy, the photosensitive resin composition can contain a hindered phenol compound to suppress substrate discoloration. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like can be mentioned, but are not limited thereto. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.,

[0096] The compounding amount of the hindered phenol compound is preferably 0.1 part by mass to 20 parts by mass, more preferably 0.5 part by mass to 10 parts by mass, based on 100 parts by mass of the polyimide precursor (A). When the compounding amount of the hindered phenol compound relative to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, for example, when a photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented. On the other hand, when it is 20 parts by mass or less, it is preferable because of excellent photosensitivity.

[0097] <Polyimide cured film and method for producing the same> The present disclosure also provides a method for producing a polyimide cured film, including a step of converting a photosensitive resin composition into polyimide. The method for producing a polyimide cured film of the present disclosure includes, for example, the following steps (1) to (5): (1) A step of applying the photosensitive resin composition of the present disclosure on a substrate to form a photosensitive resin layer on the substrate; (2) A step of heating and drying the obtained photosensitive resin layer; (3) A step of exposing the photosensitive resin layer after heating and drying; (4) A step of developing the photosensitive resin layer after exposure; and (5) A step of heat-treating the photosensitive resin layer after development to form a polyimide cured film; is included.

[0098] The photosensitive resin composition used in the method for producing a cured film preferably contains 100 parts by mass of a polyimide precursor, 0.5 to 10 parts by mass of a photosensitizer, and 100 to 300 parts by mass of a solvent, more preferably contains a photo radical polymerization initiator as the photosensitizer, and still more preferably the photosensitive resin composition is a negative type.

[0099] The specific steps in the method for producing a cured film can be carried out according to the steps (1) to (5) of the method for producing a cured film described above. Hereinafter, typical embodiments of each step will be described.

[0100] (1) A step of applying the photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate In this process, the photosensitive resin composition of the present disclosure is applied onto a substrate, and if necessary, dried thereafter to form a photosensitive resin layer. As the coating method, methods conventionally used for coating photosensitive resin compositions, for example, methods of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc., methods of spray coating with a spray coater, etc. can be used.

[0101] (2) Step of heating and drying the obtained photosensitive resin layer If necessary, the photosensitive resin composition film can be heated and dried. As the drying method, methods such as air drying, heat drying by an oven or a hot plate, vacuum drying, etc. are used. Also, it is desirable to carry out the drying of the coating film under conditions such that imidization of the (A) polyimide precursor (polyamic acid ester) in the photosensitive resin composition does not occur. Specifically, when performing air drying or heat drying, drying can be carried out under conditions of 20°C to 140°C for 1 minute to 1 hour. Thus, a photosensitive resin layer can be formed on the substrate.

[0102] (3) Step of exposing the photosensitive resin layer after heating and drying In this process, the photosensitive resin layer formed above is exposed. As the exposure apparatus, for example, exposure apparatuses such as a contact aligner, a mirror projection, a stepper, etc. are used. Exposure can be carried out through a photomask or reticle having a pattern, or directly. The light rays used for exposure are, for example, an ultraviolet light source, etc.

[0103] After exposure, for the purpose of improving photosensitivity, etc., if necessary, post-exposure bake (PEB) and / or pre-development bake may be performed with an arbitrary combination of temperature and time. The range of the bake conditions is preferably a temperature of 40 to 120°C and a time of 10 seconds to 240 seconds, but is not limited to this range as long as it does not inhibit the various properties of the negative-type photosensitive resin composition of this embodiment.

[0104] (4) Step of developing the photosensitive resin layer after exposure In this process, the photosensitive resin layer after exposure is developed to form a relief pattern. When the photosensitive resin composition is a negative type, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), an arbitrarily selected method can be used from conventionally known photoresist developing methods, for example, the spin spray method, the paddle method, the dipping method with ultrasonic treatment, etc. Further, after development, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking may be performed as needed at an arbitrary combination of temperature and time. As the developer used for development, for example, a good solvent for the negative type photosensitive resin composition, or a combination of the good solvent and a poor solvent is preferable. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water, etc. are preferable. When the good solvent and the poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative type photosensitive resin composition. Also, two or more kinds of each solvent, for example, several kinds can be combined and used. In the step of developing the photosensitive resin layer after exposure, it is preferable to perform the above coating - developing step so that a photosensitive resin layer with a film thickness of 10 μm to 15 μm is obtained. The development time is preferably 30 seconds or less, more preferably 25 seconds or less, and even more preferably 20 seconds or less. Although not bound by theory, when the development time is 30 seconds or less, a contrast is obtained due to the difference in solubility with the exposed portion, and the resolution of the pattern is improved.

[0105] (5) Step of heat-treating the photosensitive resin layer after development to form a polyimide cured film In this process, the relief pattern obtained by the above development is heated to disperse the photosensitive component, and (A) the polyimide precursor is imidized to be converted into a cured relief pattern made of polyimide. As the method of heat curing, various methods can be selected, such as those using a hot plate, those using an oven, and those using a temperature-programmable heating oven. The heating can be carried out, for example, under the conditions of 160 °C to 400 °C for 30 minutes to 5 hours. As the atmospheric gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may be used. In this way, a cured relief pattern (polyimide cured film) can be manufactured.

[0106] The method for manufacturing a polyimide cured film of the present disclosure is, for example, a method for manufacturing a cured film including coating the photosensitive resin composition of the present disclosure on a substrate, performing an exposure process, a development process, and then a heat treatment. The cured film preferably has a dielectric loss tangent of 0.003 to 0.012 when measured at 40 GHz by the perturbation method split cylinder resonator method. The dielectric loss tangent can be measured by the perturbation method split cylinder resonator method shown in the examples described later.

[0107] The present disclosure also provides a polyimide cured film obtained from the photosensitive resin composition described above. The cured film preferably has a water vapor transmission rate of less than 800, and more preferably less than 700. From the perspective of the dielectric loss tangent, the lower the water vapor transmission rate, the better the tendency for the frequency dependence of the dielectric loss tangent to be less. On the other hand, from the perspective of resolution, the lower the water vapor transmission rate, the worse the solubility of the unexposed portion during patterning, and the resolution deteriorates. Therefore, it is more preferably 500 or more and less than 800. By being less than 800, a highly reliable cured film can be obtained. For details of the method for measuring the water vapor transmission rate, refer to the following description. From the perspectives of resolution, dielectric properties, and frequency dependence in the dielectric loss tangent, it is preferable that the product (tanδ 40 ×WVTR) is within a certain range. When using the value of the dielectric loss tangent at 40 GHz, the following formula (2): 3.0 < tanδ 40 ×WVTR < 10.0 (2) It is preferable to satisfy. tanδ 40 When tanδ × WVTR is in the range of 3.0 to 10.0, a polyimide cured product excellent in resolution and dielectric properties and having little frequency dependence can be obtained. The difference in dielectric tangent at 40 GHz and 10 GHz is preferably 0.0015 or less, and preferably 0.001 or less.

[0108] From the viewpoint of achieving both low dielectric tangent and chemical resistance, the polyimide cured film obtained in the present disclosure further has the product of the dielectric tangent, the moisture vapor transmission rate, and the dissolution rate of the cured film dissolved in the chemical solution during the chemical resistance test (tanδ 40 × WVTR × DR) in a certain range. When the value of the dielectric tangent at 40 GHz is used, the following formula (3): 4.0 < tanδ 40 × WVTR × DR < 29.0 (3) It is preferable to satisfy. tanδ 40 When tanδ × WVTR × DR is in the range of 4.0 to 29.0, a polyimide cured product excellent in dielectric properties and chemical resistance and having little frequency dependence can be obtained.

[0109] <Semiconductor device> The present disclosure can also provide a semiconductor device having a cured relief pattern obtained by the above-described method for manufacturing a cured relief pattern using the photosensitive resin composition of the present disclosure. Therefore, a semiconductor device 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 manufacturing a cured relief pattern is provided. Further, the present disclosure can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern as part of a process. The semiconductor device can be manufactured by forming the cured relief pattern formed by the above-described method for manufacturing a cured relief pattern as a surface protection film, an interlayer insulating film, a rewiring insulating film, a protection film for a flip chip device, or a protection film for a semiconductor device having a bump structure, and combining it with a known method for manufacturing a semiconductor device.

[0110] The polyimide contained in the cured relief pattern (polyimide cured film) formed from the above polyimide precursor composition has the following general formula (13): [Chemical Formula] {In general formula (13), X 1 and Y 1 are the same as X 1 and Y 1 in the above general formula (4), and n 2 is an integer of 2 to 150.} It preferably has a structure represented by

[0111] <Display device> The present disclosure can also provide a display device including a display element and a cured film provided on top of the display element, using the photosensitive resin composition of the present disclosure, wherein the cured film is the above-described cured relief pattern. Here, the cured relief pattern may be laminated directly in contact with the display element, or may be laminated with another layer interposed therebetween. For example, 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 partitions for organic EL element cathodes.

[0112] In addition to the application to semiconductor devices as described above, the photosensitive resin composition of the present disclosure is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad laminates, solder resist films, and liquid crystal alignment films.

[0113] <Method for producing photosensitive resin composition> The method for producing the photosensitive resin composition of the present disclosure is a method for producing a resin composition containing (A) 100 parts by mass of a polyimide precursor, (B) 0.5 to 10 parts by mass of a photopolymerization initiator, and (C) 50 to 500 parts by mass of a solvent. The method includes a step of synthesizing the (A) polyimide precursor resin and a step of mixing the (A) polyimide precursor resin, the above (B) photopolymerization initiator, and (C) solvent within the range of the parts by mass described above to obtain a photosensitive resin composition. The synthesis step includes the following steps: (i) Reacting a tetracarboxylic dianhydride with a first compound having a reactive substituent that reacts with heat or light to produce a first compound-introduced moiety and a carboxyl group, and then reacting with a second compound having a reactive substituent that reacts with heat or light different from the first compound, or reacting a tetracarboxylic dianhydride with a second compound having a reactive substituent that reacts with heat or light to produce a second compound-introduced moiety and a carboxyl group, and then reacting with a first compound having a reactive substituent that reacts with heat or light different from the second compound, to obtain an acid component monomer having a second compound-introduced moiety, and / or (ii) Reacting a diamine compound with a second compound having a reactive substituent that reacts with heat or light to obtain a diamine monomer having a second compound-introduced moiety, Obtaining an acid component monomer and / or a diamine monomer having the second compound-introduced moiety by (i) and / or (ii) above, a monomer adjustment step, Condensing the acid component monomer and / or diamine monomer having the second compound-introduced moiety, a tetracarboxylic dianhydride, and a diamine compound to synthesize a polyimide precursor, a polymerization step, including.

[0114] As described above, by using a synthesis method (hereinafter also referred to as "pre-sealing") of introducing a second compound into a tetracarboxylic dianhydride and / or a diamine compound before polymerizing the polyimide precursor, (A) the polyimide precursor resin can have a reactive substituent derived from the second compound at the main chain terminal. In this production method, by reacting a compound having a desired structure with the raw material (monomer) before polymerization, the resin terminal can be formed more efficiently compared to the case of performing a capping reaction at the resin terminal after polymerization (hereinafter also referred to as "post-sealing").

[0115] In the present specification, the ratio of the molar number of reactive substituents bonded per unit molar amount of carboxylic acid groups derived from tetracarboxylic dianhydrides located at the main chain terminals of the polyimide precursor resin, or per unit molar amount of amine groups derived from diamine compounds located at the main chain terminals, is referred to as the "capping rate". The comparison of the capping rates can be carried out by 1 1H-NMR. That is, when the area of the peak of aromatic amide (around 10.0 ppm to 11.0 ppm) derived from the main chain is set to 1.0, the area of the proton peak of the polymerizable functional group (around 5.0 ppm to 6.5 ppm) derived from the terminal structure is defined as the "terminal capping value", and the capping rates can be compared by comparing these values. When proton peaks of polymerizable functional groups derived from the repeating structure or peaks unrelated to other polymerizable functional groups are confirmed in the vicinity of 5.0 ppm to 6.5 ppm where the proton peak of the polymerizable functional group derived from the terminal structure appears, these proton peaks are excluded from the calculation of the "terminal capping value".

[0116] When comparing pre-capping and post-capping, the pre-capping tends to have a higher peak intensity than the post-capping. The reason, although not limited to theory, is considered to be that in pre-capping, the reaction rate is high due to the reaction between monomers (low molecules), while in post-capping, the reaction rate is low because the active terminals are deactivated during polymerization or the reaction is between a polymer (high molecule) and a monomer (low molecule).

[0117] For example, Fig. 1 is an 1 example of 1H-NMR of a polyimide precursor resin in which the carboxylic acid groups derived from tetracarboxylic dianhydrides located at the main chain terminals are pre-capped. In the case of the 1H-NMR shown in Fig. 1, 1 when the area of the peak of aromatic amide at 10.4 ppm is set to 1.0, the areas of the proton peaks (symbol 1) of the polymerizable functional groups derived from the terminal structure around 5.7 ppm and around 6.1 ppm are calculated as the terminal capping values. Since proton peaks of polymerizable functional groups derived from the repeating structure (two peaks around 5.6 ppm and two peaks around 6.0 ppm) (symbol 2) are confirmed in the vicinity of the proton peak of the polymerizable functional group derived from the terminal structure, these proton peaks are excluded from the calculation of the "terminal capping value".

[0118] Figure 2 shows the comparison of 1H-NMR of the polyimide precursor resin when the amine group derived from the diamine compound located at the main chain end is pre-capped, post-capped, and not capped (unmodified). 1 In the case of the 1H-NMR shown in Figure 2, 1 also in the case of 1H-NMR, taking the area of the aromatic amide peak at 10.4 ppm as 1.0, the area of the proton peak (symbol 1) of the polymerizable functional group derived from the terminal structure near 5.7 ppm and 6.1 ppm is calculated as the terminal capping value. Near the proton peak of the polymerizable functional group derived from the terminal structure, proton peaks (two peaks around 5.6 ppm and two peaks around 6.0 ppm) (symbol 2) of the polymerizable functional group derived from the repeating structure, and a peak (6.3 ppm) unrelated to the polymerizable functional group are confirmed. Therefore, these proton peaks are excluded from the calculation of the "terminal capping value". Comparing pre-capping and post-capping, it can be seen that the peak intensity of pre-capping is higher than that of post-capping.

[0119] In the photosensitive resin composition of the present disclosure, (A) the polyimide precursor resin contains a terminal structure derived from a tetracarboxylic dianhydride at the end of the main chain, 1 by 1H-NMR, when taking the peak area of the amide group derived from the main chain structure as 1.0, the terminal capping value is preferably 0.02 or more, more preferably 0.04 or more, and still more preferably 0.06 or more. In the photosensitive resin composition of the present disclosure, (A) the polyimide precursor resin contains a terminal structure derived from a diamine at the end of the main chain, 1 by 1H-NMR, when taking the peak area of the amide group derived from the main chain structure as 1.0, the terminal capping value is preferably 0.06 or more, more preferably 0.07 or more, and still more preferably 0.08 or more. A high capping reaction rate means a high capping rate. Due to the high capping rate, the chemical resistance is improved under the synthesis conditions of excess tetracarboxylic dianhydride, and under the synthesis conditions of excess diamine, the deactivation of the reactive terminal during polymerization is suppressed, so the dielectric tangent is improved.

Examples

[0120] 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.

[0121] [Measurement and Evaluation Methods] (1) Weight-average molecular weight The weight-average molecular weight (Mw) of each photosensitive resin was measured by gel permeation chromatography (in terms of standard polystyrene). The columns used for the measurement were Shodex 805M / 806M in series manufactured by Showa Denko K.K., the standard monodisperse polystyrene was Shodex STANDARD SM-105 manufactured by Showa Denko K.K., the developing solvent was N-methyl-2-pyrrolidone, and the detector was Shodex RI-930 manufactured by Showa Denko K.K.

[0122] (2) Resolution and development time of the cured relief pattern on the Cu substrate On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625 ± 25 μm), 200 nm thick Ti and 400 nm thick Cu were sputtered in this order using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva Corporation). Subsequently, the photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and a photosensitive resin layer with a thickness of about 13.5 μm was formed by heating and drying on a hot plate at 110 °C for 3 minutes. On this photosensitive resin layer, using a mask with a test pattern, a plasma GHI (manufactured by Ultratech Inc.) equipped with an i-line filter was used to irradiate with 300 mJ / cm 2The energy was irradiated. Subsequently, this photosensitive resin layer was spray-developed using cyclopentanone as a developer with a coater developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The time of spray development at this time was defined as the development time. The wafer with the relief pattern formed on Cu was heat-treated at 230 °C for 2 hours in a nitrogen atmosphere using a temperature-rising program type curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured relief pattern made of a resin about 10 μm thick on Cu. The produced relief pattern was observed under an optical microscope to determine the size of the minimum opening pattern of the via. At this time, if the area of the opening of the obtained pattern was 1 / 2 or more of the corresponding pattern mask opening area, it was regarded as resolved, and the resolution was determined according to the following evaluation criteria based on the length of the mask opening side (the size of the opening pattern) corresponding to the one with the minimum area among the resolved openings. (Evaluation Criteria) A: The size of the minimum opening pattern is less than 10 μm B: The size of the minimum opening pattern is 10 μm or more and less than 15 μm C: The size of the minimum opening pattern is 15 μm or more and less than 20 μm D: The size of the minimum opening pattern is 20 μm or more

[0123] (3) Chemical Resistance Test On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625 ± 25 μm), 200 nm thick Ti and 400 nm thick Cu were sputtered in this order using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described later was spin-coated on this wafer using a coater developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and heated and dried on a hot plate at 110 °C for 3 minutes to form a photosensitive resin layer about 13.5 μm thick. On this photosensitive resin layer, using a mask with a test pattern, 500 mJ / cm was irradiated with a prism GHI (manufactured by Ultratech Inc.) equipped with an i-line filter. 2The wafer was irradiated with energy. Subsequently, the coating film formed on the wafer was spray-developed using cyclopentanone in a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan). Then, it was rinsed with propylene glycol methyl ether acetate to develop and remove the unexposed portion, thereby obtaining a relief pattern of the polyimide precursor. The wafer with the relief pattern formed thereon was heat-treated at 230 °C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured relief pattern made of a resin with a thickness of approximately 10 μm. The obtained polyimide pattern was immersed in a solution composed of 1 wt% potassium hydroxide, 39 wt% 3-methoxy-3-methyl-1-butanol, and 60 wt% dimethyl sulfoxide at 50 °C for 10 minutes. After washing with water and air-drying, the polyimide coating film was evaluated by measuring the film thickness and observing it under an optical microscope. The dissolution rate (DR) per unit time was calculated from the measured film thickness, and the chemical resistance of the coating film after immersion was determined according to the following evaluation criteria. (Evaluation Criteria) A: The film thickness variation of the coating film with respect to that before immersion is within ±3%, and no cracks are generated. B: The film thickness variation of the coating film with respect to that before immersion is within ±5%, and no cracks are generated. C: The film thickness variation of the coating film with respect to that before immersion is within ±7%, and no cracks are generated. D: The film thickness variation of the coating film with respect to that before immersion exceeds ±7%, or cracks are generated.

[0124] (4) Measurement of dielectric properties (relative permittivity: Dk, dielectric loss tangent: Df) On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625 ± 25 μm), 100 nm thick aluminum (Al) was sputtered using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. The photosensitive resin composition prepared by the method described later was spin-coated onto the above sputtered Al wafer substrate using a spin coater (D-spin60A type, manufactured by SOKUDO Co., Ltd.), and heat-dried at 110 °C for 180 seconds to form a photosensitive resin layer with a thickness of about 13.5 μm. Then, using an aligner (PLA-501F, manufactured by Canon Inc.), the entire surface was exposed with ghi rays having an exposure amount of 600 mJ / cm 2 ², and a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) was used to perform a heat curing treatment at 230 °C for 2 hours in a nitrogen atmosphere to produce a cured film made of resin with a thickness of about 10 μm on the Al wafer. This cured film was cut into a size of 80 mm in length and 62 mm in width (for 10 GHz measurement) and 40 mm in length and 30 mm in width (for 40 GHz measurement) using a dicing saw (manufactured by DISCO, model name DAD-2H / 6T), immersed in a 10% hydrochloric acid aqueous solution to be peeled off from the silicon wafer, and used as a film sample. After drying the film sample in an oven at 50 °C for 24 hours, the relative permittivity (Dk) and dielectric loss tangent (Df) of the film sample at 10 GHz and 40 GHz were measured by the resonator perturbation method. The details of the measurement method are as follows. (Measurement method) Perturbation method Split cylinder resonator method (Device configuration) Network analyzer: PNA Network analyzer N5224B (Manufactured by KEYSIGHT) Split cylinder resonator: CR-710 (manufactured by Kanto Electronic Application Development Co., Ltd., measurement frequency: about 10 GHz) CR-740 (manufactured by Kanto Electronic Application Development Co., Ltd., measurement frequency: about 40 GHz)

[0125] (5) Moisture permeability test On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625 ± 25 μm), 100 nm-thick aluminum (Al) was sputtered using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. The photosensitive resin composition prepared by the method described below was spin-coated onto the sputtered Al wafer substrate using a spin coater (D-spin60A type, manufactured by SOKUDO Co., Ltd.) and heated and dried at 110 °C for 180 seconds to form a photosensitive resin layer with a thickness of approximately 13.5 μm. Then, using an aligner (PLA-501F, manufactured by Canon), the entire surface was exposed with ghi rays having an exposure amount of 600 mJ / cm 2 2 , and a heat curing treatment was performed at 230 °C for 2 hours in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) to produce a cured film made of resin with a thickness of approximately 10 μm on the Al wafer. This cured film was cut into a size of 80 mm in length and 62 mm in width using a dicing saw (manufactured by DISCO, model name DAD-2H / 6T), immersed in a 10% hydrochloric acid aqueous solution to peel it off from the silicon wafer, and used as a film sample. The measurement of water vapor transmission rate was carried out according to the cup method of JIS Z0208. The amount of calcium chloride used was 40 g, and the water vapor transmission conditions were carried out at a temperature of 65 °C / humidity of 90%RH. The test was performed for 24 hours, then taken out from the thermo-hygrostat, left to stand at room temperature for 30 minutes, and weight measurement was carried out. The water vapor transmission rate (WVTR) was calculated from the following formula. WVTR ={(weight after the test)-(weight before the test)} / (0.03 2 × π) (Formula X) {In Formula X, 0.03 indicates the radius (m) of the cup} Here, the WVTR is a value for a 10-μm cured film and is a value that depends on the film thickness. For example, when the film thickness is 20 μm, it becomes 1 / 2 of the WVTR value obtained at 10 μm. The lower the WVTR value, the lower the water vapor transmission rate of the film. Also, the more hydrophobic the film is and the higher the density of the film, the lower the WVTR tends to be.

[0126] [Manufacture of diamine X-1] Replace the 5L four-necked flask with Ar, add 172.02 g of 4,4'-butylindene bis(6-tert-butyl-m-cresol), 155.84 g of 4-chloronitrobenzene, and 1.5 L of DMF, and stir. Then add 2 CO 3 186.42 g of and heat at 150 °C for 5 hours. Confirm the disappearance of the raw materials and intermediates by TLC. After cooling to room temperature, filter the reaction solution and concentrate it under reduced pressure at 80 °C. Pour the concentrated residue into 1.6 L of ion-exchanged water, add 2.5 L of ethyl acetate, and perform liquid-liquid separation and purification three times. Collect the organic layer, add 4 MgSO and dry. After drying, filter to remove impurities, add 800 mL of toluene to dissolve, and add it to 4.0 L of methanol and stir for 30 minutes. After stirring, filter to collect the filtrate and dry it at 80 °C for 12 hours. Put the dried reaction product into a 5L four-necked flask replaced with Ar, add 19.04 g of 5% Pd / C(EA) and 1.9 L of THF, and stir. Heat the flask to 40 °C, perform H2 bubbling (10 mL / min), and carry out a reduction reaction for 24 hours. Filter the reaction solution through celite, collect the fraction of the target product by silica gel chromatography, and concentrate it under reduced pressure to obtain diamine X-1.

[0127] [(A) Production of polyimide precursor] Synthesis of polyimide precursor (polymer A-1): As the acid component, put 93.7 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA) into a 1-liter separable flask, and add 175 g of γ-butyrolactone. While stirring at room temperature, add dropwise a γ-butyrolactone solution prepared separately by dissolving 4.7 g of 2-isocyanatoethyl methacrylate and 28.9 g of pyridine in 20 g of γ-butyrolactone over 5 minutes, and heat at 50 °C for 1 hour. Then add 48.7 g of 2-hydroxyethyl methacrylate (HEMA), heat at 50 °C for another 4 hours, and after the exothermic reaction ends, let it cool to room temperature. Let it stand for another 16 hours to obtain a reaction mixture.

[0128] Next, under ice-cooling, a solution prepared by dissolving 69.5 g of dicyclohexylcarbodiimide (DCC) in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, as a diamine component, a solution prepared by dissolving 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) in 110 g of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2.5 hours, 15 g of ethyl alcohol was added and stirred for 30 minutes, and then 150 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0129] The obtained reaction solution was added to 2700 g of ethyl alcohol to form a precipitate composed of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst TM 15" manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer. After the obtained precipitate was collected by filtration and vacuum dried, powdery polymer A-1 was obtained. When the weight average molecular weight (Mw) of this polymer A-1 was measured, it was 22,000. The end-capping value was 0.04, the aliphatic hydrocarbon group concentration T was 8.6 wt%, and the photosensitive group concentration S was 27.2 wt%. The "aliphatic hydrocarbon group concentration T" was calculated by converting to the polyimide of the polyimide cured film obtained by heating and curing at 350 °C (the same applies hereinafter).

[0130] Synthesis of polyimide precursor (polymer A-2): As the acid component, 93.7 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA) was placed in a separable flask with a capacity of 1 liter, and 48.7 g of 2-hydroxyethyl methacrylate (HEMA) and 175 g of γ-butyrolactone were added. While stirring at room temperature, 28.5 g of pyridine was added, and the mixture was heated at 50°C for 4 hours. After the exothermic reaction ended, it was allowed to cool to room temperature. It was further left standing for 16 hours to obtain a reaction mixture. Next, 4.7 g of 2-isocyanatoethyl methacrylate and 0.4 g of pyridine were dissolved in 20 g of γ-butyrolactone, and the γ-butyrolactone solution was added over 5 minutes while stirring, and the mixture was heated at 50°C for 7 hours. After the exothermic reaction ended, it was allowed to cool to room temperature. It was further left standing for 16 hours to obtain a reaction mixture.

[0131] Next, under ice cooling, a solution prepared by dissolving 73.2 g of dicyclohexylcarbodiimide (DCC) in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, as the diamine component, a solution prepared by dissolving 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) in 110 g of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2.5 hours, 15 g of ethyl alcohol was added and stirred for 30 minutes, and then 150 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0132] The obtained reaction solution was added to 2700 g of ethyl alcohol to form a precipitate composed of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was passed through an anion exchange resin ("Amberlyst" manufactured by Organo Corporation) TMIt was purified using "15") to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer. After filtering the obtained precipitate, it was dried under vacuum to obtain powdery Polymer A-2. When the weight average molecular weight (Mw) of this Polymer A-2 was measured, it was 15,000. The end-capping value was 0.02, the aliphatic hydrocarbon group concentration T was 8.6 wt%, and the photosensitive group concentration S was 27.2 wt%.

[0133] Synthesis of polyimide precursor (Polymer A-3): As the acid component, 93.7 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA) was placed in a 1-liter separable flask, and 48.7 g of 2-hydroxyethyl methacrylate (HEMA) and 175 g of γ-butyrolactone were added. While stirring at room temperature, 28.5 g of pyridine was added, and it was heated at 50 °C for 4 hours. After the exothermic reaction ended, it was allowed to cool to room temperature. It was further allowed to stand for 16 hours to obtain a reaction mixture.

[0134] In a separately prepared 0.5-liter three-necked flask, 41.7 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was placed as the diamine component. Then, 125 g of γ-butyrolactone was added and dissolved. While stirring under ice-cooling, 4.7 g of 2-isocyanatoethyl methacrylate was dissolved in 20 g of γ-butyrolactone. The separately prepared γ-butyrolactone solution was added to the three-necked flask over 5 minutes, and stirring was carried out under ice-cooling for 1 hour to obtain a reaction mixture solution with the diamine.

[0135] In parallel with the reaction in the 0.5-liter three-necked flask, a solution prepared by dissolving 73.2 g of dicyclohexylcarbodiimide (DCC) in 70 g of γ-butyrolactone was added dropwise to the reaction mixture in the 1-liter separable flask under ice-cooling over 40 minutes with stirring. Subsequently, the reaction mixture solution with the diamine obtained above as the diamine component was added dropwise over 60 minutes with stirring. After further stirring at room temperature for 2.5 hours, 150 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0136] The obtained reaction solution was added to 2700 g of ethyl alcohol to form a precipitate consisting of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst TM 15" manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer. After the obtained precipitate was collected by filtration and vacuum dried, powdery polymer A-3 was obtained. When the weight average molecular weight (Mw) of this polymer A-3 was measured, it was 17,000. The end-capping value was 0.09, the aliphatic hydrocarbon group concentration T was 8.6 wt%, and the photosensitive group concentration S was 27.2 wt%.

[0137] Synthesis of polyimide precursor (polymer A-4): In the synthesis of the above polymer A-1, instead of using 93.7 g of BPADA, 55.8 g of 4,4'-oxydiphthalic dianhydride (ODPA) was used, and instead of using 34.0 g of m-TB, 65.7 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used. The reaction was carried out in the same manner as the method described in the synthesis of polymer A-1 to obtain polymer A-4. When the weight average molecular weight (Mw) of this polymer A-4 was measured, it was 21,000. The end-capping value was 0.07, the aliphatic hydrocarbon group concentration T was 4.4 wt%, and the photosensitive group concentration S was 27.5 wt%.

[0138] Synthesis of polyimide precursor (Polymer A-5): In the synthesis of the above Polymer A-1, instead of 93.7 g of BPADA, 55.8 g of ODPA was used, and instead of 34.0 g of m-TB, 70.2 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane (MBAPP) was used. The reaction was carried out in the same manner as described in the synthesis of Polymer A-1, and Polymer A-5 was obtained. When the weight average molecular weight (Mw) of this Polymer A-5 was measured, it was 20,000. The end-capping value was 0.07, the aliphatic hydrocarbon group concentration T was 8.4 wt%, and the photosensitive group concentration S was 26.7 wt%.

[0139] Synthesis of polyimide precursor (Polymer A-6): In the synthesis of the above Polymer A-1, instead of 93.7 g of BPADA, 53.0 g of 3,3’,4,4’-biphenyltetracarboxylic dianhydride (BPDA) was used, and instead of 34.0 g of m-TB, 70.2 g of MBAPP was used. The reaction was carried out in the same manner as described in the synthesis of Polymer A-1, and Polymer A-6 was obtained. When the weight average molecular weight (Mw) of this Polymer A-6 was measured, it was 20,000. The end-capping value was 0.06, the aliphatic hydrocarbon group concentration T was 8.6 wt%, and the photosensitive group concentration S was 27.2 wt%.

[0140] Synthesis of polyimide precursor (Polymer A-7): In the synthesis of the above Polymer A-1, instead of 34.0 g of m-TB, 70.2 g of MBAPP was used. The reaction was carried out in the same manner as described in the synthesis of Polymer A-1, and Polymer A-7 was obtained. When the weight average molecular weight (Mw) of this Polymer A-7 was measured, it was 23,000. The end-capping value was 0.04, the aliphatic hydrocarbon group concentration T was 9.8 wt%, and the photosensitive group concentration S was 22 wt%.

[0141] Synthesis of polyimide precursor (Polymer A-8): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, except that 53.0 g of BPDA was used instead of 93.7 g of BPADA, and 64.7 g of 1,4-bis(4-aminophenoxy)-2,5-di-t-butylbenzene (DTBAB) was used instead of 34.0 g of m-TB, to obtain polymer A-8. When the weight average molecular weight (Mw) of this polymer A-8 was measured, it was 21,000. The end-capping value was 0.06, the aliphatic hydrocarbon group concentration T was 16.2 wt%, and the photosensitive group concentration S was 22.6 wt%.

[0142] Synthesis of polyimide precursor (polymer A-9): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, except that 90.4 g of diamine X-1 was used instead of 34.0 g of m-TB, to obtain polymer A-9. When the weight average molecular weight (Mw) of this polymer A-9 was measured, it was 19,000. The end-capping value was 0.04, the aliphatic hydrocarbon group concentration T was 20.7 wt%, and the photosensitive group concentration S was 19.9 wt%.

[0143] Synthesis of polyimide precursor (polymer A-10): In the synthesis of the above polymer A-1, the reaction was carried out in the same manner as the method described in the synthesis of polymer A-1, except that 39.3 g of pyromellitic dianhydride (PD) was used instead of 93.7 g of BPADA, and 90.4 g of diamine X-1 was used instead of 34.0 g of m-TB, to obtain polymer A-10. When the weight average molecular weight (Mw) of this polymer A-10 was measured, it was 13,000. The end-capping value was 0.1, the aliphatic hydrocarbon group concentration T was 25.1 wt%, and the photosensitive group concentration S was 25.8 wt%.

[0144] Synthesis of polyimide precursor (polymer A-11): In the synthesis of the above polymer A-1, a reaction was carried out in the same manner as the method described for the synthesis of polymer A-1, except that 55.8 g of ODPA was used instead of 93.7 g of BPADA, 35.1 g of MBAPP and 16.0 g of diaminodiphenyl ether (DADPE) were used instead of 34.0 g of m-TB, to obtain polymer A-11. When the weight average molecular weight (Mw) of this polymer A-11 was measured, it was 19,000. The end-capping value was 0.07, the aliphatic hydrocarbon group concentration T was 5.1 wt%, and the photosensitive group concentration S was 30.5 wt%.

[0145] Synthesis of polyimide precursor (polymer A-12): In the synthesis of the above polymer A-1, a reaction was carried out in the same manner as the method described for the synthesis of polymer A-1, except that 55.8 g of ODPA was used instead of 93.7 g of BPADA, and 90.4 g of diamine X-1 was used instead of 34.0 g of m-TB, to obtain polymer A-12. When the weight average molecular weight (Mw) of this polymer A-12 was measured, it was 15,000. The end-capping value was 0.07, the aliphatic hydrocarbon group concentration T was 22.3 wt%, and the photosensitive group concentration S was 23.7 wt%.

[0146] Synthesis of polyimide precursor (polymer A-13): In the synthesis of the above polymer A-1, a reaction was carried out in the same manner as the method described for the synthesis of polymer A-1, except that 39.3 g of PD was used instead of 93.7 g of BPADA, and 70.2 g of MBAPP was used instead of 34.0 g of m-TB, to obtain polymer A-13. When the weight average molecular weight (Mw) of this polymer A-13 was measured, it was 18,000. The end-capping value was 0.1, the aliphatic hydrocarbon group concentration T was 9.7 wt%, and the photosensitive group concentration S was 29.5 wt%.

[0147] Synthesis of polyimide precursor (polymer A-14): In the synthesis of the above polymer A-1, A-14 was obtained by carrying out the reaction in the same manner as the method described in the synthesis of polymer A-1, except that 59.2 g of hydroxybutyl methacrylate (HBMA) was used instead of 48.7 g of HEMA. When the weight average molecular weight (Mw) of this polymer A-14 was measured, it was 23,000. The end-capping value was 0.04, the aliphatic hydrocarbon group concentration T was 8.6 wt%, and the photosensitive group concentration S was 31.2 wt%.

[0148] Synthesis of polyimide precursor (polymer A-15): In the synthesis of the above polymer A-1, A-15 was obtained by carrying out the reaction in the same manner as the method described in the synthesis of polymer A-1, except that 4.1 g of 2-isocyanatoethyl methacrylate and 0.9 g of 1,1-(bisacryloyloxymethyl)ethyl isocyanate were used instead of 4.7 g of 2-isocyanatoethyl methacrylate. When the weight average molecular weight (Mw) of this polymer A-15 was measured, it was 18,000. The end-capping value was 0.04, the aliphatic hydrocarbon group concentration T was 8.6 wt%, and the photosensitive group concentration S was 27.2 wt%.

[0149] Synthesis of polyimide precursor (polymer A-16): As the acid component, 93.7 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA) was placed in a 1-liter separable flask, and 48.7 g of 2-hydroxyethyl methacrylate (HEMA) and 175 g of γ-butyrolactone were added. While stirring at room temperature, 28.5 g of pyridine was added, and the mixture was heated at 50 °C for 4 hours. After the exothermic reaction ended, it was allowed to cool to room temperature. It was allowed to stand for another 16 hours to obtain a reaction mixture.

[0150] Next, under ice-cooling, a solution prepared by dissolving 73.2 g of dicyclohexylcarbodiimide (DCC) in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, 1.4 g of allylamine was dissolved in 20 g of γ-butyrolactone, and the γ-butyrolactone solution was added over 5 minutes while stirring. Further, as a diamine component, a solution prepared by dissolving 35.7 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) in 110 g of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2.5 hours, 15 g of ethyl alcohol was added and stirred for 30 minutes. Then, 150 g of γ-butyrolactone was added, 0.05 g of 4-methoxyphenol was further added, and the mixture was stirred at 50 °C for 0.5 hour. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0151] The obtained reaction solution was added to 2700 g of ethyl alcohol to form a precipitate consisting of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst TM 15" manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer. After the obtained precipitate was collected by filtration and vacuum dried, powdery polymer A-16 was obtained. When the weight average molecular weight (Mw) of this polymer A-16 was measured, it was 16,000. The end-capping value was 0.08, the aliphatic hydrocarbon group concentration T was 8.6 wt%, and the photosensitive group concentration S was 27.2 wt%.

[0152] Synthesis of polyimide precursor (polymer A-17): In the synthesis of the above polymer A-3, instead of 93.7 g of BPADA, 55.8 g of ODPA was used, and instead of 34.0 g of m-TB, 84.6 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane (MBAPP) was used. Further, instead of 4.7 g of 2-isocyanatoethyl methacrylate, 3.2 g of 2-isocyanatoethyl methacrylate and 0.7 g of 1,1-(bisacryloyloxymethyl)ethyl isocyanate were used. The reaction was carried out in the same manner as the method described for the synthesis of polymer A-3, and A-16 was obtained. When the weight average molecular weight (Mw) of this polymer A-16 was measured, it was 21,000. The end-capping value was 0.07, the aliphatic hydrocarbon group concentration T was 8.4 wt%, and the photosensitive group concentration S was 27.5 wt%.

[0153] Synthesis of polyimide precursor (polymer A-18): In the synthesis of the above polymer A-3, m-TB was changed from 34.0 g to 40.9 g, and instead of 4.7 g of 2-isocyanatoethyl methacrylate, 2.5 g of methacrylic acid chloride was used. The reaction was carried out in the same manner as the method described for the synthesis of polymer A-3, and A-16 was obtained. When the weight average molecular weight (Mw) of this polymer A-16 was measured, it was 17,000. The end-capping value was 0.06, the aliphatic hydrocarbon group concentration T was 8.6 wt%, and the photosensitive group concentration S was 27.2 wt%.

[0154] Synthesis of polyimide precursor (polymer A-19): In the synthesis of the above polymer A-16, instead of 1.4 g of allylamine, 2.95 g of 5-norbornene-2-methylamine was used. The reaction was carried out in the same manner as the method described for the synthesis of polymer A-16, and A-19 was obtained. When the weight average molecular weight (Mw) of this polymer A-19 was measured, it was 16,000. The end-capping value was 0.08, the aliphatic hydrocarbon group concentration T was 8.6 wt%, and the photosensitive group concentration S was 27.2 wt%.

[0155] Synthesis of polyimide precursor (polymer A-20): As the acid component, 55.8 g of ODPA was placed in a separable flask with a volume of 1 liter, and 48.7 g of HEMA and 175 g of γ-butyrolactone were added. While stirring at room temperature, 28.5 g of pyridine was added to obtain a reaction mixture. After the exothermic reaction ended, it was allowed to cool to room temperature and further allowed to stand for 16 hours.

[0156] Next, under ice cooling, a solution prepared by dissolving 69.5 g of dicyclohexylcarbodiimide (DCC) in 70 g of γ-butyrolactone was added dropwise to the reaction mixture over 40 minutes while stirring. Subsequently, as the diamine component, a suspension prepared by suspending 30.9 g of DADPE in 100 g of γ-butyrolactone was added dropwise over 60 minutes while stirring. After further stirring at room temperature for 2.5 hours, 15 g of ethyl alcohol was added and stirred for 30 minutes, and then 150 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0157] The obtained reaction solution was added to 2700 g of ethyl alcohol to form a precipitate composed of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst TM 15" manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer. After the obtained precipitate was collected by filtration and vacuum dried, powdery polymer A-20 was obtained. When the weight average molecular weight (Mw) of this polymer A-20 was measured, it was 22,000. The aliphatic hydrocarbon group concentration T was 0 wt%, and the photosensitive group concentration S was 35.4 wt%.

[0158] Synthesis of polyimide precursor (polymer A-21): As the acid component, 155.1 g of ODPA was placed in a separable flask with a volume of 2 liters, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the exothermic reaction ended, it was allowed to cool to room temperature and further allowed to stand for 16 hours.

[0159] Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension prepared by suspending 120.1 g of 4,4'-diaminodiphenyl ether (DADPE) as a diamine component in 360 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 37.2 g of 2-isocyanatoethyl methacrylate was added as a terminal modifier for the diamine end and stirred for 2 hours. Then, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0160] The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then dried under vacuum to obtain powdery polymer A-21. When the weight-average molecular weight (Mw) of this polymer A-21 was measured, it was 20,000. The end-capping value was 0.05, the aliphatic hydrocarbon group concentration T was 0 wt%, and the photosensitive group concentration S was 35.4 wt%.

[0161] Synthesis of polyimide precursor (polymer A-22): In the synthesis of the above polymer A-20, A-22 was obtained by carrying out the reaction in the same manner as the method described for the synthesis of polymer A-20, except that 56.8 g of BAPB was used instead of 30.9 g of DADPE. When the weight-average molecular weight (Mw) of this polymer A-22 was measured, it was 23,000. The aliphatic hydrocarbon group concentration T was 0 wt%, and the photosensitive group concentration S was 28.8 wt%.

[0162] Synthesis of polyimide precursor (polymer A-23): In the synthesis of the above polymer A-20, A-18 was obtained by conducting the reaction in the same manner as the method described for the synthesis of polymer A-20, except that 32.8 g of m-TB was used instead of 30.9 g of DADPE. When the weight average molecular weight (Mw) of this polymer A-18 was measured, it was 19,000. The aliphatic hydrocarbon group concentration T was 6.2 wt%, and the photosensitive group concentration S was 34.9 wt%.

[0163] Synthesis of polyimide precursor (polymer A-24): In the synthesis of the above polymer A-21, A-24 was obtained by conducting the reaction in the same manner as the method described for the synthesis of polymer A-21, except that 127.37 g of m-TB was used instead of 120.14 g of DADPE. When the weight average molecular weight (Mw) of this polymer A-24 was measured, it was 21,000. The end-capping value was 0.05, the aliphatic hydrocarbon group concentration T was 6.2 wt%, and the photosensitive group concentration S was 34.9 wt%.

[0164] Synthesis of polyimide precursor (polymer A-25): In the synthesis of the above polymer A-21, A-25 was obtained by conducting the reaction in the same manner as the method described for the synthesis of polymer A-21, except that 91.0 g of m-TB was used instead of 120.1 g of DADPE, and 24.5 g of 4-vinyl aniline was used instead of 37.2 g of 2-isocyanatoethyl methacrylate. When the weight average molecular weight (Mw) of this polymer A-25 was measured, it was 20,000. The end-capping value was 0.01, the aliphatic hydrocarbon group concentration T was 6.2 wt%, and the photosensitive group concentration S was 34.9 wt%.

[0165] [Components (B) to (G)] Photoinitiator B1: 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]propanone-1-(O-acetoxyoxime) (trade name: PBG-304, manufactured by Changzhou Qiangli Electronics Co., Ltd.) Photoinitiator B2: 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (trade name: PBG-305, manufactured by Changzhou Qiangli Electronics Co., Ltd.) Photoinitiator B3: 1-[4-(phenylthio)phenyl]-3-propan-1,2-dione-2-(O-acetoxyoxime) (trade name: PBG-3057, manufactured by Changzhou Qiangli Electronics Co., Ltd.) Solvent C1: γ-butyrolactone Solvent C2: Dimethyl sulfoxide (DMSO) Silane coupling agent D-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-2: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-3: (3-triethoxysilylpropyl)-tert-butylcarbamate Silane coupling agent D-4: Ureidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-5: X-12-1214A (trade name of Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-6: Tris(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.) Radical polymerizable compound E-1: 1,9-nonanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Radical polymerizable compound E-2: 1,6-hexanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Radical polymerizable compound E-3: Diacrylate of polyoxypropylene bisphenol A (manufactured by Kyoeisha Chemical Co., Ltd.) Thermal crosslinking agent F-1: BMI-5100 (manufactured by Daiwa Kasei Kogyo Co., Ltd.) Thermal crosslinking agent F-2: SBB70P (manufactured by Asahi Kasei) Filler G-1: K180SP-CY1 (manufactured by Admatechs Co., Ltd.)

[0166] [Examples and Comparative Examples] <Example 1> As shown in Table 1, 100 g of Polymer A-1 was used as Component (A), 5 g of Photoinitiator B-1 was used as Component (B), and they were dissolved in a mixed solvent (weight ratio 90:10) composed of γ-butyrolactone and DMSO as Solvent (C). The amount of the solvent was adjusted so that the viscosity became about 40 poises, thereby obtaining a photosensitive resin composition solution. This composition was evaluated by the above-described method. The characteristics and evaluation results are shown in Table 2. Also, the characteristics of Component (A) are shown in Table 9.

[0167] <Examples 3 to 39, Comparative Examples 1 to 6> A photosensitive resin composition solution was prepared and evaluated in the same manner as in Example 1, except that the types and amounts of the components were adjusted to the ratios described in Tables 1, 3, 5, and 7. The characteristics and evaluation results are shown in Tables 2, 4, 6, and 8. Also, the characteristics of Component (A) are shown in Table 9.

[0168]

Table 1

[0169]

Table 2

[0170]

Table 3

[0171]

Table 4

[0172]

Table 5

[0173]

Table 6

[0174]

Table 7

[0175]

Table 8

[0176]

Table 9

[0177] As is clear from Tables 1 to 9, in the examples, by introducing a terminal structure in advance (pre-sealing) into the monomers before polymerization, a cured resin film having good resolution and chemical resistance and having low dielectric characteristics could be produced. In contrast, sufficient results were not obtained in the comparative examples. Also, in terms of the parameters consisting of moisture permeability and dielectric tangent, the examples showed lower values than the comparative examples, suggesting that, in addition to the above characteristics, the frequency dependence of the dielectric tangent is small.

Industrial Applicability

[0178] By using the photosensitive resin composition of the present disclosure, a cured resin film excellent in the resolution of a relief pattern and having low dielectric characteristics, low moisture permeability, and good chemical resistance can be produced, and it can be suitably used, for example, in the field of photosensitive materials useful for the production of electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Explanation of Signs

[0179] 1 Proton peak of polymerizable functional group derived from terminal 2 Proton peak of polymerizable functional group derived from repeating unit

Claims

1. (A) 100 parts by mass of a polyimide precursor resin; (B) 0.5 to 10 parts by mass of a photopolymerization initiator; (C) 50 to 500 parts by weight of a solvent; A photosensitive resin composition comprising: The polyimide precursor resin (A) includes at least one terminal structure selected from the group consisting of the following general formulas (1) to (3): 【Chemistry 1】 In the formula, W is a divalent or trivalent organic group, R 1 ~R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; m １ is a group represented by an integer of 1 to 2, m ２ is a group represented by an integer of 2 to 10, and * means bonding to the main chain of the resin. A photosensitive resin composition, wherein in a polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C, an aliphatic hydrocarbon group concentration T, which is the ratio of the total molecular weight of aliphatic hydrocarbon groups to the molecular weight of a repeating unit containing a structure derived from a tetracarboxylic dianhydride and a diamine compound, is 4 wt % to 35 wt %.

2. (A) 100 parts by mass of a polyimide precursor resin; (B) 0.5 to 10 parts by weight of a photosensitizer; (C) 100 to 300 parts by weight of a solvent; A photosensitive resin composition comprising: In the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350° C., an aliphatic hydrocarbon group concentration T, which is 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 compound, and a photosensitive group concentration S, which is the ratio of the total molecular weight of the photosensitive group to the molecular weight of the repeating unit in the (A) polyimide precursor resin, are expressed by the following formula (1): −77≦4T−3S≦44 (1) Fulfilling The polyimide precursor resin (A) is a photosensitive resin composition having, at a resin terminal, a reactive unsaturated bond that polymerizes by heat or light, different from the reactive unsaturated bond side chain contained in the repeating unit.

3. The photosensitive resin composition according to claim 1 or 2, wherein the polyimide precursor resin (A) is 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; Y 1 is a divalent organic group having 6 to 40 carbon atoms, n １ is an integer from 2 to 150; R ４ and R ５ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. ４ and R ５ At least one of the groups 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.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein a photosensitive group concentration S, which is a ratio of the total molecular weight of the photosensitive group to the molecular weight of the repeating unit in the polyimide precursor resin (A) represented by the general formula (4), is 15 wt % to 35 wt %.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the polyimide precursor resin (A) comprises a structure represented by the following general formula (6): 【Chemistry 4】 {In the formula, R ９ , R １０ are each independently an organic group having 1 to 10 carbon atoms; ３ , m ４ is an integer selected from 1 to 4, Z is selected from the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a hetero atom, and * means bonding to the main chain of the resin.

6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising (D) a silane coupling agent.

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (E) a radically polymerizable compound.

8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising (F) a thermal crosslinking agent.

9. The photosensitive resin composition according to any one of claims 1 to 8, further comprising (G) a filler.

10. The polyimide precursor resin (A) contains a terminal structure derived from a tetracarboxylic dianhydride at an end of a main chain, １ The photosensitive resin composition according to any one of claims 1 to 9, wherein a terminal capping value indicating a terminal capping rate is 0.02 or more when a peak area of ​​an amide group derived from a main chain structure is set to 1.0 in H-NMR.

11. (A) 100 parts by mass of a polyimide precursor resin; (B) 0.5 to 10 parts by mass of a photopolymerization initiator; (C) 50 to 500 parts by weight of a solvent; A photosensitive resin composition comprising: The polyimide precursor resin (A) contains a terminal structure derived from a tetracarboxylic dianhydride at an end of a main chain, １ The photosensitive resin composition has an end blocking value, which indicates the terminal blocking rate, of 0.02 or more when the peak area of ​​an amide group derived from a main chain structure is taken as 1.0 in H-NMR.

12. (A) 100 parts by mass of a polyimide precursor resin; (B) 0.5 to 10 parts by mass of a photopolymerization initiator; (C) 50 to 500 parts by weight of a solvent; A photosensitive resin composition comprising: The polyimide precursor resin (A) contains a terminal structure derived from a diamine at an end of a main chain, １ The photosensitive resin composition has an end blocking value, which indicates the terminal blocking rate, of 0.06 or more when the peak area of ​​an amide group derived from a main chain structure is taken as 1.0 in H-NMR.

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

14. A method for producing a cured film, comprising applying the resin composition according to any one of claims 1 to 12 onto a substrate, subjecting the composition to an exposure treatment, a development treatment, and then a heat treatment, wherein the cured film is an insulating film used for rewiring applications, and the cured film has a dielectric loss tangent of 3.0 × 10 measured at 40 GHz using a perturbation split cylinder resonator method. －３ ~1.3 x 10 －２ A method for producing a polyimide cured film, the range being:

15. A polyimide cured film having a dielectric loss tangent of 3.0×10 at a frequency of 40 GHz as measured by a perturbation split cylinder resonator method. －３ ~1.3 x 10 －２ and the following formula (2): 3.0<tanδ ４０ ×WVTR<10.0 (2) {In the formula, tanδ ４０ represents the dielectric tangent at a frequency of 40 GHz as determined by a perturbation type split cylinder resonator method, and WVTR represents the moisture permeability of a 10 μm-thick cured polyimide film.

16. The dielectric loss tangent at a frequency of 40 GHz using the perturbation split cylinder resonator method is 3.0 x 10 －３ ~1.3 x 10 －２ and the following formula (3): 4.0<tanδ ４０ ×WVTR×DR<29.0 (3) {In the formula, tanδ ４０ The cured polyimide film according to claim 15, wherein R is a dielectric loss tangent at a frequency of 40 GHz as determined by a perturbation type split cylinder resonator method, WVTR is a moisture permeability of the cured polyimide film converted to a film thickness of 10 μm, and DR is a dissolution rate in a chemical resistance test.

17. A method for producing a photosensitive resin composition, comprising: (A) 100 parts by mass of a polyimide precursor resin; (B) 0.5 to 10 parts by mass of a photopolymerization initiator; (C) 50 to 500 parts by weight of a solvent; Including, The method includes: a step of synthesizing the polyimide precursor resin (A); and a step of mixing the polyimide precursor resin (A), the photopolymerization initiator (B), and a solvent (C) to obtain a photosensitive resin composition, The synthesis process comprises the following steps: (i) reacting a first compound having a reactive substituent that reacts with heat or light with a tetracarboxylic dianhydride to produce a first compound-introducing portion and a carboxyl group, and then reacting with a second compound having a reactive substituent that reacts with heat or light different from the first compound, or reacting a second compound having a reactive substituent that reacts with heat or light with a tetracarboxylic dianhydride to produce a second compound-introducing portion and a carboxyl group, and then reacting with a first compound having a reactive substituent that reacts with heat or light different from the second compound, thereby obtaining an acid component monomer having a second compound-introducing portion; and / or (ii) reacting a diamine compound with a second compound having a reactive substituent that reacts with heat or light to obtain a diamine monomer having a second compound-introduced portion; a monomer preparation step of obtaining an acid component monomer and / or a diamine monomer having the second compound-introducing portion by (i) and / or (ii) of the above; a polymerization step of synthesizing a polyimide precursor by condensation reaction of an acid component monomer and / or a diamine monomer having the second compound-introducing portion, a tetracarboxylic dianhydride, and a diamine compound; Including, the polyimide precursor resin (A) has a reactive substituent derived from the second compound at a main chain terminal, A method for producing a photosensitive resin composition.

18. A method for producing a polyimide precursor resin, the method comprising the steps of: (i) reacting a first compound having a reactive substituent that reacts with heat or light with a tetracarboxylic dianhydride to produce a first compound-introducing portion and a carboxyl group, and then reacting with a second compound having a reactive substituent that reacts with heat or light different from the first compound, or reacting a second compound having a reactive substituent that reacts with heat or light with a tetracarboxylic dianhydride to produce a second compound-introducing portion and a carboxyl group, and then reacting with a first compound having a reactive substituent that reacts with heat or light different from the second compound, thereby obtaining an acid component monomer having a second compound-introducing portion; and / or (ii) reacting a diamine compound with a second compound having a reactive substituent that reacts with heat or light to obtain a diamine monomer having a second compound-introduced portion; a monomer preparation step of obtaining an acid component monomer and / or a diamine monomer having the second compound-introducing portion by (i) and / or (ii) of the above; a polymerization step of synthesizing a polyimide precursor by condensation reaction of an acid component monomer and / or a diamine monomer having the second compound-introducing portion, a tetracarboxylic dianhydride, and a diamine compound; Including, the polyimide precursor resin has a reactive substituent derived from the second compound at a main chain terminal; A method for producing a polyimide precursor resin.

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